TW201825529A - Rubber composition and pneumatic tire - Google Patents

Abstract

A main object of the present disclosure is to provide a rubber composition excellent in workability and having an excellent balance of rolling resistance and wet grip performance. The present disclosure achieves the object by providing a rubber composition comprising in a range of 1 part by mass to 30 parts by mass of a modified hydrocarbon resin and in a range of 80 parts by mass to 200 parts by mass of silica, based on 100 parts by mass of a diene based rubber, wherein the modified hydrocarbon resin is a hydrocarbon resin modified with at least one compound of an amine compound, an amide compound, and an imide compound, a weight-average molecular weight Mw is in a range of 1000 to 8000, and a softening point is in a range of 80 DEG C to 150 DEG C.

Description

Rubber composition and pneumatic tire

The present invention relates to a rubber composition which is excellent in workability and which has excellent balance between rolling resistance and wet grip performance.

In recent years, due to environmental problems and resource problems, there is a strong demand for low fuel economy of automobile tires. On the other hand, in terms of safety, for example, it is required to improve wet grip performance. a crosslinked product of a rubber composition obtained by blending vermiculite as a filler in a rubber component as compared with a crosslinked product of a rubber composition obtained by blending carbon black (hereinafter, simply referred to as a rubber crosslinked product) In other words, the rolling resistance at the time of constituting the tire becomes small. Therefore, by using a crosslinked product of a rubber composition obtained by blending vermiculite to form a tire, a tire excellent in fuel economy can be obtained.

However, even if the vermiculite is blended in the conventional rubber component, since the affinity between the rubber component and the vermiculite is insufficient, the separation is easy, and the processability of the rubber composition before crosslinking is poor, and this is crosslinked. The obtained rubber cross-linked product has a problem such as insufficient rolling resistance when the tire is formed.

In the patent document 1 (Japanese Patent Laid-Open Publication No. 2011-255881), it is described that the rubber composition is prepared by using an amine-modified conjugated diene polymer as a rubber component, thereby providing low heat generation and improvement. A pneumatic tire that runs flat with running durability. It is described in Patent Document 2 (Japanese Patent Laid-Open Publication No. 2000-53706) that a rubber is added as a rubber component by using a hydrogen addition conjugated diene polymer modified with a guanamine or a ruthenium imine at the end of a polymer chain to prepare a rubber. The composition is a tire which is excellent in abrasion resistance, weather resistance, workability, and the like, and which has little heat generation.

However, in the case where the rubber component described in Patent Document 1 and Patent Document 2 is used to produce a tire by adding the obtained rubber cross-linked product, it is difficult to balance the wet grip performance and the rolling resistance. Problems such as characteristics.

The present invention has been made in view of the above problems, and a main object thereof is to provide a rubber composition which is excellent in workability and which has excellent balance between rolling resistance and wet grip performance.

The inventors of the present invention have focused on the hydrocarbon resin which is added to the rubber composition at the same time as the rubber component, and as a result, it has been found that, with respect to the rubber composition, the hydrocarbon resin is modified by a specified amount of the amine compound and has a weight within a specified range. The modified hydrocarbon resin having a specified characteristic such as an average molecular weight, which relates to an improvement in workability, and a balance between rolling resistance and wet grip performance, further completes the present invention.

Thus, according to the present invention, it is possible to provide a rubber composition in which 1 part by mass to 30 parts by mass of the modified hydrocarbon resin and 80 parts by mass to 200 parts by mass of the vermiculite are blended with 100 parts by mass of the diene rubber. The rubber composition is characterized in that the modified hydrocarbon resin is obtained by modifying a hydrocarbon resin with at least one compound of an amine compound, a guanamine compound or a ruthenium compound; the weight average molecular weight (Mw) is It is in the range of 1000 to 8,000, and the softening point is in the range of 80 to 150 °C.

The hydrocarbon resin is a C5 petroleum resin or a C5/C9 petroleum resin, and the C5 petroleum resin or the C5/C9 petroleum resin contains 20% by mass to 70% by mass and a carbon number of the 1,3-pentadiene monomer unit. 4 to 6 alicyclic monoolefin monomer units 5 to 35% by mass, carbon number 4 to 8 acyclic monoolefin monomer units 1 to 50% by mass, alicyclic diene monomer unit 0% by mass to 10% by mass, and a hydrocarbon resin of 0% by mass to 50% by mass of the aromatic monoolefin monomer unit, and the modified hydrocarbon resin is preferably selected from the group consisting of the above-mentioned amine compound, guanamine compound and ruthenium. 0.01 parts by mass to 20 parts by mass of at least one compound of the group of imine compounds, wherein 100 parts by mass of the above hydrocarbon resin is modified, the number average molecular weight (Mn) is in the range of 500 to 4000, and the Z average molecular weight (Mz) In the range of 2000 to 25000, the ratio of the weight average molecular weight to the number average molecular weight (Mw/Mn) is in the range of 1.0 to 4.0, and the ratio of the Z average molecular weight to the weight average molecular weight (Mz/Mw) is 1.0 to 4.5. In the range.

Further, according to the present invention, there can be provided a pneumatic tire characterized in that the above rubber composition is used for a tread.

The present invention exerts an effect of providing a rubber composition excellent in workability and excellent in balance between rolling resistance and wet grip performance.

The present invention relates to a rubber composition and a pneumatic tire for use in a tread. The rubber composition of the present invention and the pneumatic tire will be described in detail below.

I. Rubber composition

The rubber composition of the present invention is a rubber composition obtained by blending 1 to 30 parts by mass of a modified hydrocarbon resin and 80 to 2 parts by mass of vermiculite with respect to 100 parts by mass of the diene rubber. The modified hydrocarbon resin is characterized in that a hydrocarbon resin is modified with at least one compound of an amine compound, a guanamine compound or a ruthenium compound; and the weight average molecular weight (Mw) is in the range of 1,000 to 8,000. And the softening point is in the range of 80 ° C to 150 ° C.

According to the present invention, the rubber composition can be obtained by, for example, containing a modified hydrocarbon resin in a specified amount relative to the diene rubber, thereby obtaining a rubber composition excellent in workability and excellent in balance between rolling resistance and wet grip performance. Wherein the modified hydrocarbon resin is modified with at least one compound selected from the group consisting of an amine compound, a guanamine compound, and a quinone compound (hereinafter referred to as an amine compound), and has a designation A modified hydrocarbon resin having the characteristics of weight average molecular weight and softening point.

Here, the reason why a rubber composition excellent in workability and excellent balance between rolling resistance and wet grip performance can be obtained by using the above modified hydrocarbon resin is not clear, but it is estimated as follows. In other words, the modified hydrocarbon resin is obtained by modifying the hydrocarbon resin with an amine compound having high affinity with the filler in the rubber composition, whereby the dispersibility of the filler can be improved. Further, by setting the molecular weight and the softening point of the modified hydrocarbon resin to a predetermined value, it is possible to obtain an excellent compatibility with the diene rubber. Therefore, the modified hydrocarbon resin is excellent in compatibility with the diene rubber, and is excellent in dispersion of a filler such as vermiculite, thereby promoting the fixation of the terminal group of the diene rubber to the filler or the like. Regarding the obtained rubber composition, the loss coefficient tan δ of the crosslinked product at 60 ° C can be lowered, and the loss coefficient tan δ at 0 ° C can be appropriately increased. As a result, in the case of manufacturing a tire using such a rubber composition, it is possible to form a tire or the like which has a superior balance between rolling resistance and wet grip performance.

As described above, by including a predetermined amount of the above modified hydrocarbon resin with respect to the diene rubber, it is possible to obtain a rubber composition which is excellent in workability and has excellent balance between rolling resistance and wet grip performance.

Further, the rubber composition can obtain a rubber composition having a superior balance between rolling resistance and wet grip performance by containing a specified amount of vermiculite. On the other hand, when the amount of the vermiculite blended is less than 80 parts by mass, the wet grip performance is deteriorated, and if it exceeds 200 parts by mass, the rolling resistance is deteriorated. On the other hand, in the case where the amount of the vermiculite blended is 80 parts by mass or more, the workability is deteriorated. Then, the rubber composition can suppress the decrease in workability and improve the balance of rolling resistance and wet grip performance by blending a predetermined amount of the modified hydrocarbon resin with vermiculite.

The rubber composition of the present invention contains a diene rubber, a modified hydrocarbon resin, and a vermiculite. Hereinafter, each component contained in the rubber composition of the present invention will be described in detail.

A. Modified hydrocarbon resin

The modified hydrocarbon resin is a modified product of a hydrocarbon resin derived from an amine compound.

In the following, the hydrocarbon resin before the modification of the amine compound (hereinafter referred to as the case of the pre-modification resin), the amine compound modified and the modified hydrocarbon resin (hereinafter referred to as a modified resin) Detailed instructions are given.

Hydrocarbon resin

The hydrocarbon resin is a raw material resin before upgrading by an amine compound.

The hydrocarbon resin may be a rubber composition which is excellent in workability and which has excellent balance between rolling resistance and wet grip performance by being modified by an amine compound.

In the present invention, the hydrocarbon resin is preferably a C5-based petroleum resin or a C5/C9-based petroleum resin. The reason for this is that the above-mentioned petroleum resin can stably impart a rubber composition which is excellent in workability and has excellent balance between rolling resistance and wet grip performance.

The above-mentioned C5-based petroleum resin refers to a hydrocarbon resin obtained by polymerizing a monomer composition containing at least one kind of a monomer contained in a C ₅ fraction obtained by thermally cracking a gas oil.

The monomer contained in the C ₅ fraction may, for example, be a conjugated diene monomer having 4 to 5 carbon atoms such as 1,3-pentadiene, isoprene or cyclopentadiene, which is in the present invention. Preferably, the monomer composition is 1,3-pentadiene as the C ₅ fraction, that is, the hydrocarbon resin is preferably a 1,3-pentadiene monomer unit.

Further, the monomer contained in the C ₅ fraction and the monomer contained in the C ₉ fraction described later may be a monomer contained in the C ₅ fraction or the C ₉ fraction when the light oil is thermally cracked. For example, the monomer contained in the C ₅ fraction is not limited to a monomer which is obtained by thermally cracking a gas oil as a C ₅ fraction, and may be a monomer obtained by another synthesis method or the like.

The above-mentioned C5/C9 petroleum resin refers to a hydrocarbon resin obtained by polymerizing a monomer, wherein the monomer contains at least one kind of a monomer contained in a C ₅ fraction obtained by thermally cracking a light oil, and the light oil is subjected to At least one species of the monomer contained in the C ₉ fraction obtained by thermal cracking.

Further, examples of the monomer contained in the C ₉ fraction include aromatic monoolefins having 8 to 10 carbon atoms such as styrene, α-methylstyrene, vinyltoluene, anthracene, and benzofuran.

More specifically, the C5-based petroleum resin or the C5/C9-based petroleum resin may be an alicyclic monoolefin monomer unit having at least a 1,3-pentadiene monomer unit and a carbon number of 4 to 6. And a non-cyclic monoolefin monomer unit having 4 to 8 carbon atoms, and optionally a hydrocarbon resin containing an alicyclic diene monomer unit and an aromatic monoolefin monomer unit, wherein 20% by mass to 70% by mass of pentadiene monomer unit, 5% by mass to 35% by mass of alicyclic monoolefin monomer unit having 4 to 6 carbon atoms, and acyclic monoolefin monomer unit having 4 to 8 carbon atoms The hydrocarbon resin is preferably 1% by mass to 50% by mass, 0% by mass to 10% by mass of the alicyclic diene monomer unit, and 0% by mass to 50% by mass of the aromatic monoolefin monomer unit. The reason for this is that the above-mentioned hydrocarbon resin is used as the above-mentioned hydrocarbon resin, that is, by using the above-mentioned specified monomer unit and a ratio of a hydrocarbon resin as the pre-modification resin. The hydrocarbon resin can impart a rubber composition which is excellent in workability and has excellent balance between rolling resistance and wet grip performance.

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 67% by mass, wherein It is preferably in the range of 30% by mass to 65% by mass, particularly preferably in the range of 33% by mass to 63% by mass. The reason for this is that the modified hydrocarbon resin can provide a rubber composition which is excellent in workability and has excellent 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 is a hydrocarbon compound having 4 to 6 carbon atoms in the molecular structure having one ethylenically unsaturated bond 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 5 mass% to 35% by mass, and may be in the range of 8 mass% to 33 mass%. Preferably, it is preferably in the range of 10% by mass to 32% by mass, particularly preferably in the range of 13% by mass to 30% by mass. The reason for this is that the above-mentioned modified hydrocarbon resin can provide a rubber composition which is excellent in workability and has excellent balance between rolling resistance and wet grip performance.

Further, in the alicyclic monoolefin having 4 to 6 carbon atoms, the ratio of each compound conforming thereto may be any ratio, and is not particularly limited, but it is preferably at least cyclopentene, and cyclopentene is used. The proportion of the alicyclic monoolefin having 4 to 6 carbon atoms is 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 which has one ethylenically unsaturated bond in the molecular structure and has 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 and 2-pentyl a pentene such as alkene, 2-methyl-1-butene, 3-methyl-1-butene or 2-methyl-2-butene; 1-hexene, 2-hexene, 2-methyl Hexene such as 1-pentene; heptene such as 1-heptene, 2-heptene, 2-methyl-1-hexene; 1-octene, 2-octene, 2-methyl-1 An octene such as heptene or diisobutylene (2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-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 1% by mass to 50% by mass, and may be in the range of 5% by mass to 45% by mass. Preferably, it is preferably in the range of 10% by mass to 42% by mass, particularly preferably in the range of 15% by mass to 40% by mass. The reason for this is that the above-mentioned modified hydrocarbon resin can provide a rubber composition which is excellent in workability and has excellent balance between rolling resistance and wet grip performance.

Further, in the acyclic monoolefin having 4 to 8 carbon atoms, the ratio of each compound (including an isomer) conforming thereto may be any ratio, and is not particularly limited, but includes at least one selected from the group consisting of 2-methyl Preferably, at least one of the group consisting of 2-butene, isobutylene and diisobutylene is a total of 2-methyl-2-butene, isobutylene and diisobutylene in an acyclic monoolefin having 4 to 8 carbon atoms. The proportion of the amount is preferably 50% by mass or more.

The pre-modification resin may also contain an alicyclic diene in its raw material. The alicyclic diene has 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 multimer of cyclopentadiene such as cyclopentadiene or dicyclopentadiene, methylcyclopentadiene, and methylcyclopentadiene. Polymer.

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. The reason for this is that the above-mentioned modified hydrocarbon resin can provide a rubber composition which is excellent in workability and has excellent balance between rolling resistance and wet grip performance.

The pre-modification resin may also contain an aromatic monoolefin in its raw material. The aromatic monoolefin is an aromatic compound having an ethylenically unsaturated bond in its molecular structure. Specific examples of the aromatic monoolefin include aromatic monoolefins having 8 to 10 carbon atoms contained in the C ₉ fraction such as styrene, α-methylstyrene, vinyltoluene, hydrazine or benzofuran.

The content of the aromatic monoolefin monomer unit in the pre-modification resin may be in the range of 0% by mass to 50% by mass, preferably in the range of 0% by mass to 45% by mass, wherein The range of the mass% to 43% by mass is preferable, and particularly preferably in the range of 0% by mass to 40% by mass.

Further, in the above aromatic monoolefin monomer unit, the ratio of each compound (including an isomer) conforming thereto may be any ratio, and is not particularly limited, but may be set to contain at least 8 to 10 carbon atoms. The proportion of the total amount of the aromatic monoolefins having a carbon number of 8 to 10 is preferably 30% by mass or more, more preferably 40% by mass or more, and more preferably 50% by mass or more. Especially 60% by mass is preferred. The reason for this is that the modified hydrocarbon resin can provide a rubber composition which is excellent in workability and has excellent balance between rolling resistance and wet grip performance.

The resin before modification includes 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, and alicyclic In addition to the diolefin monomer unit and the aromatic monoolefin monomer unit, it is also possible to obtain a modified hydrocarbon resin which imparts a rubber composition having excellent workability and excellent balance between rolling resistance and wet grip performance. Other monomer units may be included.

The other monomer used for constituting the other monomer unit is not particularly limited as long as it is an addition polymerization polymer which can be copolymerized with 1,3-pentadiene or the like other than the above monomer. . Among the above other monomers, for example, 1,3-butadiene, 1,2-butadiene, isoprene, 1,3-hexadiene, 1,4-pentadiene, etc. An unsaturated hydrocarbon having 4 to 6 carbon atoms other than pentadiene; an alicyclic monoolefin having 7 or more carbon atoms such as cycloheptene; an acyclic monoolefin having 4 to 8 carbon atoms such as ethylene, propylene or decene; .

However, the content of the other monomer unit in the pre-modification resin in the pre-modification resin may be any modified hydrocarbon resin having the above-mentioned specified characteristics, and specifically, it is usually 0% by mass. In the range of 30% by mass, it is 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. The reason for this is that the modified hydrocarbon resin can provide a rubber composition which is excellent in workability and has excellent balance between rolling resistance and wet grip performance.

The method of producing the pre-modification resin is not particularly limited as long as the polymerizable component (monomer mixture A) having a monomer constituting the monomer unit is appropriately subjected to addition polymerization. For example, a pre-modification resin can be obtained by addition polymerization using a cationic polymerization catalyst of the Friedel-Crafts type.

As a method for preferably producing a pre-modification resin, a method having a polymerization step as described below: a combination of an aluminum halide (A) and a halogenated hydrocarbon (B) as a polymerization catalyst, and The above monomer mixture A is polymerized, wherein the halogenated hydrocarbon (B) is selected from a halogenated hydrocarbon (B1) comprising a tertiary carbon atom bonded to a halogen atom, and a carbon atom adjacent to the carbon-carbon unsaturated bond. A group of halogenated hydrocarbons (B2) in which a halogen atom is bonded.

Further, the amount of each monomer contained in the monomer mixture A may be set to be the same as the content of each monomer unit in the hydrocarbon resin. Therefore, the alicyclic monoolefin monomer unit containing 20% by mass to 70% by mass of the 1,3-pentadiene monomer unit and 4 to 6 carbon atoms is produced in an amount of 5 to 35% by mass and 4 to 8 carbon atoms. 1% by mass to 50% by mass of the acyclic monoolefin monomer unit, 0% by mass to 10% by mass of the alicyclic diene monomer unit, and 0% by mass to 50% by mass of the aromatic monoolefin monomer unit In the case of the resin resin of the pre-resin, the above production method, more specifically, may be set as a method having the following polymerization step: 20% by mass to 70% by mass of the 1,3-pentadiene monomer, and 4 carbon atoms ～6 alicyclic monoolefin monomer 5 mass% to 35 mass%, carbon number 4-8 acyclic monoolefin monomer 1% by mass to 50% by mass, alicyclic diene monomer 0% by mass to ～ The monomer mixture A of 10% by mass and 0% by mass to 50% by mass of the aromatic monoolefin is polymerized.

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

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

By using the halogenated hydrocarbon (B) in combination with the aluminum halide (A), the activity of the polymerization catalyst can be extremely excellent.

Specific examples of the halogenated hydrocarbon (B1) in which a tertiary carbon atom and a halogen atom are bonded to each other include tertiary t-butyl chloride and tertiary t-butyl bromide. 2-chloro-2-methylbutane, triphenylchloromethane. Among these, in view of achieving an excellent balance between activity and ease of handling, it is preferable to use tertiary chlorobutane.

Examples of the unsaturated bond in the halogenated hydrocarbon (B2) in which a carbon atom adjacent to a carbon-carbon unsaturated bond is bonded to a halogen atom include a carbon-carbon double bond and a carbon-carbon triple bond. A carbon-carbon conjugated double bond comprising an aromatic ring or the like. Specific examples of such a compound include α-chlorobenzyl, α-brominated bromide, (1-chloroethyl)benzene, and allyl chloride. 3-Chloro-1-propyne, 3-chloro-1-butene, 3-chloro-1-butyne, cinnamic chloride. Among these, α-chlorotoluene is preferably used from the viewpoint of excellent balance between activity and ease of handling. Further, the halogenated hydrocarbons (B) may be used alone or in combination of two or more.

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

In the polymerization reaction, the order of adding the components of the monomer mixture and the polymerization catalyst to the polymerization reactor is not particularly limited, and it may be added in any order, but the polymerization reaction is preferably controlled from the above. From the viewpoint of accurately controlling the weight average molecular weight and the like, it is preferred to add a part of the monomer mixture and a component of the polymerization catalyst to the polymerization reactor, and after starting the polymerization reaction, the residual portion of the polymerization catalyst is added to Polymerization reactor.

In the production of the pre-modification resin, it is preferred to first mix the aluminum halide (A) with the alicyclic monoolefin. The reason for this is that by contacting the aluminum halide (A) with an alicyclic monoolefin, gel formation can be prevented, and a pre-modification resin which controls the weight average molecular weight or the like via a preferable precision can be obtained.

The amount of the alicyclic monoolefin to be mixed with the aluminum halide (A) is preferably at least 5 times (mass ratio) of the amount of the aluminum halide (A). If the amount of the alicyclic monoolefin is too small, the effect of preventing gel formation is insufficient. The mass ratio of the alicyclic monoolefin to the aluminum halide (A) is preferably 5:1 to 120:1, preferably 10:1 to 100:1, and more preferably 15:1 to 80:1. . If more alicyclic monoolefins are used in this ratio, the catalytic activity is lowered and the polymerization becomes insufficient.

In the case of mixing the aluminum halide (A) with the alicyclic monoolefin, the order of the input is not particularly limited, and the aluminum halide (A) may be introduced into the alicyclic monoolefin, and vice versa, in the aluminum halide (A). The alicyclic monoolefin is charged. Mixing is usually accompanied by heat generation, so a suitable diluent can also be used. As a diluent, the solvent mentioned later can be used.

Preferably, the mixture is carried out as described above, and after the mixture M of the aluminum halide (A) and the alicyclic monoolefin is prepared, the mixture a and the mixture M containing at least the 1,3-pentadiene and the acyclic monoolefin are subjected to a mixture M. mixing. The aforementioned mixture a may also contain an alicyclic diene.

The preparation method of the mixture a is not particularly limited, and the pure mixture compound may be separately mixed to obtain the target mixture a, and a mixture of the target monomers containing a fraction derived from a light oil lysate or the like may be used, for example, to obtain the target mixture a. For example, in order to incorporate 1,3-pentadiene or the like into the mixture a, it is preferred to use a C ₅ fraction obtained by extracting isoprene and cyclopentadiene (including a polymer thereof).

It is preferred to further mix the halogenated hydrocarbon (B) with the mixture a and the mixture M. The order of input of these three is not particularly limited.

From the viewpoint of more preferably controlling the polymerization reaction, it is preferred to add a solvent to the polymerization reaction system and carry out the polymerization reaction. The type of the solvent is not particularly limited as long as it does not interfere with the polymerization reaction, but is preferably a saturated aliphatic hydrocarbon or an aromatic hydrocarbon. Examples of the saturated aliphatic hydrocarbon to be used as a solvent include n-pentane, n-hexane, 2-methylpentane, 3-methylpentane, n-heptane, 2-methylhexane, and 3 -methylhexane, 3-ethylpentane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethyl a chain-like saturated aliphatic hydrocarbon having 5 to 10 carbon atoms such as pentane, 2,2,3-trimethylbutane or 2,2,4-trimethylpentane; cyclopentane, cyclohexane, cycloglycan A cyclic saturated aliphatic hydrocarbon having a carbon number of 5 to 10, such as an alkane or a cyclooctane. Examples of the aromatic hydrocarbon to be used as the solvent include aromatic hydrocarbons having a carbon number of 6 to 10 such as benzene, toluene or xylene. The solvent may be used singly or in combination of two or more. The amount of the solvent to be used is not particularly limited, but is preferably in the range of 10 parts by mass to 1,000 parts by mass, and preferably 50 parts by mass to 500 parts by mass, per 100 parts by mass of the polymerizable component (monomer mixture A). The range is preferred. 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 C ₅ fraction may be added to the polymerization reaction system, and an addition polymerizable component may be added. A component as a monomer mixture is used, and a non-addition polymerizable component is used as a solvent.

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

The method for producing the pre-modification resin is at least the above-described polymerization step, but may have other steps as needed. As the other step, for example, after the polymerization step, the solvent-insoluble catalyst residue formed by adding the polymerization terminator in the polymerization step and deactivating the polymerization catalyst may be removed by filtration or the like. a solvent residue removal step; after the polymerization reaction by the polymerization step is stopped, the unreacted monomer and the solvent are removed, and the low molecular weight oligomer component is removed by steam distillation or the like, and cooled, thereby obtaining a solid The recovery step of the pre-modification resin, and the like.

2. Amine compounds

The amine compound is at least one compound selected from the group consisting of an amine compound, a guanamine compound, and a quinone compound.

(1) Amine compound

The above amine compound is a compound having an amine structure in which a hydrogen atom of 0 to 2 and one or more hydrocarbon groups form a covalent bond on nitrogen.

The amine compound may be a rubber composition having an amine structure and the modified hydrocarbon resin is excellent in workability and has excellent balance between rolling resistance and wet grip performance, and for example, a bond with a nitrogen atom may be used. When the amount of the hydrocarbon group is in the range of 1 to 3, a primary amine, a secondary amine, and a tertiary amine can also be used.

Further, as the hydrocarbon group, an aliphatic hydrocarbon group and an aromatic hydrocarbon group can be used. Further, the aromatic hydrocarbon group means a group in which a bond directly to a nitrogen atom is a base of an aromatic ring, and even if it has an aromatic ring such as a benzyl group, a portion directly bonded to a nitrogen atom is not an aromatic ring, and It is included in the aliphatic hydrocarbon base.

Further, the aliphatic hydrocarbon group may be any structure including a chain aliphatic group and a cyclic aliphatic group, or may be an unsaturated group. Further, the cyclic aliphatic group and the aromatic hydrocarbon group may be a carbocyclic group containing only carbon as an atom constituting the cyclic structure, but may be a heterocyclic group containing an atom other than carbon.

Further, the aliphatic hydrocarbon group and the aromatic hydrocarbon group may also be substituted with a substituent in which a hydrogen atom contained in the aliphatic hydrocarbon group and the aromatic hydrocarbon group is substituted with a substituent. Examples of the substituent include an amine structure or an atom other than carbon such as a nitrogen atom, an oxygen atom or a sulfur atom, such as -OCH ₃ , and a bond with at least one of a hydrogen atom, an aliphatic hydrocarbon group and an aromatic hydrocarbon group. Therefore, the above-mentioned amine compound is not limited to a rubber composition which is excellent in workability and has excellent balance between rolling resistance and wet grip performance, and is not limited to one amine structure in the molecule. As the monoamine, for example, a diamine, a triamine or the like having two or more amine structures which form a covalent bond via the above hydrocarbon group can also be used. Further, in the case where the amine compound has two or more amine structures, two or more amine structures may have the same structure or may be a different structure. For example, the amine compound can be set to: a two amine structure comprising a primary amine structure and a secondary amine structure; comprising two secondary amine structures, wherein one secondary amine structure forms a bond with another nitrogen structure of the secondary amine structure The structure of the hydrocarbon group of the knot is different.

The molecular weight of the above-mentioned amine compound may be a bond which can be stably formed with the resin before the modification, and may be, for example, in the range of 50 to 500, and preferably in the range of 100 to 300.

Examples of the primary amine include 1-hexylamine, 1-heptylamine, and 1-octylamine, and an amine having a carbon number of 6 to 20 in total as a hydrocarbon group to form a bond; The amine or the like which forms a bond as a heteroaromatics contained in the aromatic hydrocarbon group of the hydrocarbon group, and preferably an amine having a carbon number of 8 to 12 in the compound to form a bond is used. Wait.

Examples of the above secondary amine include 1,6-bis(ethylamino)hexane, 1,2-bis(tributylamino)ethane, and N'-benzyl-N,N-. a dimethylethylenediamine, N-benzyl-N,N'-dimethylethylenediamine or the like having an aliphatic hydrocarbon group having a total carbon number of 6 to 20 as a hydrocarbon group to form a bonded amine; The amine or the like which forms a bond as a heteroaromatic group contained in the aromatic hydrocarbon group of the hydrocarbon group, and preferably an amine or the like having a carbon number of 8 to 12 in total in the compound to form a bond may be used.

Examples of the tertiary amine include N'-benzyl-N,N-dimethylethylenediamine, N-benzyl-N,N'-dimethylethylenediamine, and the like, and carbon among the compounds. The amine having a total of 6 to 20 aliphatic hydrocarbon groups as a hydrocarbon group to form a bond; an amine having a heteroaromatic group contained in an aromatic hydrocarbon group as a hydrocarbon group, and the like, wherein carbon is preferably used in the compound. The total number is 8 to 12, and the aliphatic hydrocarbon group forms a bonded amine or the like.

Further, in the case of a secondary amine structure and a tertiary amine structure as in the case of N'-benzyl-N,N-dimethylethylenediamine, the amine compound conforms to both the secondary amine and the tertiary amine.

Further, N'-benzyl-N,N-dimethylethylenediamine has a hydrogen atom substituted with (1) benzyl (carbon number 7) and (2) vinyl (-C ₂ H ₅ ) An aliphatic hydrocarbon group (-C ₂ H ₄ -N-(CH ₃ ) ₂ : carbon number 4) of an amine-forming structure is used as a hydrocarbon group constituting the secondary amine structure, and is an aliphatic hydrocarbon group having at least a carbon number of 7 as a constituent second Hydrocarbyl group of the amine structure. Further, N'-benzyl-N,N-dimethylethylenediamine has one hydrogen atom in (1) two methyl groups (carbon number 1) and (2) vinyl group (-C ₂ H ₅ ). An aliphatic hydrocarbon group substituted with an amine structure (-(C ₂ H ₄ )-NH-CH ₂ -C ₆ H ₅ : carbon number 9) as a hydrocarbon group constituting a tertiary amine structure, and having at least a carbon number of 9 The aliphatic hydrocarbon group serves as a hydrocarbon group constituting the tertiary amine structure.

Examples of the diamine include 1,6-bis(ethylamino)hexane, 1,2-bis(tributylamino)ethane, and 1,4-bis(aminomethyl) ring. Hexane, 4-amino-1-diethylaminopentane, N-benzyl-N,N'-dimethylethylenediamine, etc., among the compounds, aliphatic having a total carbon number of 6-20 a hydrocarbon group which forms a bonded amine as a hydrocarbon group; an amine which forms a bond as a heteroaromatic group contained in the aromatic hydrocarbon group of a hydrocarbon group, and the like, wherein an aliphatic group having a total carbon number of 8 to 12 among the compounds is preferably used. The hydrocarbon group forms a bonded amine or the like.

Examples of the triamine include a bis(4-aminobutyl)amine and a bis(6-aminohexyl)amine. Among them, an aliphatic hydrocarbon group having a total carbon number of 6 to 20 is used as a hydrocarbon group to form a bond. The amine having a bond; an amine or the like which forms a bond as a heteroaromatic group contained in the aromatic hydrocarbon group of the hydrocarbon group, and preferably an amine having a carbon number of 8 to 12 in total in the compound to form a bond Wait.

The above amine compound may be contained alone or in combination of two or more.

(2) guanamine compound

The guanamine compound may be a compound having one or more indoleamine bonds in the molecule, and for example, those represented by the following formula (1) can be used.

[Chemical 1]

(In the formula (1), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group.)

The hydrocarbon group in the above R ¹ to R ³ can be set to be the same as the content described in the above-mentioned "(1) amine compound". Further, R ¹ to R ³ may be the same functional groups or may be different functional groups.

In addition, the hydrocarbon group in the above R ¹ to R ³ may be a rubber composition which is excellent in workability and which has excellent balance between rolling resistance and wet grip performance as long as it is a modified hydrocarbon resin, and may be included as a rubber composition. The aliphatic hydrocarbon group of the hydrocarbon group and a part of the hydrogen atom of the aromatic hydrocarbon group are substituted into a guanamine structure or an amine structure. In other words, the guanamine compound is not limited to a monoamine having only one guanamine structure in the molecule, and two or more types having a covalent bond via R ¹ to R ³ as a hydrocarbon group may be used. The indoleamine structure, such as diamine, tridecylamine and the like. Further, the guanamine compound may be an amine structure having both a guanamine structure and a bond formed by R ¹ to R ³ as a hydrocarbon group.

The molecular weight of the above guanamine compound is not particularly limited as long as it can be stably combined with the resin before the modification, and may be, for example, in the range of 50 to 500, and preferably in the range of 100 to 300.

As the above-described guanamine compound, specifically, the guanamine compound described in Japanese Patent Laid-Open Publication No. 2000-53706 can be used, and more specifically, N,N-dimethylformamide or acetamide can be preferably used. , N,N-diethylacetamide, aminoacetamide, N,N-dimethyl-N', N'-dimethylaminoacetamide, N,N-dimethylamino Acetamine, N,N-ethylaminoacetamide, N,N-dimethyl-N'-ethylaminoacetamide, acrylamide, N,N-dimethyl decylamine, N,N-dimethylmethacrylamide, nicotinamide, isonicotinium amide, pyridine carbenamide, N,N-dimethylisonicotinamine, butylamine, phthalate Formamide, N,N,N',N'-tetramethylphthalamide, oxalidamide and N,N,N',N'-tetramethylglucamine, 2-furancarboxylic acid Indoleamine, N,N-dimethyl-2-furancarboxylic acid decylamine, quinoline-2-carboxylic acid decylamine, N-ethyl-N-methyl-quinolinecarboxylic acid decylamine, N-acetyl hydrazine Ethylenediamine or the like, among which N-ethylmercaptoethylenediamine or the like is preferably used.

The above guanamine compound may be contained alone or in combination of two or more.

(3) quinone imine compound

The quinone imine compound may be a compound having one or more quinone imine bonds in the molecule, and for example, a cyclic quinone imine compound represented by the following formula (2) or (3) may be used.

[Chemical 2]

(In the formulae (2) and (3), R ⁴ , R ⁵ and R ⁶ and R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or a hydrocarbon group.)

The hydrocarbon group in the above R ⁴ to R ⁹ can be set to be the same as the content described in the above-mentioned "(1) amine compound". Further, R ⁴ to R ⁹ may be the same functional groups, or may be different functional groups.

In addition, the hydrocarbon group in the above-mentioned R ⁴ to R ⁹ may be a rubber composition which is excellent in workability and excellent in balance between rolling resistance and wet grip performance, and may be contained as a hydrocarbon group. One of the aliphatic hydrocarbon group and the hydrogen atom of the aromatic hydrocarbon group is substituted with a quinone imine structure, a guanamine structure or an amine structure. In other words, the above-described quinone imine compound is not limited to a monoquinone imine having only one quinone imine structure in the molecule, and two having a bond formed via the above-mentioned hydrocarbon group R ⁷ to R ⁹ may be used. More than one quinone imine structure such as diimine, triazine or the like. Further, the quinone imine compound may be at least one of a guanidinium structure having a quinone imine structure and a bond structure and an amine structure formed by the above-mentioned R ⁷ to R ⁹ as a hydrocarbon group.

The molecular weight of the above quinone imine compound may be set to be in a range of from 50 to 500, and preferably in the range of from 100 to 300, as long as it can be stably combined with the resin before the modification.

As the above-mentioned quinone imine compound, specifically, the quinone imine compound described in Japanese Patent Laid-Open Publication No. 2000-53706 can be used, and more specifically, butylenediamine and N-methylbutane are preferably used. Yttrium imine, maleimide, N-methyl maleimide, phthalimide, N-methylphthalimide, di-n-butenylene For the imine or the like, an N-alkylbutyleneimine compound such as N-methylbutyleneimine is preferably used.

The above quinone imine compound may be contained alone or in combination of two or more.

(4) Amine compounds

The amine compound is at least one compound selected from the group consisting of an amine compound, a guanamine compound, and a quinone compound. Therefore, the amine compound may be one containing only an amine compound, only a guanamine compound, or only a quinone compound, or a compound containing an amine compound and a guanamine compound, including an amine compound, ruthenium. A compound of three kinds of amine compounds and quinone imine compounds. In the present invention, it is preferred that the above amine compound contains a guanamine compound.

The modified hydrocarbon resin is obtained by modifying a hydrocarbon resin with an amine compound as described above.

Here, the term "modified" means that the amine compound is bonded to the hydrocarbon resin by a covalent bond.

In addition, when the amount of the hydrocarbon resin is changed from 0.01 parts by mass to 20 parts by mass per 100 parts by mass of the amine compound, the mass of the portion derived from the amine compound bonded to 100 parts by mass of the hydrocarbon resin is 0.01 part by mass. ～20 parts by mass.

The content of the amine-based compound, that is, the content of the portion derived from the amine compound bonded to 100 parts by mass of the hydrocarbon resin of the pre-modification resin, can be set in the range of 0.01 part by mass to 20 parts by mass. It is preferably in the range of 0.1 part by mass to 10 parts by mass, more preferably in the range of 0.1 part by mass to 8 parts by mass, particularly preferably in the range of 0.1 part by mass to 5 parts by mass. The reason for this is that the modified hydrocarbon resin can provide a rubber composition which is excellent in workability and has excellent balance between rolling resistance and wet grip performance.

The amine modification method using the pre-modification resin of the above-described amine compound may be a method in which the amine compound can be bonded to the pre-modification resin by a covalent bond.

As such an amine upgrading method, a suitably known method can be used. Specifically, as the above-described amine upgrading method, a pre-modification resin, an amine compound, and a peroxide initiator can be used, whereby the resin is freely produced in the pre-modification resin by a peroxide initiator. And a method of reacting this with an amine compound; a method of mixing an amine compound with a pre-modification resin having an active terminal, and the like.

In the above-described amine upgrading method, the amount of the amine-based compound to be added to the pre-modification resin may be an amine-based compound which can be combined with a desired amount, for example, an amine-based compound in a modified hydrocarbon resin. The content is the same amount or more.

The reaction conditions in the above-described amine modification method using a radical may be such that the desired amount of the amine compound and the pre-modification resin can be combined, depending on the type of the resin before the modification and the type of the amine compound. If it is set as appropriate, for example, the reaction temperature may be set to 0 ° C to 200 ° C and the reaction time may be 5 minutes to 20 hours.

Further, the above amine modification method may be carried out, for example, in an organic solvent. The organic solvent can be set to be the same as the solvent described in the above section "1. Hydrocarbon resin" which can be used for the polymerization reaction of the resin before reforming. The above amine modification method may be, for example, a method of performing amine modification in a solvent used for polymerization of the resin before reforming.

The peroxide initiator may be any one which can bond a desired amount of the amine compound to the pre-modification resin, and for example, an inorganic peroxide such as sodium persulfate or dicumyl hydroperoxide can be used. A known peroxide initiator such as an organic peroxide such as diisopropylbenzene hydroperoxide. In addition, as described above, for example, Japanese Patent Publication No. 2004-285230 and the like can be used.

The amount of the peroxide initiator to be used may be appropriately set in accordance with the amount of the amine compound added, etc., as long as the desired amount of the amine compound can be combined with the pre-modification resin.

The above amine modification method may be a method of combining an amine compound with a pre-modification resin via a known decane coupling agent as needed. Further, the method of bonding the decane coupling agent to the pre-modification resin can be set to be the same as the above-described amine modification method.

As the decane coupling agent, for example, a difunctional decane coupling agent having a vinyl group and a reaction functional group capable of forming a bond with a nitrogen atom contained in the amine compound can be used. The functional group for the reaction may, for example, be a hydroxyl group, a carboxyl group, a ketone group, an epoxy group, a halogen group or a sulfonic acid group. Among them, a hydroxyl group, a carboxyl group or the like is preferred. Further, the difunctional decane coupling agent having such a vinyl group and a reactive functional group may be appropriately selected from known decane coupling agents.

Further, the blending amount of the decane coupling agent used as a spacer between the amine compound and the pre-modification resin also includes a compound which is not combined with an amine compound, and is usually included as a pre-modification resin. Part of it.

The method of combining the pre-modification resin and the amine-based compound in which a conventional decane coupling agent is combined may, for example, be a method in which a pre-modification resin in which a conventional decane coupling agent is combined and an amine-based compound are mixed and heat-treated. .

The heat treatment conditions can be set, for example, at a temperature of 50 ° C to 300 ° C for 5 minutes to 20 hours.

In the above heat treatment, a diluent, an anti-gelling agent, a reaction accelerator, or the like may be present as needed. Such a diluent can be set to be the same as the solvent described in the above-mentioned "1. Hydrocarbon Resin" which can be used for the polymerization reaction of the resin before reforming. The heat treatment may be, for example, a method carried out in a solvent used for polymerization of the resin before reforming.

Further, as the amine modification method, the amine compound may be bonded to the pre-modification resin by reacting a nitrogen atom of the amine compound with an acidic group such as a carboxyl group or an acid anhydride group contained in the pre-modification resin. The method.

As the acidic group, an acidic group introduced into the pre-modification resin by using a polymerizable component (monomer mixture A) containing a monomer having an acidic group can be used, and an acid can be used by performing a pre-modification resin. The acidic base introduced by upgrading.

Here, as a method of acid-modifying the resin before the modification, a known method can be used. For example, when a carboxyl group is introduced as an acidic group, a pre-modification resin and an unsaturated carboxylic acid are mixed and carried out. Heat treatment method. Further, in the acid reforming method, in the case where an acid anhydride group is introduced as an acidic group, a method in which a pre-modification resin and an unsaturated dicarboxylic anhydride are mixed and heat-treated is mentioned.

Examples of the unsaturated carboxylic acid used for introducing a carboxyl group include carbon number 8 or less such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and citraconic acid. Ethylene unsaturated carboxylic acid, and conjugated diene such as 3,6-endomethyl-1,2,3,6-tetrahydrofurfuric acid and α,β-unsaturated dicarboxylic acid having 8 or less carbon atoms Diels-Alder adduct.

Examples of the unsaturated dicarboxylic acid anhydride used for introducing the acid anhydride group include α,β-unsaturated dicarboxylic anhydride having a carbon number of 8 or less, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, and, for example, 3 , a conjugated diene of 6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride and a Diers-Adel-addition of α,β-unsaturated dicarboxylic anhydride having a carbon number of 8 or less Wait.

Further, the blending amount of the acid modifier such as an unsaturated carboxylic acid introduced to acid-modify the pre-modification resin also includes a compound which is not combined with an amine compound, and is usually included as a pre-modified resin. portion.

The reaction conditions of the acid reforming reaction can be, for example, 5 minutes to 20 hours at a temperature of 50 ° C to 300 ° C.

The acid modification reaction may also include a diluent, an anti-gelling agent, a reaction accelerator, and the like as needed.

In addition, as a reaction which couples an acidic group and an amine type compound, the method of mixing the pre-modification resin and the amine-type compound after the modification of the resin and acid after the modification, and heat-processing is mentioned. The method of performing the heat treatment can be set, for example, in the same manner as the heat treatment method described below: a heat treatment method in which the pre-modification resin in which the above-described existing decane coupling agent is combined and an amine-based compound are combined.

The following formulas (4) to (6) disclose that the above amine modification method uses maleic anhydride as the unsaturated dicarboxylic anhydride, and the amine compound and the anhydrous carboxylic acid group which has been introduced as an acidic group have been modified. An example of a method in which the pre-mass resin A is reacted to obtain a modified hydrocarbon resin B. Further, the following formula (4) discloses an example in which a diamine compound containing two amine structures is used as an amine compound. Further, the following formulas (5) and (6) disclose an example in which a guanamine compound containing an amine structure and a guanamine structure is used as an amine compound, and the formula (5) reveals a guanamine structure contained in an amine compound. In the case where the nitrogen atom is reacted with an acidic group, the formula (6) is an example in which a nitrogen atom of an amine structure contained in the amine compound is reacted with an acidic group.

[Chemical 3]

The above-mentioned amine upgrading reaction may also be a secondary modification reaction in which an amine-based compound which has been bonded to a modified hydrocarbon resin is reacted with a modified hydrocarbon resin or the like after a primary modification reaction in which the resin and the amine-based compound are combined before the modification. .

The secondary modification reaction is, for example, as shown in the following formulas (7) and (8), and the amine structure or the guanamine structure contained in the amine compound which has been bonded to the modified hydrocarbon resin. The reaction is carried out by an acidic group or the like contained in a hydrocarbon resin or the like.

Further, the secondary reforming reaction may be carried out for the same modified hydrocarbon resin as the modified hydrocarbon resin combined by one primary modification reaction, or may be generated for the different modified hydrocarbon resin or the pre-modification resin. And produce a crosslinked modified hydrocarbon resin.

Further, the formula (7) discloses that the above secondary reforming reaction is carried out by reacting a nitrogen atom of an amine structure contained in an amine compound bonded to a modified hydrocarbon resin with an acidic group contained in the same modified hydrocarbon resin. An example of the formation of a guanamine structure. Further, the formula (8) discloses that the secondary modification reaction is bonded to the nitrogen atom of the indoleamine structure contained in the amine compound of the modified hydrocarbon resin, and the same acidic group which has reacted with the amine compound is re-executed. An example of a new cyclic quinone imine structure formed by the reaction.

[Chemical 4]

3. Modified hydrocarbon resin

The weight average molecular weight (Mw) of the modified hydrocarbon resin is not particularly limited as long as it is in the range of 1,000 to 8,000, but it is preferably in the range of 1,200 to 6,000, particularly preferably in the range of 1,400 to 4,500. . This is because the weight average molecular weight (Mw) is within the above range, and the modified hydrocarbon resin can be excellent in compatibility with the diene rubber. Further, as a result, with respect to the crosslinked product of the rubber composition, the modified hydrocarbon resin is liable to lower the loss coefficient tan δ at 60 ° C, and it is excellent in rolling resistance. Further, the reason is that, by the weight average molecular weight (Mw) within the above range, the modified hydrocarbon resin is liable to increase the loss coefficient tan δ at 0 ° C, and it is excellent in rolling resistance.

The number average molecular weight (Mn) of the above modified hydrocarbon resin can be set in the range of 500 to 4,000, preferably in the range of 550 to 3,000, particularly preferably in the range of 600 to 2,500. This is because the modified hydrocarbon resin can be excellent in compatibility with the diene rubber by the number average molecular weight (Mn) within the above range. Further, as a result, with respect to the crosslinked product of the rubber composition, the modified hydrocarbon resin is liable to lower the loss coefficient tan δ at 60 ° C, and it is excellent in rolling resistance.

The Z average molecular weight (Mz) of the above modified hydrocarbon resin can be set in the range of 2,000 to 25,000, preferably in the range of 3,000 to 20,000, particularly preferably in the range of 4,000 to 15,000. The reason for this is that the modified hydrocarbon resin can be excellent in compatibility with the diene rubber by the Z average molecular weight (Mz) within the above range. Further, as a result, with respect to the crosslinked product of the rubber composition, the modified hydrocarbon resin is liable to lower the loss coefficient tan δ at 60 ° C, and excellent rolling resistance can be obtained.

Further, in the present invention, the number average molecular weight (Mn), the weight average molecular weight (Mw), and the Z average molecular weight (Mz) of the modified hydrocarbon resin are polyphenylenes obtained by measurement by high performance liquid chromatography. Ethylene conversion value. More specifically, the measurement of the number average molecular weight, the weight average molecular weight, and the Z average molecular weight can be performed by using "HLC-8320GPC" manufactured by Tosoh Corporation as a measuring device, and the column system is connected with "TSKgel SuperMultiporeHZ" manufactured by Tosoh Corporation. The tetrahydrofuran was used as a solvent and measured at a flow rate of 40 ° C and 1.0 mL/min.

The ratio (Mw/Mn) of the weight average molecular weight to the number average molecular weight of the modified hydrocarbon resin may be set in the range of 1.0 to 4.0, preferably in the range of 1.2 to 3.5, particularly in the range of 1.4 to 3.0. The range is preferred. The reason for this is that the modified hydrocarbon resin can be excellent in compatibility with the diene rubber by the above ratio. As a result, with respect to the crosslinked product of the rubber composition, since the modified hydrocarbon resin is liable to lower the loss coefficient tan δ at 60 ° C, excellent wet grip performance can be obtained.

The ratio (Mz/Mw) of the Z average molecular weight to the weight average molecular weight of the modified hydrocarbon resin may be set in the range of 1.0 to 4.5, preferably in the range of 1.0 to 4.0, particularly in the range of 1.0 to 3.5. The range is preferred. The reason for this is that the modified hydrocarbon resin can be excellent in compatibility with the diene rubber by the above ratio. As a result, with respect to the crosslinked product of the rubber composition, since the modified hydrocarbon resin is liable to lower the loss coefficient tan δ at 60 ° C, excellent wet grip performance can be obtained.

The softening point of the modified hydrocarbon resin is not particularly limited as long as it is in the range of 80 ° C to 150 ° C, but it is preferably in the range of 85 ° C to 145 ° C, particularly in the range of 90 ° C to 140 ° C. Preferably. The reason for this is that the modified hydrocarbon resin can be excellent in compatibility with the diene rubber by the softening point within the above range. As a result, as for the crosslinked product of the rubber composition, since the modified hydrocarbon resin is liable to lower the loss coefficient tan δ at 60 ° C, excellent rolling resistance can be obtained. Further, the reason is that, by the softening point within the above range, the modified hydrocarbon resin easily increases the loss coefficient tan δ at 0 ° C, and can be excellent in wet grip performance.

Further, the softening point in the present invention is a value measured for a modified hydrocarbon resin, for example, in accordance with JIS K 6863.

The blending amount of the modified hydrocarbon resin is not particularly limited as long as it is 1 part by mass to 30 parts by mass based on 100 parts by mass of the diene rubber, but it is 5 parts by mass to 20 parts by mass based on 100 parts by mass of the diene rubber. The scope of the serving is preferred. The reason for this is that the rubber composition is excellent in workability and has a superior balance between rolling resistance and wet grip performance by the above-mentioned blending amount. In addition, in the case where the modified hydrocarbon resin includes a modified C5-based petroleum resin and a modified C5/C9 petroleum resin, and the like, two or more modified hydrocarbon resins are included, the above modification is made. The blending amount of the hydrocarbon resin can be set to the total amount of all the modified hydrocarbon resins.

Further, the blending amount of the modified hydrocarbon resin is preferably in the range of 1% by mass to 30% by mass based on the blending amount of the vermiculite, and more preferably in the range of 3% by mass to 25% by mass.

As a method for producing the modified hydrocarbon resin, a method having an amine reforming step of using 0.01 to 20 parts by mass of the above amine compound to use the mass of the hydrocarbon resin 100 as a pre-modified resin can be used. A modified amine modification step. In addition, the method of modifying the amine-based compound, that is, the method of modifying the amine, etc., can be set to be the same as that described in the item of "2. Amine-based compound", and the description herein is omitted.

B. Diene rubber

As the diene rubber, any diene rubber which can be blended with the modified hydrocarbon resin and vermiculite to the rubber composition can be used. For the diene rubber, for example, a diene rubber described in JP-A-2015-189873 can be used. More specifically, the diene rubber may, for example, be natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), or propylene. Nitrile-butadiene copolymer rubber (NBR), ethylene-propylene-diene terpolymer rubber (EPDM), etc., of which styrene-butadiene copolymer rubber, natural rubber, etc. are preferred. The reason for this is that a rubber composition having excellent workability and excellent balance between rolling resistance and wet grip performance can be obtained by using the above diene rubber. The diene rubber may be used alone or in combination of two or more kinds.

Further, the diene rubber is not particularly limited in molecular weight and microstructure, and may be terminally modified by an amine, a guanamine, a mercapto group, an alkoxysilyl group, a carboxyl group or a hydroxyl group, or may be subjected to a ring. Oxidation. The diene rubber may be a hydrogen addition product, but it is preferred that the hydrogen addition is not performed.

C. Meteorite

The vermiculite is blended with the diene rubber and the modified hydrocarbon resin to the rubber composition.

As such a vermiculite, it is possible to impart a rubber composition which is excellent in workability and excellent balance between rolling resistance and wet grip performance by blending with a diene rubber and the above hydrocarbon resin in a rubber composition. For example, the same as the vermiculite described in Japanese Patent Laid-Open Publication No. 2016-3274 can be used. More specifically, the above-mentioned vermiculite, dry vermiculite, wet vermiculite, citric acid gel and precipitated vermiculite can be used. Further, the type of the vermiculite may be two or more kinds alone or in combination.

Silica aforementioned BET specific surface area (in accordance with ISO5794 / 1 for measurement) may be set in a range of ^{100m 2 / g ~ 400m 2 /} g , of which in the range of ^{150m 2 / g ~ 350m 2 /} g are preferred.

The amount of the above-mentioned vermiculite is not particularly limited as long as it is 80 parts by mass to 200 parts by mass based on 100 parts by mass of the diene rubber, but it is 90 parts by mass to 150 parts by mass based on 100 parts by mass of the diene rubber. The range is better. The reason for this is that the rubber composition is excellent in workability and has a superior balance between rolling resistance and wet grip performance by the above-mentioned blending amount within the above range.

D. Other ingredients

The rubber composition of the present invention contains a diene rubber, a modified hydrocarbon resin, and a vermiculite, but may contain other components as necessary.

As the above other components, a necessary amount of a blending agent may be blended, for example, a decane coupling agent, a crosslinking agent, a crosslinking accelerator, a crosslinking activation agent, an anti-aging agent, an active agent, and a processing oil. (process oil), plasticizer, lubricant, adhesive, etc. In addition, the content of such other components and the content thereof can be set as described in, for example, Japanese Patent Publication No. 2016-30795.

The above other ingredients may include fillers other than vermiculite. As the filler other than the above-mentioned vermiculite, a general user of the rubber composition can be used, and examples thereof include carbon black, clay, diatomaceous earth, talc, barium sulfate, calcium carbonate, magnesium carbonate, metal oxide, mica, and hydroxide. Aluminum, various metal powders, wood powder, glass powder, ceramic powder, etc., in addition to inorganic hollow fillers such as glass balloons and silica balloons; An organic hollow filler such as difluoroethylene and a polydifluoroethylene copolymer. Among these fillers, for example, carbon black or the like can be used as described in Japanese Patent Laid-Open Publication No. 2016-30795.

In the present invention, it is preferred that the above filler is carbon black or the like. The reason for this is that the rubber composition is excellent in wet grip performance by the above filler.

In addition, the filler may be used alone or in combination of two or more.

The content of the filler other than the vermiculite may be any rubber composition which is excellent in workability and has excellent balance between rolling resistance and wet grip performance.

The content is, for example, 120 parts by mass or less based on 100 parts by mass of the diene rubber.

E. Rubber composition

In the method for producing the rubber composition of the present invention, the components may be kneaded by a usual method, and for example, a component obtained by removing a component which is unstable to heat such as a crosslinking agent or a crosslinking accelerator may be removed from the diene rubber. After the kneading, a component which is unstable to heat such as a crosslinking agent or a crosslinking accelerator is mixed in the kneaded product to obtain a target composition. The kneading temperature of the component obtained by removing the component which is unstable to heat and the diene rubber is preferably in the range of 80 ° C to 200 ° C, and preferably in the range of 120 ° C to 180 ° C. The kneading time is preferably from 30 seconds to 30 minutes. 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, and it is preferably carried out after cooling to 80 ° C or lower.

As a crosslinking method of the rubber composition of the present invention as a rubber crosslinked product, a known crosslinking method can be used, and for example, a molding machine corresponding to a desired shape, for example, an extruder, A method in which a molding machine, a compressor, a roll, and the like are injection molded, and a crosslinking reaction is performed by heating to fix a shape to form a crosslinked product. In this case, molding and crosslinking can be simultaneously performed even if crosslinking is carried out after molding is performed in advance. The molding temperature is usually in the range of 10 ° C to 200 ° C, and 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, in the range of 2 minutes to 12 hours. The range is preferably in the range of 3 minutes to 6 hours.

Further, depending on the shape and size of the rubber crosslinked product, even if the surface is crosslinked, the inside is not sufficiently crosslinked. Therefore, the crosslinking method may be further heated to perform secondary crosslinking.

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

The rubber composition of the present invention achieves a superior balance between rolling resistance and wet grip performance. Further, the rubber composition of the present invention utilizes such characteristics, and is preferably used for, for example, a tread of a tire (tread running surface, tread base), a carcass, a side wall, a bead Among the various parts of the tire such as the bead part, among various tires such as an all-season tire, a high-performance tire, and a studless tire, it is preferably used in a tread or a carcass. It is preferable to use a tread which is a low-burning tire in various parts of the tire such as a bead and a bead portion, and it is particularly preferable to use it as a tread running surface.

II. Pneumatic tires

Next, the pneumatic tire of the present invention will be described. The pneumatic tire of the present invention is characterized in that the above rubber composition is used for a tread.

The tread is formed by using the rubber composition described above, that is, the rubber composition is used, and usually the crosslinked product of the rubber composition is contained.

The rubber composition used to form such a tread and the crosslinked product thereof can be set to be the same as those described in the above-mentioned "I. Rubber composition", and thus the description thereof will be omitted.

The pneumatic tire may be formed by using the rubber composition as the tread, or may be formed by using the rubber composition in other portions.

The tread formed by using the above rubber composition may be a part of the tread or the whole of the tread, but it is preferable to include at least a tread running surface.

Further, as a method of producing the pneumatic tire of the present invention, a method of producing a pneumatic tire having a tread formed using the above composition may be used, and a known method for producing a pneumatic tire may be used.

The present invention is not limited to the above embodiment. The above-described embodiments are exemplified, and those having substantially the same configuration as the technical idea described in the patent application scope of the present invention and having the same effects are included in the technical scope of the present invention.

The embodiment will be described below.

The examples and comparative examples are listed below, and the present invention will be more specifically described. Further, the parts and % in each example are based on mass unless otherwise specified.

Various measurements were made in accordance with the following methods.

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

A resin such as a modified hydrocarbon resin as a sample is subjected to gel permeation chromatography to obtain a number average molecular weight (Mn), a weight average molecular weight (Mw), and a Z average molecular weight (Mz) in terms of standard polystyrene. The molecular weight distribution is represented by the ratio of Mw/Mn and Mz/Mw. In addition, the gel permeation chromatography analysis was carried out using "HLC-8320GPC" manufactured by Tosoh Corporation as a measuring device, and the column was connected with three "TSKgel SuperMultiporeHZ" manufactured by Tosoh Co., Ltd., and tetrahydrofuran was used as a solvent. The flow rate was measured at °C and 1.0 mL/min.

[softening point (°C)]

The resin such as the modified hydrocarbon resin as a sample was measured in accordance with JIS K 6863.

[Moneyy viscosity (ML1+4)]

The rubber composition as a sample was measured by the following conditions in accordance with JIS K 6300-1:2001. This characteristic is expressed by an index in which a reference sample (Comparative Example 1 described later) is set to 100.・Test temperature: 100°C ・Type of rotor: L shape ・Use test machine: Shimadzu viscometer SMV-300J manufactured by Shimadzu Corporation

[tensile strength (MPa), elongation (%) and tensile stress (MPa) of 200% elongation]

For the test piece of the rubber cross-linked product as a sample, tensile strength (MPa), elongation (%), and 200% elongation tensile stress were measured in accordance with JIS K 6251:2010. Tensile stress (MPa)). These characteristics are expressed by an index that sets a reference sample (Comparative Example 1 described later) to 100. Further, the 200% elongation tensile stress (MPa) is a value obtained by dividing the tensile strength at 200% elongation of the test piece by the initial sectional area of the test piece.・Test piece production method: After the sheet is formed by pressurization and vulcanization, punching processing is performed. The shape of the test piece: Dumbbell shape No. 3 and test piece take direction: Parallel direction with respect to texture (test) Number of sheets: 3 ・Measurement temperature: 23 °C ・Test speed: 500 mm/min ・Use test machine: TENSOMETER 10k manufactured by ALPHA TECHNOLOGIES Co., Ltd. ・Testing machine capacity: load cell type 1kN

[loss tangent tan δ]

The test piece of the rubber cross-linked product as a sample was subjected to the following measurement conditions using JIS K 7244-4, and the loss tangent tan δ at 0 ° C and 60 ° C was measured using dynamic strains of 0.5% and 10 Hz. This characteristic is expressed by an index which sets a reference sample (comparative example 1 mentioned later) to 100. In addition, the higher the tangent tan δ at 0 ° C, the better the wet grip performance, and the lower the tangent tan δ at 60 ° C, the better the rolling resistance. Measurement item: dynamic storage elastic modulus E': dynamic loss elastic modulus E": loss tangent tan δ ・ sample preparation method: punching the sheet and test piece shape: Length 50 mm × width 2 mm × thickness 2 mm ・Number of test pieces: 1 ・Clamp spacing: 20 mm

[Manufacturing Example 1]

In the polymerization reactor, a mixture of 47.3 parts of cyclopentane and 28.3 parts of cyclopentene was charged into a polymerization reactor, and after raising the temperature to 70 ° C, 0.75 parts of aluminum chloride (mixture M ₁ ) was added. Next, a mixture a _{1 of} 3.6 parts of 1,3-pentadiene, 6.2 parts of isobutylene, 0.1 part of dicyclopentadiene, 0.3 parts of C4-C6 unsaturated hydrocarbon, and 5.7 parts of C4-C6 saturated hydrocarbon was maintained. (70 ° C) for 60 minutes, continuously added to the polymerization reactor containing the aforementioned mixture M ₁ while carrying out polymerization. Thereafter, an aqueous sodium hydroxide solution was added to the polymerization reactor to terminate the polymerization reaction. Further, the kinds and amounts of the components in the polymerization reactor at the time of the polymerization were shown in Table 1. After the precipitate formed by the polymerization stop was removed by filtration, the obtained polymer solution was charged into a distillation pot, and heated under a nitrogen atmosphere to remove the polymerization solvent and the unreacted monomer. Next, at 240 ° C or higher, saturated steam was blown while the low molecular weight oligomer component was distilled off.

肆[3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionic acid]nepentaerythritol (pentaerythritol tetrakis [3- (3,5-) was added to 100 parts of the resin in a molten state. Di-t-butyl-4-hydroxyphenyl) propionate]) (manufactured by BASF Corporation, trade name Irganox 1010) 0.2 parts as an antioxidant, followed by addition of 2.0 parts of maleic anhydride and after addition reaction at 230 ° C for 1 hour 1.5 parts of N-benzyl-N,N'-dimethylethylenediamine was added as an amine compound, and the addition reaction was carried out at 200 ° C for 1 hour. Thereafter, the molten resin was taken out from the distillation pot and left to stand at room temperature to obtain a modified hydrocarbon resin of Production Example 1. The number average molecular weight, the weight average molecular weight, the Z average molecular weight, the molecular weight distribution, and the softening point of the modified hydrocarbon resin of Production Example 1 obtained were measured. These measurement results are shown in Table 1 below.

Further, the values of the amine compound (parts) and the pre-modification resin (100 parts) in Table 1 are calculated using the acid-modified maleic anhydride as a part of the raw material of the pre-modification resin. Further, the amount of the amine compound added per 100 parts of the monomer mixture of the pre-modification resin and the maleic anhydride described in Table 1 is shown.

[Production Examples 2 to 8]

The modified hydrocarbon resin was obtained in the same manner as in Production Example 1 except that the kind, amount, and polymerization temperature of the components added to the polymerization reactor were changed as shown in Table 1 below. With respect to the obtained resins of Production Examples 2 to 8, the number average molecular weight, the weight average molecular weight, the Z average molecular weight, the molecular weight distribution, and the softening point were measured in comparison with the modified hydrocarbon resin of Production Example 1.

Further, the diisobutylene, the aromatic monoolefin, and the toluene which are not described in Production Example 1 are mixed with 1,3-pentadiene or the like to be subjected to polymerization. Further, as the aromatic monoolefin, styrene is used.

Further, in Production Example 6 and Production Example 7, the acid modification by maleic anhydride and the amine modification by the amine compound were not carried out, and an unmodified hydrocarbon resin was obtained.

[Table 1]

[Example 1]

In the Banbury mixer, an oil-extended emulsion polymerized styrene butadiene rubber (E-SBR) (trade name "Nipol 1739", manufactured by Nippon Seon Co., Ltd., combined The amount of styrene: 40%, the vinyl bond content of the butadiene unit portion: 13.5 mol%, weight average molecular weight: 690,000, molecular weight distribution (Mw / Mn): 3.98, glass transition temperature (Tg): −35 °C, containing 96.3 parts of an extender oil of 37.5 parts with respect to 100 parts of the diene rubber (content of diene rubber: 70 parts, content of filler oil: 26.3 parts), solution polymerization of styrene Ethylene rubber (S-SBR) (trade name "Nipol NS 616", manufactured by Nippon Zeon Co., Ltd., Muni viscosity (ML1+4, 100 °C): 62) 15.0 parts, and natural rubber (NR) (SIR20) 15.0 parts After kneading for 30 seconds, 60.0 parts of a vermiculite (trade name "Zeosil 1165MP" made by Rodia Co., Ltd.), 20.0 parts of carbon black (manufactured by CABOT Japan Co., Ltd., trade name "N234"), and a decane couple were added. Mixture: bis[3-(triethoxyindolyl)propane] (bis[3-(triethoxy) 9.0 parts of silyl)propyl]tetrasulfide) (trade name "Si69" manufactured by Degussa Co., Ltd.) and 10.0 parts of modified hydrocarbon resin obtained in Production Example 1. After kneading for 90 seconds, vermiculite (manufactured by Rodia Co., Ltd.) was added. "Zeosil 1165MP") 40.0 parts, 3.0 parts of zinc oxide, 2.0 parts of stearic acid and anti-aging agent: N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine (large In an amount of 2.0 parts, the product was added to the processing oil (manufactured by Shin-Nippon Oil Co., Ltd., trade name "AROMAX T-DAE") in 15.0 parts. Thereafter, the starting temperature was 90° C. and kneading was carried out, and after kneading at 145° C. to 155° C. for 60 seconds or more (primary mixing), the kneaded product was discharged from the mixer.

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

Next, using the two rolls of 50 ° C, 1.7 parts of sulfur was added to the obtained kneaded product, and a vulcanization accelerator: N-cyclohexyl-2-benzothiazolesulfenamide. (CBS product name "NOCCELER CZ-G", manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.), 1.8 parts, and benzophenone (DPG trade name "NOCCELER D", manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.) 1.7 copies, etc. After kneading (curing agent vulcanization), a sheet-like rubber composition was taken out.

Further, the kneading conditions of primary mixing, secondary mixing, and vulcanization agent kneading were set to the conditions shown below.

(Combination conditions for primary mixing and secondary mixing) ・Testing machine: LAYO PLASTOMILL Bamburi mixer B-600 manufactured by Toyo Seiki Co., Ltd. ・Filling rate: 70 to 75 vol% ・Rotor rotation number: 50 rpm ・Starting test Set temperature: 90 ° C

(Kneading conditions for vulcanizing agent kneading) ・Testing machine: Ikeda Machinery Co., Ltd. Electric heating type high temperature roller machine ・Roll size: 6φ×16 ・Front roller rotation number: 24 rpm ・ Front and rear roller rotation ratio: 1:1.22・Roller temperature: 50°C±5°C ・Flip times: 2 times left and right ・Passing rounding width: Roller interval is about 0.8mm ・Rolling into a cylindrical shape: 5 times

[Examples 2 to 5 and Comparative Examples 1 to 3]

In addition to the modified hydrocarbon resin obtained in Production Examples 2 to 8 (manufacturing Examples 6 to 7 are unmodified hydrocarbon resins), the modified hydrocarbon resin obtained in Production Example 1 was used instead of the following, as shown in the following Table 2. Example 1, and a rubber composition was obtained.

〔Evaluation〕

The rubber compositions obtained in the examples and the comparative examples were subjected to pressure crosslinking at a pressurization pressure of about 8 MPa and a pressurization temperature of 160 ° C for 40 minutes, and then matured in a constant temperature room at 23 ° C to prepare 150 pieces. Test piece of rubber cross-linked product of mm × 150 mm × thickness 2 mm.

With respect to the rubber composition and the rubber cross-linked product obtained in the examples and the comparative examples, the Muini viscosity of the rubber composition, the tensile strength (MPa), the elongation (%), and the loss tangent tan δ of the rubber cross-linked product were measured. The results are shown in Table 2 below.

[Table 2]

From Tables 1 and 2, it was confirmed that in the examples, the loss tangent tan δ at 0 ° C was high, and the loss tangent tan δ at 60 ° C was low. From this result, it was confirmed that both excellent rolling resistance and wet grip performance were obtained.

Further, in the case where the diene rubber and the modified hydrocarbon resin are contained, since the rolling resistance and the wet grip performance are excellent, it is confirmed that the rubber composition is mixed with excellent compatibility. Excellent processability. Further, it was confirmed that the rubber composition had excellent dispersibility of vermiculite and excellent workability even in the case of containing vermiculite.

That is, it can be confirmed from Tables 1 and 2 that a predetermined amount of the amine-based compound is modified and has a characteristic such as a weight average molecular weight and a softening point, and particularly includes, for example, a weight average of a specified amount relative to the diene rubber. The molecular weight (Mw), and the ratio (Mw/Mn) of the weight average molecular weight to the number average molecular weight (Mn) are moderately low and the softening point is moderately high, whereby the rubber composition has excellent processability. It has excellent rolling resistance and wet grip performance.

no.

Claims (3)

A rubber composition obtained by blending 1 to 30 parts by mass of a modified hydrocarbon resin and 80 to 2 parts by mass of vermiculite with respect to 100 parts by mass of the diene rubber, and is characterized in that it is a rubber composition. The modified hydrocarbon resin is obtained by modifying a hydrocarbon resin with at least one compound of an amine compound or a guanamine compound or a ruthenium compound; the weight average molecular weight (Mw) is in the range of 1,000 to 8,000, and The softening point is in the range of 80 ° C to 150 ° C. The rubber composition according to claim 1, wherein the hydrocarbon resin is a C5 petroleum resin or a C5/C9 petroleum resin, and the C5 petroleum resin or the C5/C9 petroleum resin comprises: 1,3-pentadiene 20% by mass to 70% by mass of the monomer unit, 5% by mass to 35% by mass of the alicyclic monoolefin monomer unit having 4 to 6 carbon atoms, and 1% by mass of the acyclic monoolefin monomer unit having 4 to 8 carbon atoms ～50% by mass, alicyclic diolefin monomer unit 0% by mass to 10% by mass, and aromatic monoolefin monomer unit 0% by mass to 50% by mass of a hydrocarbon resin, the modified hydrocarbon resin system The resin is obtained by modifying 100 parts by mass of the hydrocarbon resin in an amount of 0.01 parts by mass to 20 parts by mass based on at least one compound selected from the group consisting of the amine compound, the guanamine compound, and the quinone compound; Mn) is in the range of 500 to 4000; Z average molecular weight (Mz) is in the range of 2000 to 25000; ratio of weight average molecular weight to number average molecular weight (Mw/Mn) is in the range of 1.0 to 4.0; Z average molecular weight The ratio (Mz/Mw) to the weight average molecular weight is in the range of 1.0 to 4.5. A pneumatic tire characterized by using the rubber composition according to claim 1 or 2 for a tread.