JP2018002862A - Modified hydrocarbon resin and elastomer composition for tire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a modified hydrocarbon resin providing an elastomer composition for tire which is excellent in workability and has excellent balance between rolling resistance and wet grip performance.SOLUTION: A modified hydrocarbon resin is obtained by modification of 100 pts.mass of a hydrocarbon resin containing 20-70 mass% of a 1,3-pentadiene monomer unit, 5-35 mass% of an alicyclic monoolefin monomer unit having 4 to 6 carbon atoms, 1-50 mass% of an acyclic monoolefin monomer unit having 4 to 8 carbon atoms, 0-10 mass% of an alicyclic diolefin monomer unit and 0-50 mass% of an aromatic monoolefin monomer unit with 0.01-20 pts.mass of at least one compound selected from the group consisting of an amine compound, an amide compound and an imide compound, the number average molecular weight (Mn) is in a range of 500-4,000, the weight average molecular weight (Mw) is in a range of 1,000-8,000, the Z average molecular weight (Mz) is in a range of 2,000-25,000, a ratio (Mw/Mn) of the weight average molecular weight to the number average molecular weight is in a range of 1.0-4.0, a ratio (Mz/Mw) of the Z average molecular weight to the weight average molecular weight is in a range of 1.0-4.5, and a softening point temperature is in a range of 80-150°C.SELECTED DRAWING: None

Description

  The present invention relates to a modified hydrocarbon resin that provides an elastomer composition for tires that is excellent in workability and has a good balance between 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, while, for example, improvement in wet grip properties is required from the viewpoint of safety. 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.

Patent Document 1 describes that by preparing a rubber composition using an amine-modified conjugated diene polymer as an elastomer, a pneumatic tire with low heat generation and improved run-flat running durability can be provided. Has been.
In Patent Document 2, by preparing a rubber composition using a hydrogenated conjugated diolefin polymer in which a polymer chain terminal is modified with an amide or imide as an elastomer, the rubber composition is excellent in wear resistance, weather resistance, processability, and the like. Further, it is described that a tire or the like with less heat generation can be obtained.

JP 2011-255881 A JP 2000-53706 A

  However, with the elastomers described in Patent Document 1 and Patent Document 2, 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 elastomer. There is a problem such as.

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

  As a result of diligent investigation on the hydrocarbon resin added to the tire elastomer composition together with the elastomer, the present inventors have obtained a predetermined amount of amine-based hydrocarbon resin containing a predetermined monomer unit in a predetermined ratio. A modified hydrocarbon resin modified by a compound and having a predetermined characteristic such as a number average molecular weight within a predetermined range is an improvement in processability, both rolling resistance and wet grip performance for an elastomer composition for a tire. The present invention has been completed by finding that it is involved in the improvement of the balance.

  Thus, according to the present invention, 1,3-pentadiene monomer unit 20 mass% to 70 mass%, C 4-6 alicyclic monoolefin monomer unit 5 mass% to 35 mass%, carbon number 4-8 acyclic monoolefin monomer units 1% by mass to 50% by mass, alicyclic diolefin monomer units 0% by mass to 10% by mass, and aromatic monoolefin monomer units 0% by mass Obtained by modifying 100 parts by mass of hydrocarbon resin containing -50% by mass with 0.01-20 parts by mass of at least one compound selected from the group consisting of amine compounds, amide compounds and imide compounds The number average molecular weight (Mn) is in the range of 500 to 4000, the weight average molecular weight (Mw) is in the range of 1000 to 8000, and the Z average molecular weight (Mz) is in the range of 2000 to 25000. ,number The ratio of the weight average molecular weight to the 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. Within this range, a modified hydrocarbon resin characterized by having a softening point temperature in the range of 80 ° C to 150 ° C is provided.

  Moreover, according to this invention, the elastomer composition for tires characterized by including at least 1 type of elastomer, at least 1 type of filler, and the above-mentioned modified hydrocarbon resin is provided.

  The filler is preferably silica.

  INDUSTRIAL APPLICABILITY The present invention has an effect of providing a 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 modified hydrocarbon resin and an elastomer composition for tires using the same.
Hereinafter, the modified hydrocarbon resin and the tire elastomer composition of the present invention will be described in detail.

A. Modified Hydrocarbon Resin The 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 5% by mass to 35%. 1% by mass to 50% by mass of an acyclic monoolefin monomer unit having 4 to 8 carbon atoms, 0% by mass to 10% by mass of an alicyclic diolefin monomer unit, and an aromatic monoolefin monomer 100 parts by mass of a hydrocarbon resin containing 0% by mass to 50% by mass of a body unit is modified with 0.01 to 20 parts by mass of at least one compound selected from the group consisting of amine compounds, amide compounds and imide compounds. The number average molecular weight (Mn) is in the range of 500 to 4000, the weight average molecular weight (Mw) is in the range of 1000 to 8000, and the Z average molecular weight (Mz) is 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. It is in the range of 0.0 to 4.5, and the softening point temperature is in the range of 80 ° C to 150 ° C.

According to the present invention, the modified hydrocarbon resin includes at least one selected from the group consisting of a predetermined amount of an amine compound, an amide compound, and an imide compound as the hydrocarbon resin containing the predetermined monomer unit in a predetermined ratio. Modified with two compounds (hereinafter sometimes referred to as amine compounds), etc., and with respect to a predetermined number average molecular weight, weight average molecular weight, Z average molecular weight, ratio of weight average molecular weight to number average molecular weight, weight average molecular weight By having characteristics such as the ratio of the Z average molecular weight and the softening point temperature, it is possible to obtain an elastomer composition for tires that is excellent in workability and has a good balance between rolling resistance and wet grip performance.
Here, by using the modified hydrocarbon resin, 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, by using the hydrocarbon resin of the predetermined monomer unit and ratio, and further having the predetermined characteristics, the modified hydrocarbon resin of the present invention has a weight average molecular weight (Mw) and a weight average. The ratio (Mw / Mn) between the molecular weight and the number average molecular weight (Mn) is appropriately low, and the softening point temperature can be appropriately high.
Therefore, when the modified hydrocarbon resin of the present invention is mixed with an elastomer or the like to form an elastomer composition, the modified hydrocarbon resin is excellent in compatibility with the elastomer and excellent in silica dispersion. By promoting the fixing of the elastomer end groups to silica, for example, the obtained elastomer composition has a low loss coefficient tan δ at 60 ° C. and a moderate loss coefficient tan δ at 0 ° C. Can be high.
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.
Moreover, since the 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 modified hydrocarbon resin is modified with a predetermined amount of an amine compound and includes a predetermined amount of an amine-modified site, so that, for example, it is excellent in dispersion of silica and promotes fixing of an elastomer end group to silica. As a result of suppressing heat generated by friction between silica and movement of the end groups of the elastomer, for example, the obtained elastomer composition has an effect of reducing the loss coefficient tan δ of the cross-linked product at 60 ° C. Can do.
For this reason, a modified hydrocarbon resin obtained by modifying a hydrocarbon resin containing the predetermined monomer unit at a predetermined ratio with a predetermined amount of an amine compound is excellent in workability, rolling resistance and wetness. The tire elastomer composition having an excellent balance of grip performance can be provided.

The modified hydrocarbon resin of the present invention is a modified product of an amine compound of a hydrocarbon resin.
Hereinafter, a hydrocarbon resin before being modified with an amine-based compound (hereinafter, simply referred to as “pre-modified resin”), an amine-based compound and a modified hydrocarbon resin (hereinafter, simply referred to as “modified resin”). Will be described in detail.

1. Hydrocarbon Resin The hydrocarbon resin is a raw material resin before being modified with an amine compound, and is a 1,3-pentadiene monomer unit 20% by mass to 70% by mass and a C 4-6 alicyclic mono. Olefin monomer unit 5 mass% to 35 mass%, C 4-8 acyclic monoolefin monomer unit 1 mass% to 50 mass%, alicyclic diolefin monomer unit 0 mass% to 10 mass% It contains 0% by mass to 50% by mass of an aromatic monoolefin monomer unit.

The content of the 1,3-pentadiene monomer unit in the resin before modification may be in the range of 20% by mass to 70% by mass, and preferably in the range of 25% by mass to 67% by mass. In particular, it is preferably in the range of 30% by mass to 65% by mass, and particularly preferably in the range of 33% by mass to 63% by mass. When the content is within the above-described range, the 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.
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 5% by mass to 35% by mass, and in the range of 8% by mass to 33% by mass. In particular, it is preferably in the range of 10% by mass to 32% by mass, and more preferably in the range of 13% by mass to 30% by mass. When the content is within the above-described range, the 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.
In addition, in a C4-C6 alicyclic monoolefin, the ratio of each compound applicable to this may be arbitrary ratios, Although it does not specifically limit, It is preferable that cyclopentene is contained at least, and C4-C6 The proportion of cyclopentene in the alicyclic monoolefin is more preferably 50% by mass or more.

An 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 and 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- And 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 1% by mass to 50% by mass, and in the range of 5% by mass to 45% by mass. In particular, it is preferably in the range of 10% by mass to 42% by mass, and particularly preferably in the range of 15% by mass to 40% by mass. When the content is within the above-described range, the 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.
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, but 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 alicyclic monoolefin having 4 to 6 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 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.

The resin before modification may contain an aromatic monoolefin 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 50% by mass, preferably in the range of 0% by mass to 45% by mass, Especially, it is preferable to exist in the range of 0 mass%-43 mass%, and it is especially preferable to exist in the range of 0 mass%-40 mass%. When the content is within the above-described range, the 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.

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 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.
The other monomer used to constitute such other monomer unit may be a compound having addition polymerizability other than the above-described monomers and capable of addition copolymerization with 1,3-pentadiene or the like. 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. Unsaturated hydrocarbons such as cycloheptene, and other non-cyclic monoolefins 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 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-modified resin is not particularly limited as long as the polymerizable component (monomer mixture A) having a monomer capable of constituting the 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-modification resin, the following aluminum halide (A), halogenated hydrocarbon (B1) in which a halogen atom is bonded to a tertiary carbon atom, and carbon-carbon non-carbon are described. In combination with a halogenated hydrocarbon (B) selected from the group consisting of halogenated hydrocarbons (B2) in which a halogen atom is bonded to a carbon atom adjacent to the saturated bond, a polymerization catalyst is used, The method which has the superposition | polymerization process to superpose | polymerize can be mentioned.
Moreover, the addition amount of each monomer contained in the monomer mixture A can be the same as the content of each monomer unit in the hydrocarbon resin.
Therefore, as a pre-modification resin, 1,3-pentadiene monomer unit 20 mass% to 70 mass%, C 4-6 alicyclic monoolefin monomer unit 5 mass% -35 mass%, carbon number 4 To 8 acyclic monoolefin monomer units 1 mass% to 50 mass%, alicyclic diolefin monomer units 0 mass% to 10 mass%, and aromatic monoolefin monomer units 0 mass% to More specifically, in the case of producing a hydrocarbon resin containing 50% by mass, the above-described production method is more specifically composed of 20% by mass to 70% by mass of 1,3-pentadiene and 5% by mass of alicyclic monoolefin having 4 to 6 carbon atoms. % To 35% by mass, 4 to 8 carbon acyclic monoolefin 1% to 50% by mass, alicyclic diolefin 0% to 10% by mass, and aromatic monoolefin 0% to 50% by mass A polymerization step of polymerizing the monomer mixture A containing How to you can be cited.

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 the 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 in 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 in that 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 the above. 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 use amount of the halogenated hydrocarbon (B) 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 the alicyclic monoolefin to the 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 blend 1,3-pentadiene or the like into the mixture a, a C5 fraction after extracting isoprene and cyclopentadiene (including its multimer) can be suitably 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. 5-10 chain saturated aliphatic hydrocarbons; cyclic saturated aliphatic hydrocarbons having 5 to 10 carbon atoms such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane. 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. Although the usage-amount of a solvent is not specifically limited, It is preferable that it exists in the range of 10 mass parts-1,000 mass parts with respect to 100 mass parts of polymeric components (monomer mixture A), and 50 mass parts- 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 in 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.

The method for producing the pre-modified resin has at least the polymerization step, but may have other steps as necessary.
Examples of the other steps include, for example, a catalyst residue that is generated when a polymerization terminator is added in the polymerization step after the polymerization step to inactivate the polymerization catalyst, and the catalyst residue insoluble in the solvent is removed by filtration or the like. After the polymerization reaction is stopped by the removal step and the polymerization step, the unreacted monomer and solvent are removed, and the low molecular weight oligomer component is removed by steam distillation or the like, followed by cooling to obtain a solid unmodified resin. It can have a recovery process.

2. Amine-based compound The amine-based compound is at least one compound selected from the group consisting of an amine compound, an amide compound, and an imide compound.

(1) Amine compound The amine compound is a compound having an amine structure in which 0 to 2 hydrogen atoms and one or more hydrocarbon groups are covalently bonded to nitrogen.

The amine compound has an amine structure, and the modified hydrocarbon resin of the present invention can provide an elastomer composition for a tire having excellent workability and a good balance between rolling resistance and wet grip performance. What is necessary is just to have a hydrocarbon group couple | bonded with a nitrogen atom in the range of 1-3, for example, a primary amine, a secondary amine, and a tertiary amine can be used.
As the hydrocarbon group, an aliphatic hydrocarbon group and an aromatic hydrocarbon group can be used.
In addition, the aromatic hydrocarbon group refers to a group in which the site directly bonded to the nitrogen atom is an aromatic ring, and even if it has an aromatic ring such as a benzyl group, the site bonded directly to the nitrogen atom Those in which is not an aromatic ring are included in the aliphatic hydrocarbon group.
In addition, the aliphatic hydrocarbon group may include any structure of a chain aliphatic group and a cyclic aliphatic group, and may include an unsaturated group. Furthermore, 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.
Furthermore, as the aliphatic hydrocarbon group and the aromatic hydrocarbon group, a substituted product in which a hydrogen atom contained in the aliphatic hydrocarbon group and the aromatic hydrocarbon group is substituted with a substituent can also be used. As a substituent, at least one of a hydrogen atom, an aliphatic hydrocarbon group, and an aromatic hydrocarbon group is bonded via an atom other than carbon such as an amine structure or a nitrogen atom such as —OCH ₃ , an oxygen atom, or a sulfur atom. Can be mentioned. Therefore, as the amine compound, if the modified hydrocarbon resin of the present invention is excellent in workability and can provide an elastomer composition for a tire excellent in the balance of rolling resistance and wet grip performance, It is not limited to a monoamine having only one amine structure in the molecule, and for example, diamines, triamines and the like having two or more amine structures covalently bonded through the hydrocarbon group can also be used. When the amine compound has two or more amine structures, the two or more amine structures may be the same structure or different structures. For example, an amine compound includes two amine structures, a primary amine structure and a secondary amine structure, includes two secondary amine structures, and one secondary amine structure is the other secondary amine structure. The hydrocarbon groups bonded to nitrogen may have different structures.

  The molecular weight of the amine compound is not particularly limited as long as it can be stably bonded to the resin before modification, and can be, for example, in the range of 50 to 500, particularly in the range of 100 to 300. Preferably there is.

Examples of the primary amine include amines in which aliphatic hydrocarbon groups having 6 to 20 carbon atoms in total are bonded as hydrocarbon groups such as 1-hexylamine, 1-heptylamine, and 1-octylamine, Examples of the hydrocarbon group include amines to which a heteroaromatic group contained in an aromatic hydrocarbon group is bonded, and among others, amines to which a total of 8 to 12 carbon atoms in the compound are bonded. Can be preferably used.
Examples of the secondary amine include 1,6-bis (ethylamino) hexane, 1,2-bis (tert-butylamino) ethane, N′-benzyl-N, N-dimethylethylenediamine, and N-benzyl-N. , N′-dimethylethylenediamine and other hydrocarbon groups in which a total of 6 to 20 carbon atoms of aliphatic hydrocarbon groups are bonded, and heteroaromatic groups contained in aromatic hydrocarbon groups are bonded as hydrocarbon groups The amine etc. which the C8-C12 aliphatic hydrocarbon group in total in the compound couple | bonded can be used preferably.
Examples of the tertiary amine include fatty acids having 6 to 20 carbon atoms in total in the compound as hydrocarbon groups such as N′-benzyl-N, N-dimethylethylenediamine and N-benzyl-N, N′-dimethylethylenediamine. Examples include amines to which aromatic hydrocarbon groups are bonded, and amines to which heteroaromatic groups contained in aromatic hydrocarbon groups are bonded as hydrocarbon groups. Among them, fatty acids having 8 to 12 carbon atoms in total in the compound An amine or the like to which an aromatic hydrocarbon group is bonded can be preferably used.
In addition, when it has a secondary amine structure and a tertiary amine structure like N'-benzyl-N, N-dimethylethylenediamine, the amine compound corresponds to both a secondary amine and a tertiary amine. It is.
In addition, N′-benzyl-N, N-dimethylethylenediamine has (1) benzyl group (carbon number 7) and (2) ethylene group (—C ₂ H ₅ ) as hydrocarbon groups constituting the secondary amine structure. In which one hydrogen atom has an aliphatic hydrocarbon group (—C ₂ H ₄ —N— (CH ₃ ) ₂ : carbon number 4) substituted with an amine structure, and has at least 7 carbon atoms. Having a hydrocarbon group.
Further, N′-benzyl-N, N-dimethylethylenediamine has (1) two methyl groups (1 carbon number) and (2) ethylene group (—C ₂ H) as hydrocarbon groups constituting the tertiary amine structure. ₅ ) one hydrogen atom has an aliphatic hydrocarbon group (— (C ₂ H ₄ ) —NH—CH ₂ —C ₆ H ₅ : carbon number 9) substituted with an amine structure, It has at least an aliphatic hydrocarbon group having 9 carbon atoms.

Examples of the diamine include 1,6-bis (ethylamino) hexane, 1,2-bis (tert-butylamino) ethane, 1,4-di (aminomethyl) cyclohexane, 4-amino-1-diethylaminopentane, N -Amine having a total of 6 to 20 carbon atoms bonded as a hydrocarbon group such as benzyl-N, N'-dimethylethylenediamine as a hydrocarbon group, and a heterocycle included in an aromatic hydrocarbon group as a hydrocarbon group The amine etc. which the aromatic couple | bonded can be mentioned, Especially, the amine etc. which the C8-C12 aliphatic hydrocarbon group in total in the compound couple | bonded can be used preferably.
Examples of the triamine include amines and carbons bonded with aliphatic hydrocarbon groups having a total of 6 to 20 carbon atoms in the compound as hydrocarbon groups such as bis (4-aminobutyl) amine and bis (6-aminohexyl) amine. Examples of the hydrogen group include amines to which a heteroaromatic group contained in an aromatic hydrocarbon group is bonded. Among them, amines having a total of 8 to 12 carbon atoms in an aliphatic hydrocarbon group are combined. It can be preferably used.

  The said amine compound may contain only 1 type and may contain 2 or more types.

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

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

The hydrocarbon group for R _{1 to} R ₃ can be the same as that described in the section “(1) Amine compound”. Further, R _{1 to} R ₃ may be the same functional group or different functional groups.
Further, the hydrocarbon groups represented by R ₁ to R ₃ are modified hydrocarbon resin of the present invention is excellent in workability, and can give a tire elastomer composition having an excellent balance of rolling resistance and wet grip performance As long as it is possible, a part of the hydrogen atoms of the aliphatic hydrocarbon group and the aromatic hydrocarbon group contained as the hydrocarbon group may be substituted with an amide structure or an amine structure.
That is, the amide compound is not limited to a monoamide having only one amide structure in the molecule, and has two or more amide structures covalently bonded via R _{1 to} R ₃ as the hydrocarbon group, For example, diamide, triamide and the like can be used.
The amide compound may have an amide structure and an amine structure bonded via R _{1 to} R ₃ as the hydrocarbon group.

  The molecular weight of the amide compound is not particularly limited as long as it can be stably bonded to the resin before modification, and can be, for example, in the range of 50 to 500, particularly in the range of 100 to 300. Preferably there is.

  As the amide compound, specifically, an amide compound described in JP-A-2000-53706 can be used, and more specifically, N, N-dimethylformamide, acetamide, N, N-diethylacetamide. , Aminoacetamide, N, N-dimethyl-N ′, N′-dimethylaminoacetamide, N, N-dimethylaminoacetamide, N, N-ethylaminoacetamide, N, N-dimethyl-N′-ethylaminoacetamide, acrylamide N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, nicotinamide, isonicotinamide, picolinic acid amide, N, N-dimethylisonicotinamide, succinic acid amide, phthalic acid amide, N, N, N ′ , N′-tetramethylphthalamide, oxamide and N, , N ′, N′-tetramethyloxamide, 2-furancarboxylic acid amide, N, N-dimethyl-2-furancarboxylic acid amide, quinoline-2-carboxylic acid amide, N-ethyl-N-methyl-quinolinecarboxylic acid Acid amides, N-acetylethylenediamine and the like can be mentioned, among which N-acetylethylenediamine and the like can be preferably used.

  The amide compound may include only one type, or may include two or more types.

(3) Imide compound As said imide compound, what is necessary is just a compound which has one or more imide bonds in a molecule | numerator, For example, the cyclic imide compound represented by following formula (2) or (3) can be used.

(R ₄ , R ₅ and R ₆ and R ₇ , R ₈ and R ₉ in formulas (2) and (3) are each independently a hydrogen atom or a hydrocarbon group.)

The hydrocarbon group for R _{4 to} R ₉ can be the same as that described in the section “(1) Amine compound”. R _{4 to} R ₉ may be the same functional group or different functional groups.
Further, the hydrocarbon groups in R _{4 to} R ₉ described above can provide the tire elastomer composition in which the modified hydrocarbon resin of the present invention has excellent processability and excellent balance between rolling resistance and wet grip performance. As long as it is possible, a part of the hydrogen atoms of the aliphatic hydrocarbon group and aromatic hydrocarbon group contained as the hydrocarbon group may be substituted with an imide structure, an amide structure or an amine structure. .
That is, the imide compound is not limited to a monoimide having only one imide structure in the molecule, and has two or more imide structures bonded via R _{7 to} R ₉ as the hydrocarbon group. Diimide, triimide and the like can also be used.
The imide compound may have an amide structure and at least one of an amide structure and an amine structure bonded via R _{7 to} R ₉ as the hydrocarbon group.

  The molecular weight of the imide compound is not particularly limited as long as it can be stably bonded to the resin before modification, and can be, for example, in the range of 50 to 500, and in particular, in the range of 100 to 300. Preferably there is.

  As the imide compound, specifically, an imide compound described in JP 2000-53706 A can be used, and more specifically, succinimide, N-methyl succinimide, maleimide, N-methyl. Maleimide, phthalimide, N-methylphthalimide, bismaleimide and the like can be mentioned, and among them, N-alkylmaleimide compounds such as N-methylmaleimide can be preferably used.

  The imide compound may include only one type or may include two or more types.

(4) Amine compound The amine compound is at least one compound selected from the group consisting of an amine compound, an amide compound, and an imide compound.
Accordingly, the amine compound may include only an amine compound, only an amide compound, or only an imide compound, and may include two types of compounds, an amine compound and an amide compound, an amine compound, It may contain three kinds of compounds, an amide compound and an imide compound.
In the present invention, the amine compound preferably includes an amide compound.

The modified hydrocarbon resin of the present invention is obtained by modifying 100 parts by mass of a hydrocarbon resin with 0.01 to 20 parts by mass of an amine compound.
Here, “obtained by modification” means that the amine compound is bonded to the hydrocarbon resin by a covalent bond.
Moreover, what was obtained by modifying 100 parts by mass of a hydrocarbon resin with 0.01 to 20 parts by mass of an amine compound is derived from an amine compound that is bonded to 100 parts by mass of the hydrocarbon resin. It means that the mass of the site to be within the range of 0.01 to 20 parts by mass.
As content of the said amine compound, ie, content of the site | part originating in the amine compound couple | bonded with respect to 100 mass parts of hydrocarbon resins which are resin before modification | denaturation, the range of 0.01 mass part-20 mass parts And preferably within the range of 0.1 to 10 parts by weight, more preferably within the range of 0.1 to 8 parts by weight, especially 0.1 parts by weight. It is preferably within the range of 5 parts by mass to 5 parts by mass. When the content is within the above-described range, the 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.

The amine-modifying method of the resin before modification using the amine compound may be any method that allows the amine-based compound to be bonded to the resin before modification by a covalent bond.
As such an amine modification method, a known method can be appropriately used.
Specifically, as the amine modification reaction, by mixing a resin before modification, an amine compound and a peroxide initiator, free radicals are generated in the resin before modification by the peroxide initiator. Can be used, such as a method of reacting an amine compound with an amine compound, a method of mixing an amine compound with a pre-denaturing resin having an active terminal, and the like.

In the above-described amine modification method, the amount of the amine compound added to the pre-modified resin may be any amount that can bind a desired amount of the amine compound. For example, the amine compound in the modified hydrocarbon resin. The amount can be the same amount or more.
The reaction conditions in the amine modification method using free radicals described above are not particularly limited as long as a desired amount of amine compound can be bound to the resin before modification, and the kind of resin before modification and the kind of amine compound. 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 amine 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 amine modification method may be, for example, a method in which amine 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 amine compound to the resin before modification. For example, an inorganic peroxide such as sodium persulfate, diisopropylbenzene hydroperoxide, etc. Known peroxide initiators such as organic peroxides can be used.
In addition, about such an inorganic peroxide, an organic peroxide, etc., the thing as described in Unexamined-Japanese-Patent No. 2004-285230 etc. can be used, for example.
The amount of the peroxide initiator used is not particularly limited as long as a desired amount of the amine compound can be bound to the pre-modification resin, and is appropriately set according to the addition amount of the amine compound. .

The amine modification method may be a method in which an amine compound is bonded to a pre-modification resin via a known silane coupling agent, if 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 amine modification method.
As the silane coupling agent, for example, a bifunctional silane coupling agent having a vinyl group and a reactive functional group capable of binding to a nitrogen atom contained in an amine compound can be used.
Examples of the functional group for reaction include a hydroxyl group, a carboxy group, a ketone group, an epoxy group, a halogen group, and a sulfonic acid group. Among them, a hydroxyl group, a carboxyl group, and the like are preferable.
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.
In addition, the amount of the silane coupling agent used as a spacer between the amine compound and the resin before modification, including those not bonded to the amine compound, is usually included as part of the resin before modification. It is what
Examples of the method for bonding the pre-modified resin bonded with the silane coupling agent and the amine compound include, for example, a method in which the pre-modified resin bonded with the silane coupling agent and the amine compound are mixed and heat-treated. Can do.
As said heat processing conditions, it shall carry out for 5 minutes-20 hours within the range of temperature 50 degreeC-300 degreeC, for example.
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.

Moreover, as the above-mentioned amine modification method, a method in which an amine compound is bonded to a resin before modification 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 resin before modification. It may be.
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.
The acid modification method may include a method in which an acid anhydride group is introduced as an acidic group, and the resin before modification and the unsaturated dicarboxylic acid anhydride are mixed and heat-treated.
Examples of unsaturated carboxylic acids used for introducing carboxyl groups include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid and the like, and ethylenically unsaturated carboxylic acids having 8 or less carbon atoms, and Examples include Diels-Alder adducts of conjugated dienes such as 3,6-endomethylene-1,2,3,6-tetrahydrophthalic acid and α, β-unsaturated dicarboxylic acids having 8 or less carbon atoms.
Examples of unsaturated dicarboxylic acid anhydrides used for introducing acid anhydride groups include α, β-unsaturated dicarboxylic acid anhydrides having 8 or less carbon atoms, such as maleic anhydride, itaconic anhydride, citraconic anhydride, and 3 Diels-Alder adducts of conjugated dienes such as 1,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride and α, β-unsaturated dicarboxylic anhydrides having 8 or less carbon atoms. .
In addition, the blending amount of an acid modifier such as an unsaturated carboxylic acid introduced to acid-modify such a pre-modification resin, including those not bound to an amine compound, is usually It is included as a part.
As the reaction conditions for the acid modification reaction, for example, the reaction can be performed within a temperature 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 amine compound include a method in which a resin before modification or a resin before modification after acid modification and an amine 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 amine compound.

In the following formulas (4) to (6), the amine modification method described above is carried out by adding an amine to the resin A before modification in which a maleic anhydride is used as an unsaturated dicarboxylic anhydride and a carboxylic anhydride group as an acidic group is introduced. The example which is a method of obtaining the modified | denatured hydrocarbon resin B by making a system compound react is shown.
Moreover, following formula (4) shows the example which uses the diamine compound containing two amine structures as an amine compound.
Further, the following formulas (5) and (6) show examples in which an amide compound containing an amine structure and an amide structure is used as the amine compound, and the formula (5) shows an amide structure contained in the amine compound. Is reacted with an acidic group, and formula (6) shows an example in which a nitrogen atom of an amine structure contained in an amine compound reacts with an acidic group.

The amine modification reaction is a secondary modification reaction in which the amine compound bonded to the modified hydrocarbon resin is further reacted with the modified hydrocarbon resin after the primary modification reaction in which the amine compound is bonded to the pre-modified resin. It may occur.
As the secondary modification reaction, for example, as shown in the following formulas (7) and (8), an amine structure or an amide structure contained in an amine compound bonded to the modified hydrocarbon resin may be further modified. And the like which react with an acidic group or the like contained in the like.
Further, the secondary modification reaction may occur for the same modified hydrocarbon resin as the modified hydrocarbon resin bonded by the primary modification reaction, or may occur for a different modified hydrocarbon resin or a pre-modified resin, It may produce a crosslinked modified hydrocarbon resin.
In the formula (7), the secondary modification reaction is such that the nitrogen atom of the amine structure contained in the amine compound bonded to the modified hydrocarbon resin reacts with an acidic group contained in the same modified hydrocarbon resin. Thus, an example of newly generating an amide structure will be shown. Further, the formula (8) shows that the secondary modification reaction is carried out with respect to the same acidic group as that in which the nitrogen atom of the amide structure contained in the amine compound bonded to the modified hydrocarbon resin is reacted with the amine compound. An example in which a cyclic imide structure is newly generated by reacting again is shown.

3. Modified Hydrocarbon Resin The number average molecular weight (Mn) of the modified hydrocarbon resin is not particularly limited as long as it is within the range of 500 to 4000, but is preferably within the range of 550 to 3000. In particular, it is more preferable to be in the range of 600 to 2500. This is because when the number average molecular weight (Mn) is within the above range, the modified hydrocarbon resin can be excellent in compatibility with the elastomer. As a result, the modified hydrocarbon resin can easily reduce the loss coefficient tan δ at 60 ° C. of the crosslinked product of the elastomer composition, and can be excellent in rolling resistance.

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 in particular, in the range of 1,200 to 6,000. It is preferable to be within a range of 1,400 to 4,500, in particular. This is because when the weight average molecular weight (Mw) is within the above range, the modified hydrocarbon resin can be excellent in compatibility with the elastomer. As a result, the modified hydrocarbon resin can easily reduce the loss coefficient tan δ at 60 ° C. of the crosslinked product of the elastomer composition, and can be excellent in rolling resistance.
Further, when the weight average molecular weight (Mw) is within the above-mentioned range, the modified hydrocarbon resin can easily increase the loss coefficient tan δ at 0 ° C. and has excellent rolling resistance. Because it can.

  The Z-average molecular weight (Mz) of the 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. It is preferable that it is within a range of 4,000 to 1,5000. This is because when the Z average molecular weight (Mz) is within the above-mentioned range, the modified hydrocarbon resin can be excellent in compatibility with the elastomer. As a result, the modified hydrocarbon resin can easily reduce the loss coefficient tan δ at 60 ° C. of the crosslinked product of the elastomer composition, and can be excellent in rolling resistance.

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 determined as polystyrene converted values by high performance liquid chromatography.
More specifically, the number average molecular weight, the weight average molecular weight and the Z average molecular weight are measured by using “HLC-8320GPC” manufactured by Tosoh Corporation as a measuring device, and three “TSKgel SuperMultipore HZ” manufactured by Tosoh Corporation are connected. And measured with a tetrahydrofuran as a solvent at 40 ° C. and a flow rate of 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 is not particularly limited as long as it is in the range of 1.0 to 4.0, but 1.2. It is preferably in the range of -3.5, and more preferably in the range of 1.4-3.0. This is because when the ratio is within the above-described range, the modified hydrocarbon resin can be excellent in compatibility with the elastomer. As a result, the modified hydrocarbon resin can easily reduce the loss coefficient tan δ at 60 ° C. of the crosslinked product of the elastomer composition, and can be excellent in wet grip performance. .

  The ratio (Mz / Mw) of the Z-average molecular weight to the weight-average molecular weight of the 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 ˜4.0, and more preferably in the range of 1.0 to 3.5. This is because when the ratio is within the above-described range, the modified hydrocarbon resin can be excellent in compatibility with the elastomer. As a result, the modified hydrocarbon resin can easily reduce the loss coefficient tan δ at 60 ° C. of the crosslinked product of the elastomer composition, and can be excellent in wet grip performance. .

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 is preferably in the range of 85 ° C to 145 ° C, particularly 90 ° C. More preferably, it is in the range of ~ 140 ° C. This is because when the softening point is within the above range, the modified hydrocarbon resin can be excellent in compatibility with the elastomer. As a result, the modified hydrocarbon resin can easily reduce the loss coefficient tan δ at 60 ° C. of the crosslinked product of the elastomer composition, and can be excellent in rolling resistance.
In addition, since the softening point is within the above range, the modified hydrocarbon resin can easily increase the loss coefficient tan δ at 0 ° C. and can have excellent wet grip performance. is there.
The softening point in the present invention is a value measured according to JIS K 6863 for a modified hydrocarbon resin, for example.

The 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 modified hydrocarbon resin can provide an elastomer composition for tires that is excellent in workability and excellent in the balance between rolling resistance and wet grip performance.
Therefore, the 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 modified hydrocarbon resin, a method having an amine modification step of modifying 100 parts by mass of the hydrocarbon resin, which is a pre-modified resin, with 0.01 to 20 parts by mass of the amine compound is used. it can.
The method of modifying with the amine compound, that is, the amine modifying method, and the like can be the same as the contents described in the above section “2. Amine 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 includes at least one elastomer, at least one filler, and the above-described modified hydrocarbon resin.

  According to the present invention, by using the above-described 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 has an elastomer, a filler, and a modified hydrocarbon resin.
Hereafter, each component of the elastomer composition for tires of this invention is demonstrated in detail.

1. Modified Hydrocarbon Resin The content of the modified hydrocarbon resin is not particularly limited as long as it can provide an elastomer composition for tires that is excellent in workability and has a good balance between rolling resistance and wet grip performance.
The content is, for example, a ratio with respect to 100 parts by mass of the elastomer, and can be within a range of 0.1 parts by mass to 50 parts by mass, and particularly preferably within a range of 1 part by mass to 30 parts by mass. 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 modified hydrocarbon resin can be the same as the contents described in the section “A. 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 an elastomer 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. Also, 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 is, for example, a ratio with respect to 100 parts by mass of the elastomer and can be within a range of 30 parts by mass to 250 parts by mass, and particularly preferably within a range of 30 parts by mass to 200 parts by mass. , Preferably in the range of 40 parts by weight to 150 parts by weight, and particularly preferably in the range of 50 parts by weight 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 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, for example, JP-A-2006-30795.

  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 of 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. In 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 a heating method, a general method used for crosslinking of the elastomer composition such as press heating, steam heating, oven heating, hot air heating, or the like 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.

[Number average molecular weight, weight average molecular weight, Z average molecular weight and molecular weight distribution]
About the modified hydrocarbon resin as a sample, gel permeation chromatography analysis is performed to determine the number average molecular weight (Mn), the weight average molecular weight (Mw) and the Z average molecular weight (Mz) in terms of standard polystyrene. It was shown by the ratio of Mw / Mn and Mz / Mw. 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 modified hydrocarbon resin as a sample was measured according to JIS K 6863.

[Mooney viscosity (ML1 + 4)]
About the elastomer composition used as a sample, it measured on condition of the following according to JISK6300-1: 2001.
Test temperature: 100 ° C
・ Type of rotor: L type ・ Testing machine: Shimadzu Mooney Viscometer SMV-300J manufactured by Shimadzu Corporation

[Tensile strength (MPa), elongation (%), and 200% elongation tensile stress (MPa)]
About the test piece of the elastomer crosslinked material used as a sample, in accordance with JIS K 6251: 2010, tensile strength (tensile stress (MPa)), elongation (elongation (%)), and 200% tensile stress (tensile stress (tensile stress (%)) MPa)).
The 200% tensile strength ((MPa)) is a value obtained by dividing the tensile force when 200% elongation is given to the test piece by the initial cross-sectional area of the test piece.
-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
-Test machine: TENSOMETER ₁₀ 0k manufactured by ALPHA TECHNOLOGIES
・ Test machine capacity: Load cell type 1kN

[Loss tangent tan δ]
The loss tangent tan δ at 0 ° C. and 60 ° C. was measured under the following measurement conditions for the test piece of the crosslinked elastomer product as a sample under the following measurement conditions under the conditions of dynamic strain 0.5% and 10 Hz. . 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] (manufactured by BASF, trade name: Irganox 1010) as an antioxidant 0.2 part was added, and then 2.0 parts of maleic anhydride was added, followed by addition reaction at 230 ° C. for 1 hour, and then 1.5 parts of N-benzyl-N, N′-dimethylethylenediamine as an amine compound. And an addition reaction was carried out at 200 ° 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 modified hydrocarbon resin of Example 1. For the resulting modified hydrocarbon resin of Example 1, the number average molecular weight, 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 amine compound (parts) / resin before modification (100 parts) in Table 1 were calculated using maleic anhydride used for acid modification as part of the raw material of the resin before modification. The addition amount (parts) of an amine compound per 100 parts in total of the monomer mixture constituting the pre-modification resin described in 1 and maleic anhydride.

[Examples 2 to 5 and Comparative Examples 1 to 4]
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. In addition, the diisobutylene, aromatic monoolefin, and toluene which are not described in Example 1 were mixed with 1, 3- pentadiene etc., and used for superposition | polymerization.
Styrene was used as the aromatic monoolefin.
In Comparative Examples 1 and 2, an unmodified hydrocarbon resin was obtained without performing acid modification with maleic anhydride and amine modification with an amine compound.

[Production and Evaluation of Elastomer Composition and Crosslinked Elastomer]
In a Banbury mixer, 100 parts of solution-polymerized styrene-butadiene rubber (S-SBR) is masticated for 30 seconds, and then 53.0 parts of silica (trade name “Zeosil 1115MP” manufactured by Rhodia), silane coupling agent: screw 7.0 parts of [3- (triethoxysilyl) propyl] tetrasulfide (Degussa, trade name “Si69”) and 10 parts of the modified hydrocarbon resin obtained in Example 1 were added, and after kneading for 90 seconds, 37.0 parts of silica (trade name “Zeosil 1115MP” manufactured by Rhodia), 3.0 parts of zinc oxide, 2.0 parts of stearic acid and anti-aging agent: N-phenyl-N ′-(1,3-dimethylbutyl) Add 2.0 parts of p-phenylenediamine (trade name “NOCRACK 6C”, manufactured by Ouchi Shinsei Co., Ltd.), knead for 90 seconds, and then process oil (new 30 parts by Nippon Oil Co., Ltd. (trade name “Aromax T-DAE”) 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.

About the elastomer composition and elastomer crosslinked product produced using the modified hydrocarbon resin of Example 1 obtained, Mooney viscosity of the elastomer composition, tensile strength (MPa) of elastomer crosslinked product, elongation (%), 200 % Tensile stress (MPa) and loss tangent tan δ were measured. The results are shown in Table 1.
For the obtained 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. Tensile strength (MPa), elongation (%), 200% tensile stress (MPa) 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: Laboratory Plast Mill, Banbury mixer B-600 manufactured by Toyo Seiki Seisakusho Co., Ltd.
-Filling ratio: 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, a material excellent in both rolling resistance and wet grip performance is modified with a predetermined amount of an amine compound and has a weight with respect to a predetermined number average molecular weight, weight average molecular weight, Z average molecular weight, number average molecular weight. Those having characteristics such as the ratio of the average molecular weight, the ratio of the Z average molecular weight to the weight average molecular weight, and the softening point temperature, such as the weight average molecular weight (Mw) and the ratio of the weight average molecular weight to the number average molecular weight (Mn) (Mw / Mn) was confirmed to be a modified hydrocarbon resin having a moderately low softening point temperature.
As described above, the hydrocarbon resin containing the predetermined monomer unit in a predetermined ratio is modified with a predetermined amount of an amine compound, and the weight average molecular weight, the softening point temperature, and the like are within a predetermined range. It was confirmed that by using a hydrocarbon resin, it is possible to obtain an elastomer composition for a tire that is excellent in workability and has a good balance between rolling resistance and wet grip performance.

Claims (3)

1,3-pentadiene monomer unit 20 mass% to 70 mass%,
5 to 35% by mass of an alicyclic monoolefin monomer unit having 4 to 6 carbon atoms,
1 to 50 mass% of 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 50% by mass of an aromatic monoolefin monomer unit, an amine compound, an amide compound and an imide It is obtained by modification with 0.01 to 20 parts by mass of at least one compound selected from the group consisting of compounds,
The number average molecular weight (Mn) is in the range of 500 to 4000;
The weight average molecular weight (Mw) is in the range of 1000-8000,
Z average molecular weight (Mz) is in the range of 2000-25000,
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,
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 modified hydrocarbon resin having a softening point temperature in the range of 80 ° C to 150 ° C.   A tire elastomer composition comprising: at least one elastomer; at least one filler; and the modified hydrocarbon resin according to claim 1.   The tire elastomer composition according to claim 2, wherein the filler is silica.