JP7240203B2 - PETROLEUM-BASED AROMATIC-CONTAINING OIL, RUBBER COMPOSITION, TIRE, AND METHOD FOR MAKING TIRE - Google Patents

Description

TECHNICAL FIELD The present invention relates to a petroleum-based aromatic-containing oil, a rubber composition, a tire, and a method for producing a tire.

In general, rubber products are often blended with process oil in order to improve the processability and softening properties of the rubber composition. For example, synthetic rubber such as SBR (styrene-butadiene copolymer rubber) is compounded with an extender oil during its synthesis (rubber compounding oil). In addition, processed rubber products such as tires are mixed with process oil in order to improve processability and quality of the processed rubber products. In addition, although expressions are divided into extension oil and processing oil here, these are sometimes collectively referred to as process oil.
On the other hand, in Europe, there is a regulation (REACH regulation) that prohibits the use of rubber compounding oil containing a specific amount or more of a specific carcinogenic polycyclic aromatic compound in the manufacture of tires or tire parts. Applied from 2010. Therefore, there is a demand for rubber compounding oils that conform to the REACH regulations.

The trend toward fuel efficiency in the automobile field is attracting a great deal of attention, and there is a demand for further improvements in fuel efficiency of tires. With the start of the tire labeling system in January 2010, tires are strongly required to improve "rolling resistance performance" indicating fuel efficiency and "wet grip performance" indicating braking performance. However, rolling resistance performance and wet grip performance are generally in a contradictory relationship, and achieving both at a high level is a challenge.

To improve the rolling resistance performance of a tire, there are methods such as reducing air resistance, devising a tread pattern, and suppressing the hysteresis loss of the rubber composition, that is, the tread compound itself. In recent years, compounds containing silica have become popular as a reinforcing material, which is one of the tire formulations. When silica is simply blended, silica particles tend to aggregate together in the compound, causing energy loss due to friction between silica molecules during rubber deformation. On the other hand, with the aim of improving rolling resistance performance while maintaining wet grip performance, a method of controlling the form of silica by applying terminal-modified silica or a silane coupling agent has been proposed.
According to Patent Document 1, a first base kneading step of kneading a rubber component, hydrated calcium carbonate, and a silane coupling agent, and kneading the kneaded product obtained by the first base kneading step and silica. A tire rubber composition obtained by a manufacturing method including a second base kneading step is disclosed. According to this, it is said that it is possible to obtain a rubber composition for tires that has excellent dispersibility of silica and can improve fuel economy, wet grip performance, and wear resistance in a well-balanced manner.

JP 2012-153787 A

However, tires are required to further improve "rolling resistance performance" and "wet grip performance" and to achieve both of these. Various approaches from rubber members other than silica and silane coupling agents are expected to meet such demands.

The present invention has been made to solve the above-mentioned problems, and enables the production of a rubber composition having excellent rolling resistance performance and wet grip performance, and a petroleum aromatic-containing oil that satisfies the REACH regulations. intended to provide
Another object of the present invention is to provide a rubber composition that contains a petroleum-based aromatic-containing oil that satisfies REACH regulations and that is excellent in rolling resistance performance and wet grip performance.
Another object of the present invention is to provide a tire containing the petroleum-based aromatic-containing oil and a method for producing the tire.

As a result of intensive studies to solve the above problems, the present inventors found that by blending an oil containing the following specific amounts of a saturated component and, among aromatic components, a bicyclic aromatic component in particular, the rolling The inventors have found that it is possible to produce a rubber composition having excellent resistance performance and wet grip performance, and have completed the present invention.
That is, one aspect of the present invention is the following petroleum-based aromatic-containing oil, rubber composition, tire, and tire manufacturing method.

(1) The ratio of saturated content by the clay gel method is 45% by mass or less,
The ratio of bicyclic aromatics fractionated using HPLC is 16% by mass or more and 29% by mass or less with respect to 100% by mass of aromatics by the clay gel method ,
The content of benzo(a)pyrene is 1 mass ppm or less,
A petroleum-based aromatic-containing oil having a total content of specific aromatic compounds of 1) to 8) below of 10 ppm by mass or less.
1) Benzo(a)pyrene (BaP)
2) Benzo(e)pyrene (BeP)
3) Benzo(a)anthracene (BaA)
4) Chrysene (CHR)
5) benzo(b)fluoranthene (BbFA)
6) benzo(j)fluoranthene (BjFA)
7) Benzo(k)fluoranthene (BkFA)
8) Dibenzo(a,h)anthracene (DBAhA).
(2) The petroleum-based aromatic-containing oil according to (1) above, wherein the ratio of saturated content according to the clay gel method is 22% by mass or more.
(3) In (1) or (2) above, wherein the ratio of the bicyclic aromatic fraction fractionated using the HPLC is less than 23% by mass with respect to 100% by mass of the aromatic content by the Claygel method. A petroleum aromatic-containing oil as described.
(4) The petroleum-based aromatic-containing oil according to any one of (1) to (3) above, wherein the ratio of saturated components by the clay gel method is 36% by mass or less.
(5) The ratio of the bicyclic aromatic fraction fractionated using the HPLC is 22% by mass or less with respect to 100% by mass of the aromatic content by the Clay gel method , the above (1) to (4). A petroleum-based aromatic-containing oil according to any one of the above.
(6) The petroleum-based aromatic-containing oil according to any one of (1) to (5), which is an extender oil or process oil used by being mixed with rubber.
(7) A rubber composition comprising the petroleum-based aromatic-containing oil according to any one of (1) to (6) above and a rubber.
(8) A tire containing the petroleum-based aromatic-containing oil according to any one of (1) to (6).
(9) Manufacture of the tire according to claim 8, comprising blending and vulcanizing the rubber and the petroleum-based aromatic-containing oil according to any one of (1) to (6). Method.

According to the present invention, it is possible to produce a rubber composition excellent in rolling resistance performance and wet grip performance, and to provide a petroleum-based aromatic-containing oil that satisfies the REACH regulations.
Moreover, according to the present invention, it is possible to provide a rubber composition that contains a petroleum-based aromatic-containing oil that satisfies REACH regulations and that is excellent in rolling resistance performance and wet grip performance.
Further, according to the present invention, a tire containing the petroleum-based aromatic-containing oil and a method for manufacturing the tire can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is process drawing explaining an example of the manufacturing method of the petroleum-based aromatic containing oil of one Embodiment of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is process drawing explaining an example of the process of preparing the tire composition of one Embodiment of this invention.

Embodiments of the petroleum-based aromatic-containing oil, rubber composition, tire, and tire manufacturing method of the present invention are described below.

<<Petroleum-based aromatic-containing oil>>
The petroleum-based aromatic-containing oil of the embodiment has a saturated content by the Claygel method, a bicyclic aromatic content fractionated using HPLC, a benzo (a) pyrene content, and a specific aromatic compound The content satisfies a specific numerical range. A rubber composition or tire containing a petroleum aromatic-containing oil that satisfies the following numerical ranges for these items has preferable tan δ (50° C.) and tan δ (0° C.) values, wet grip performance and rolling resistance performance. are compatible.

Here, "wet grip performance" means so-called braking performance, and tan δ (0°C) obtained by a dynamic viscoelasticity test is an index thereof. "Rolling resistance performance" is so-called fuel efficiency performance, and tan δ (50°C) obtained by a dynamic viscoelasticity test is an index thereof.

The above "petroleum-based" means containing a petroleum-derived hydrocarbon oil. The above-mentioned "aromatic-containing oil" means that the ratio of saturates by the clay gel method and the ratio of bicyclic aromatics fractionated using HPLC satisfy the following numerical ranges.
The petroleum-based aromatic-containing oil of the embodiment is not particularly limited in production method or classification as long as it satisfies the numerical ranges of the above items. Distillation fractions, vacuum distillation residues, deasphalted oils, solvent extraction raffinates, hydrorefined oils, dewaxed oils, solvent extraction extracts, etc., and oils produced by the below-described process for producing petroleum aromatic-containing oils. It is preferable to contain The content of the petroleum-derived hydrocarbon oil in the petroleum-based aromatic-containing oil may be 50% by mass or more, 80% by mass or more, or 95% by mass or more.

Each item relating to the properties of the petroleum-based aromatic-containing oil of the embodiment will be described below.

The components of petroleum oil can be classified into saturates, aromatics, and extreme components (% by mass) by the Claygel method. The following values for saturates, aromatics, or extreme components (% by mass) according to the Claygel method are values for 100% by mass of the total amount of saturates, aromatics, and extreme components.

The petroleum-based aromatic-containing oil of the embodiment has a saturated content of 45% by mass or less, preferably 36% by mass or less, more preferably 30% by mass or less, as determined by the clay gel method. The petroleum-based aromatic-containing oil of the embodiment preferably has a saturated content of 5% by mass or more, more preferably 20% by mass or more, and more preferably 22% by mass or more by the clay gel method. preferable. As an example of the numerical range of the above numerical values, the petroleum-based aromatic-containing oil of the embodiment may have a saturated content ratio of 5% by mass or more and 45% by mass or less by the clay gel method, or 20% by mass or more and 36% by mass. % or less, or 22% by mass or more and 30% by mass or less.
When the ratio of the above saturated content satisfies the above numerical value, the tan δ (50 ° C.) and tan δ (0 ° C.) values of the rubber composition or tire containing the oil become preferable, wet grip performance and rolling resistance performance are compatible.
This is because the saturate content has a moderate balance as the polarity of hydrocarbons and exhibits a certain affinity for rubber and a certain affinity for rubber compounding agents. It is believed that the physical properties of the produced rubber composition or tire can be made suitable when the ratio is within the above range.

In the petroleum-based aromatic-containing oil of the embodiment, the proportion of aromatics by the clay gel method is preferably 50% by mass or more, more preferably 51% by mass or more, and 58% by mass or more. More preferred. In the petroleum-based aromatic-containing oil of the embodiment, the aromatic content ratio by the clay gel method is preferably 74% by mass or less, more preferably 70% by mass or less, and 69% by mass or less. More preferred. As an example of the numerical range of the above numerical values, the petroleum-based aromatic-containing oil of the embodiment may have an aromatic content ratio of 50% by mass or more and 74% by mass or less by the clay gel method, or 51% by mass or more and 70% by mass. % by mass or less, or 58% by mass or more and 69% by mass or less.
When the ratio of the aromatic content satisfies the above numerical value, the rubber composition or tire containing the oil has preferable tan δ (50 ° C.) and tan δ (0 ° C.) values, wet grip performance and rolling resistance performance is compatible.
This is because the aromatic content exhibits a high affinity for rubber, and the physical properties of the rubber composition or tire to be produced can be improved by setting the proportion of the aromatic content within the above range. This is thought to be because it is possible.

In the petroleum-based aromatic-containing oil of the embodiment, the ratio of the pole component by the clay gel method is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 3% by mass or more. preferable. In the petroleum-based aromatic-containing oil of the embodiment, the ratio of the pole component by the clay gel method is preferably 11% by mass or less, more preferably 10% by mass or less, and further preferably 9% by mass or less. preferable. As an example of the numerical range of the above numerical values, the petroleum-based aromatic-containing oil of the embodiment may have a ratio of polar components determined by the clay gel method of 1% by mass or more and 11% by mass or less, or 2% by mass or more and 10% by mass. % or less, or 3% by mass or more and 9% by mass or less.
The ratio of the above polar components has a conflicting relationship with the above ratios of saturated and aromatic components. Alternatively, the tan δ (50° C.) and tan δ (0° C.) values of the tire become favorable, and both wet grip performance and rolling resistance performance are achieved.

The proportions (% by mass) of saturates, aromatics, and polar components by the Clay-Gel method are determined according to ASTM D2007-11 Standard Test Method for Characteristic Groups in Rubber Extender and Processing Oils and Other Petroleum-Derived Oils by the Clay-Gel Absorption Chromatographic It shall be obtained according to the provisions of Method.

In the petroleum-based aromatic-containing oil of the embodiment, the ratio of bicyclic aromatics fractionated by HPLC is 16% by mass or more, and 17% by mass or more with respect to 100% by mass of the aromatic content. It is preferably 19% by mass or more, and even more preferably 20% by mass or more. In the petroleum-based aromatic-containing oil of the embodiment, the ratio of bicyclic aromatics fractionated by HPLC is 29% by mass or less with respect to 100% by mass of the aromatics, and less than 23% by mass. It is preferably 22% by mass or less, more preferably 22% by mass or less. As an example of the numerical range of the above numerical values, in the petroleum aromatic-containing oil of the embodiment, the ratio of bicyclic aromatics fractionated using HPLC is 16 mass% with respect to 100 mass% of the aromatic content. % or more and 29% by mass or less, 17% by mass or more and less than 23% by mass, 19% by mass or more and 22% by mass or less, or 20% by mass or more and 22% by mass or less. may Here, when the ratio of the bicyclic aromatic group satisfies the above numerical value, the rubber composition or tire containing the oil has preferable tan δ (50° C.) and tan δ (0° C.) values. Both grip performance and rolling resistance performance are achieved.
As can be seen from the data shown in the examples below, the ratio of aromatics having two or more rings among the aromatics greatly contributes to achieving both wet grip performance and rolling resistance performance. Among them, the bicyclic aromatic component has favorable properties from the viewpoint of satisfying the REACH regulations in addition to improving wet grip performance and rolling resistance performance.

In the petroleum-based aromatic-containing oil of the embodiment, the ratio of 1-ring aromatics fractionated using HPLC is preferably 48% by mass or more with respect to 100% by mass of the aromatic content, and 60% by mass. %, more preferably more than 62% by mass. In the petroleum-based aromatic-containing oil of the embodiment, the ratio of 1-ring aromatics fractionated using HPLC is preferably 80% by mass or less with respect to 100% by mass of the aromatic content, and 78% by mass. % or less, more preferably 76% by mass or less. As an example of the numerical range of the above numerical values, in the petroleum aromatic-containing oil of the embodiment, the ratio of 1-ring aromatics fractionated using HPLC is 48 mass% with respect to 100 mass% of the aromatic content. % or more and 80 mass % or less, more than 60 mass % and 78 mass % or less, or more than 62 mass % and 76 mass % or less.
The ratio of the single-ring aromatic component is in conflict with the ratio of the aromatic component having two or more rings. The tan δ (50° C.) and tan δ (0° C.) values of the oil-containing rubber composition or tire are favorable, and both wet grip performance and rolling resistance performance are achieved.

In the petroleum-based aromatic-containing oil of the embodiment, the proportion of aromatics having three or more rings fractionated by HPLC is preferably 4% by mass or more with respect to 100% by mass of the aromatics, It is more preferably 5% by mass or more, and even more preferably 6% by mass or more. In the petroleum-based aromatic-containing oil of the embodiment, the proportion of aromatics having three or more rings fractionated by HPLC is preferably 20% by mass or less with respect to 100% by mass of the aromatics, It is more preferably 18% by mass or less, and even more preferably less than 16% by mass. As an example of the numerical range of the above numerical values, in the petroleum-based aromatic-containing oil of the embodiment, the ratio of aromatics having three or more rings fractionated using HPLC is It may be 4% by mass or more and 20% by mass or less, 5% by mass or more and 18% by mass or less, or 6% by mass or more and less than 16% by mass.
When the ratio of the above three-ring or more aromatic group satisfies the above numerical value, the tan δ (50 ° C.) and tan δ (0 ° C.) values of the rubber composition or tire containing the oil are preferable, and wet Both grip performance and rolling resistance performance can be achieved, and furthermore, it can be made good from the point of satisfying the REACH regulation.

Aromatic fractionation using HPLC shall be obtained under the measurement conditions described in Examples below.

The petroleum-based aromatic-containing oil of the embodiment is
The content of benzo(a)pyrene is 1 mass ppm or less,
The total content of the specific aromatic compounds (PAHs) in 1) to 8) below is 10 mass ppm or less.
1) Benzo(a)pyrene (BaP)
2) Benzo(e)pyrene (BeP)
3) Benzo(a)anthracene (BaA)
4) Chrysene (CHR)
5) benzo(b)fluoranthene (BbFA)
6) benzo(j)fluoranthene (BjFA)
7) Benzo(k)fluoranthene (BkFA)
8) Dibenzo(a,h)anthracene (DBAhA).

Since the content of these benzo (a) pyrene and the above specific aromatic compounds (PAHs) is within the above range, a safer rubber that complies with the regulation of content in extender oil under REACH regulations It can be used as a blended oil.

The content of these compounds can be obtained by separating and concentrating the target component, preparing a sample to which an internal standard substance is added, and quantitatively analyzing it by GC-MS analysis.
The content of benzo(a)pyrene and specific aromatic hydrocarbons (PAHs) is determined according to European Standard EN 16143:2013 Petroleum products - Determination of content of Benzo(a)pyrene (BaP) and selected polycyclic aromatic hydrocarbons (PAH) in extender oils - Shall be determined according to the provisions of Procedure using double LC cleaning and GC/MS analysis.

The petroleum-based aromatic-containing oil of the embodiment preferably has a kinematic viscosity at 100° C. of 8 mm ² /s or more, more preferably 10 mm ² /s or more, and 14 mm ² /s or more. More preferred. The petroleum-based aromatic-containing oil of the embodiment preferably has a kinematic viscosity at 100° C. of less than 25 mm ² /s, more preferably 23 mm ² /s or less, and preferably 22 mm ² /s or less. More preferred. As an example of the numerical range of the above numerical values, the petroleum-based aromatic-containing oil of the embodiment may have a kinematic viscosity at 100° C. of 8 mm ² /s or more and less than 25 mm ² /s, or 10 mm ² /s It may be in the range of 23 mm ² /s to 23 mm 2 /s or 14 mm ² /s to 22 mm ² /s. When the kinematic viscosity value satisfies the above numerical value, the viscosity of the rubber composition or tire containing the petroleum aromatic-containing oil is preferable, so tan δ (50 ° C.) and tan δ (0 ° C.) is more preferable, and the compatibility between wet grip performance and rolling resistance performance is even more preferable. Furthermore, when the kinematic viscosity is equal to or less than the upper limit, the transfer and workability for blending the petroleum aromatic-containing oil into rubber will be good.

Kinematic viscosity at 100° C. shall be obtained according to the provisions of JIS K2283:2000.

The petroleum-based aromatic-containing oil of the embodiment preferably has an aniline point of 52° C. or higher, more preferably 56° C. or higher, and even more preferably 60° C. or higher. The petroleum-based aromatic-containing oil of the embodiment preferably has an aniline point of 95° C. or lower, more preferably 92° C. or lower, even more preferably 88° C. or lower, and 84° C. or lower. Especially preferred. As an example of the numerical range of the above numerical values, the petroleum-based aromatic-containing oil of the embodiment may have an aniline point in the range of 52 ° C. or higher and 95 ° C. or lower, or in the range of 52 ° C. or higher and 92 ° C. or lower. It may be in the range of 56° C. or higher and 88° C. or lower, or in the range of 60° C. or higher and 84° C. or lower. The aniline point is the temperature at which equal amounts of aniline and oil are mixed, and is an index of rubber compatibility. If the aniline point is equal to or lower than the above upper limit, the oil and aniline will melt together without excessive heating, and rubber compatibility is high, which is preferable. That is, when the aniline point value satisfies the above numerical value, the petroleum aromatic-containing oil has a good affinity for rubber, and the physical properties of the produced rubber composition or tire can be further improved. .

The aniline point shall be determined according to the provisions of ASTM D611-12 Standard Test Methods for Aniline Point and Mixed Aniline Point of Petroleum Products and Hydrocarbon Solvents.

The petroleum-based aromatic-containing oil of the embodiment preferably has a glass transition point (Tg) of −60° C. or higher, more preferably −56° C. or higher, and even more preferably −54° C. or higher. . The petroleum-based aromatic-containing oil of the embodiment preferably has a glass transition point (Tg) of −34° C. or lower, more preferably −36° C. or lower, and even more preferably −38° C. or lower. . As an example of the numerical range of the above numerical values, the petroleum-based aromatic-containing oil of the embodiment may have a glass transition point (Tg) in the range of -60 ° C. or higher and -34 ° C. or lower, and -56 ° C. or higher - It may be in the range of 36°C or lower, or in the range of -54°C or higher and -38°C or lower. If the glass transition point satisfies the above numerical value, the physical properties of the rubber composition or tire to be produced can be made more favorable, which is important for improving wet grip performance and rolling resistance performance.

The glass transition point is obtained under the measurement conditions described in Examples below.

The petroleum-based aromatic-containing oil of the embodiment preferably has a viscosity specific gravity constant (VGC) of 0.85 or more, more preferably 0.86 or more, and even more preferably 0.87 or more. . The petroleum-based aromatic-containing oil of the embodiment preferably has a viscosity specific gravity constant (VGC) of 0.92 or less, more preferably 0.91 or less, and even more preferably 0.90 or less. . As an example of the numerical range of the above numerical values, the petroleum aromatic-containing oil of the embodiment may have a viscosity specific gravity constant (VGC) of 0.85 or more and 0.92 or less, or 0.86 or more and 0.91 It may be less than or equal to 0.87 or more and 0.90 or less. The viscosity-specific gravity constant is an index that expresses the composition of the oil. In general, the higher the paraffinicity, the lower the value, and the higher the aromaticity, the higher the value. If the value of the viscosity specific gravity constant satisfies the above value, the physical properties of the rubber composition or tire containing the petroleum aromatic-containing oil will be preferable, so tan δ (50 ° C.) and tan δ (0 °C) becomes even more preferable, and the compatibility between wet grip performance and rolling resistance performance becomes even more preferable.

The viscosity specific gravity constant (VGC) shall be determined according to the provisions of ASTM D2140-08 Standard Practice for Calculating Carbon-Type Composition of Insulating Oils of Petroleum Origin.

The petroleum-based aromatic-containing oil of the embodiment preferably has a %CA of 8 or more, more preferably 9 or more, and even more preferably 10 or more, by ring analysis. The petroleum-based aromatic-containing oil of the embodiment preferably has a % CA of 28 or less, more preferably 26 or less, and even more preferably 24 or less by ring analysis. As an example of the numerical range of the above numerical values, the petroleum aromatic-containing oil of the embodiment may have a % CA of 8 or more and 28 or less by ring analysis, may be 9 or more and 26 or less, or may be 10 or more and 24 It may be below.
When the above % CA satisfies the above numerical value, the amount of highly carcinogenic polycyclic aromatics is suppressed, and at the same time, the oil tends to have an aromatic property that improves compatibility with rubber. The tan δ (50° C.) and tan δ (0° C.) values of the rubber composition or tire to be contained are favorable, and the compatibility between wet grip performance and rolling resistance performance is even more favorable.

%CA shall be determined according to the provisions of ASTM D2140-08 Standard Practice for Calculating Carbon-Type Composition of Insulating Oils of Petroleum Origin.

The petroleum-based aromatic-containing oil of the embodiment is suitably used as an extender oil or process oil mixed with rubber.

[Method for producing petroleum-based aromatic-containing oil]
Hereinafter, a method for producing a petroleum-based aromatic-containing oil according to an embodiment will be described. According to this method, the petroleum-based aromatic-containing oil of the present invention can be produced. In addition, the petroleum-based aromatic-containing oil of the present invention is not limited to one produced by the method for producing a petroleum-based aromatic-containing oil according to the following embodiment.

The method for producing a petroleum-based aromatic-containing oil according to an embodiment includes:
A step of obtaining an extract obtained by further solvent-extracting the raffinate obtained by solvent extraction, or
A step of obtaining a raffinate obtained by further solvent-extracting the extract obtained by solvent extraction, or
An extract obtained by further solvent-extracting the raffinate obtained by solvent extraction and a raffinate obtained by further solvent-extracting the raffinate obtained by solvent extraction or a base oil refined from the raffinate is mixed. and the step of
A substance to be subjected to solvent extraction includes a vacuum distillation fraction obtained by vacuum-distilling a residue obtained by atmospheric distillation of crude oil. In solvent extraction, an extract is obtained by extracting a target object of solvent extraction with a solvent having an affinity for aromatic hydrocarbons, and separating and recovering the solvent and the extract. Various crude oils such as paraffinic crude oil and naphthenic crude oil can be used as the starting raw material, either singly or in combination. Paraffinic crude oil is particularly preferred.

Hereinafter, an extract obtained by further solvent-extracting the raffinate obtained by solvent extraction, a raffinate obtained by further solvent-extracting the raffinate obtained by solvent extraction, or a base oil refined from the raffinate will be described.
FIG. 1 is a process diagram illustrating an example of a method for producing a petroleum-based aromatic-containing oil according to an embodiment. Crude oil is first processed in an atmospheric distillation unit (not shown) to obtain an atmospheric distillation residue. The atmospheric distillation residue is sent to a vacuum distillation apparatus 10 and vacuum-distilled to obtain a vacuum distillation fraction 11 . The vacuum distillation fraction 11 is sent to the first solvent extraction unit 30a. In the first solvent extraction unit 30a, the vacuum distillation fraction 11 is separated into a raffinate 31a and an extract 33a. The separated raffinate 31a is sent to the second solvent extraction device 30b. The second solvent extractor 30b separates the raffinate 31a into a raffinate 31b and an extract 33b. The raffinate 31b is hydrorefined in a hydrorefining unit 40 to obtain a hydrorefined oil 41, and further dewaxed in a dewaxing unit 50 to obtain a dewaxed oil 51. The obtained dewaxed oil 51 and the extract 33b can be mixed to obtain the petroleum aromatic-containing oil 62.

Here, the case of obtaining the petroleum aromatic-containing oil 62 by mixing the dewaxed oil 51 and the extract 33b has been described, but instead of the dewaxed oil 51, the raffinate 31b or the hydrorefined oil 41 is used. , may be mixed with the extract 33b.

Also, the extract 33b may be the petroleum-based aromatic-containing oil 62 .

Although not shown, the raffinate obtained by further solvent-extracting the extract 33a may be used as the petroleum-based aromatic-containing oil.

Vacuum distillation is carried out under conditions where the end point of the distillate is 580°C or higher in terms of normal pressure or under conditions where the initial boiling point of the residue is 450°C or higher. It is preferable because it can be easily adjusted within the range of .
In order to obtain the extracts 33a and 33b, the solvent extraction is preferably performed with a solvent having selective affinity for aromatic hydrocarbons. The solvent having selective affinity for aromatic hydrocarbons may be a polar solvent and one or more selected from the group consisting of furfural, phenol and N-methyl-2-pyrrolidone can be used. . The specific extraction conditions for making the extract yield within the above range depend on the composition of the deasphalted oil, so it cannot be determined unambiguously, but it is possible by appropriately selecting the solvent ratio, pressure, temperature, etc. is. In general, tower top temperature: preferably 100 to 155° C., more preferably 100 to 140° C., tower bottom temperature: preferably 40 to 120° C., more preferably 50 to 110° C., ratio of solvent to oil 1: preferably is 1 to 5, more preferably 1.5 to 4.5.
On the other hand, in the solvent extraction, in order to obtain the raffinates 31a and 31b, it is preferable to perform a solvent refining process in which extraction is performed with a solvent having an affinity for aromatic hydrocarbons. One or more of furfural, phenol and N-methyl-2-pyrrolidone can be used as the solvent with selective affinity for aromatic hydrocarbons. In this solvent refining step, the conditions for refining a normal lubricating base oil, for example, when furfural is used as an extraction solvent, the top temperature: preferably 60 to 150 ° C., more preferably 70 to 140 ° C., the bottom temperature : preferably 40 to 90°C, more preferably 50 to 80°C, solvent to oil ratio: preferably 0.5 to 4, more preferably 1 to 3.
Further, if desired, the raffinate is dewaxed by hydrorefining and/or solvent dewaxing or hydrodewaxing treatment to obtain a more preferable base oil. The hydrorefining is carried out in the presence of a catalyst in which one or more active metals such as nickel, cobalt, and molybdenum are supported on a carrier such as alumina or silica-alumina, at a hydrogen pressure of 5 to 15 MPa, a temperature of 250 to 400 ° C., It is preferable to carry out under the conditions of a liquid hourly space velocity (LHSV) of 1 to 5 h ^-1 . In addition, the solvent dewaxing is preferably performed, for example, in a mixed solvent of methyl ethyl ketone/toluene at a solvent/oil ratio (volume ratio) of 1/1 to 5/1 at a temperature of -10 to -40°C. Hydrodewaxing is preferably carried out in the presence of a zeolite catalyst under conditions of a hydrogen pressure of 5 to 15 MPa, a temperature of 300 to 400° C. and an LHSV of 1 to 5 Hr−1.
Hydrorefining removes impurities, such as sulfur and nitrogen, that adversely affect the use and storage of process oil as hydrogenated light reactants by contacting feedstock oil with high-temperature, high-pressure hydrogen in the presence of a catalyst. As a result, the stability and hue can be improved. Solvent dewaxing is carried out by mixing one or more solvents selected from the group consisting of acetone, methyl ethyl ketone, benzene, and toluene with the feedstock oil, followed by a cooling process to precipitate wax fractions including normal paraffin. It is possible to improve the low-temperature fluidity by separating and removing this by filtering it with a filter.
The petroleum-based aromatic-containing oil of the embodiment can be produced by extracting the raffinate obtained as described above with a solvent.
Alternatively, the petroleum-based aromatic-containing oil of the embodiment can be produced from a raffinate obtained by further solvent-extracting the extract obtained as described above.
Alternatively, the oil of the embodiment is obtained by mixing the extract obtained as described above and the base oil in a mass ratio of 95/5 to 5/95, particularly preferably 80/20 to 20/80. Aromatic-containing oils can be produced.

<<Rubber composition>>
The rubber composition of the embodiment will be described below. In addition, the rubber composition of the present invention is not limited to the following rubber composition.
FIG. 2 is a process diagram illustrating an example of the process of preparing a tire composition from raw rubber. A tire composition, which is a raw material of a tire, contains raw rubber and various compounding agents. Synthetic rubber may be blended with extender oil during its synthesis, and a rubber composition containing extender oil in advance (also referred to as oil-extended rubber) may be used as the raw material rubber (Fig. 2 (a )reference). Alternatively, raw rubber containing no extender oil (also referred to as non-oil-extended rubber) may be used (see FIG. 2(b)). Process oil and various compounding agents are added to the raw rubber (see FIGS. 2(a) and 2(b)).
The raw rubber (rubber composition), which is an oil-extended rubber, can be obtained by subjecting monomers to a polymerization reaction, and can be produced by adding an extender oil in the process. For example, a method of subjecting a reaction liquid containing a monomer that is a rubber raw material of a raw rubber and an extender oil to a polymerization reaction, or a method of subjecting a reaction liquid containing a monomer that is a rubber raw material of a raw rubber to a polymerization reaction, An oil-extended rubber can be produced by adding an extender oil to a polymer solution (Fig. 2(a)).
The tire composition (rubber composition) is prepared by kneading the raw rubber, the petroleum-based aromatic-containing oil according to the present invention, and the compounding agent using, for example, a known rubber kneader such as a roll, a mixer, or a kneader. , can be manufactured. The tire composition can be vulcanized under any conditions.
In the present specification, a rubber composition containing raw rubber and the petroleum-based aromatic-containing oil (extender oil or process oil) of the embodiment is referred to as a rubber composition.
The rubber composition of the embodiment is suitable as a rubber composition for tires used for manufacturing tires. As one embodiment, the present invention provides a tire composition containing raw rubber, the petroleum aromatic-containing oil according to the present invention, and a compounding agent. A tire composition is a concept included in the rubber composition of the embodiment. The tire composition (rubber composition) may be vulcanized or unvulcanized.
In addition, although expressions are divided into extender oil and process oil here, these are sometimes collectively referred to as process oil.

Compositions of the rubber composition and the tire composition are described below.

As raw material rubber, elastomeric polymers can be used, such as natural rubber, isoprene rubber, butadiene rubber, 1,2-butadiene rubber, styrene-butadiene rubber, isoprene-butadiene rubber, styrene-isoprene-butadiene rubber, ethylene. - Diene rubbers such as propylene-diene rubber, halogenated butyl rubber, halogenated isoprene rubber, halogenated isobutylene copolymer, chloroprene rubber, butyl rubber and halogenated isobutylene-p-methylstyrene rubber, nitrile rubber, chloroprene rubber, butyl rubber, ethylene-propylene rubber (EPDM, EPM), ethylene-butene rubber (BBM), chlorosulfonated polyethylene, acrylic rubber, olefin rubber such as fluororubber, epichlorohydrin rubber, polysulfide rubber, silicone rubber, urethane rubber, etc. polystyrene elastomeric polymers (SBS, SIS, SEBS), polyolefin elastomeric polymers, polyvinyl chloride elastomeric polymers, polyurethane elastomeric polymers, polyester elastomeric polymers or A thermoplastic elastomer such as a polyamide-based elastomeric polymer may also be used. In addition, these can be used individually or as arbitrary blends.
From the viewpoint of compatibility with petroleum aromatic-containing oils, the elastomeric polymer is selected from the group consisting of natural rubber, isoprene rubber, styrene-butadiene rubber, butadiene rubber, butyl rubber, chloroprene rubber, and acrylonitrile rubber. At least one kind is preferable. Furthermore, from the viewpoint that it can be suitably used in the tread portion that exhibits rolling resistance performance and wet grip performance as tire performance, the elastomeric polymer is a group consisting of natural rubber, isoprene rubber, styrene-butadiene rubber, and butadiene rubber. It is preferably at least one selected from

As the extender oil or process oil, the petroleum-based aromatic-containing oil according to the embodiment can be used.

Compounding agents include fillers, anti-aging agents, antioxidants, cross-linking agents (vulcanizing agents), cross-linking accelerators, resins, plasticizers, vulcanization accelerators, vulcanization accelerator aids (vulcanization aids), etc. is mentioned.

Examples of fillers include carbon black, silica, and silane compounds (silane coupling agents), with silica and/or silane coupling agents being preferred.
Carbon black is classified into hard carbon and soft carbon based on particle size. Soft carbon has a low reinforcing property against rubber, and hard carbon has a strong reinforcing property against rubber. When the rubber composition of the embodiment contains carbon black, it is preferable to use hard carbon, which has particularly strong reinforcing properties. Carbon black is preferably blended in an amount of 10 to 250 parts by mass, more preferably 20 to 200 parts by mass, and 30 to 50 parts by mass with respect to 100 parts by mass of the elastomeric polymer. is more preferred.
Examples of silica include, but are not particularly limited to, dry process white carbon, wet process white carbon, colloidal silica, and precipitated silica. Among these, wet process white carbon containing hydrous silicic acid as a main component is preferable. These silicas can be used alone or in combination of two or more. The specific surface area of these silicas is not particularly limited, but the nitrogen adsorption specific surface area (BET method) is usually in the range of 10 to 400 m ² /g, preferably 20 to 300 m ² /g, more preferably 120 to 190 m ² /g. In some cases, it is suitable for improving reinforcement, wear resistance and heat build-up. Here, the nitrogen adsorption specific surface area is a value measured by the BET method according to ASTM D3037-81.
Although the silane compound is not particularly limited, a sulfur-containing silane coupling agent is preferable, and bis(3-triethoxysilylpropyl)disulfide is more preferable.

Examples of cross-linking agents (vulcanizing agents) include powdered sulfur, precipitated sulfur, highly dispersible sulfur, surface-treated sulfur, and insoluble sulfur.

Examples of vulcanization accelerators include thiuram-based agents such as tetramethylthiuram disulfide (TMTD) and tetraethylthiuram disulfide (TETD), aldehyde/ammonia-based agents such as hexamethylenetetramine, guanidine-based agents such as diphenylguanidine, and dibenzothiazyldisulfide (DM ), and cyclohexylbenzothiazylsulfenamides such as N-cyclohexyl-2-benzothiazolylsulfenamide.

Auxiliary vulcanization accelerators include fatty acids such as acetyl acid, propionic acid, butanoic acid, stearic acid, acrylic acid, and maleic acid, zinc acetylate, zinc propionate, zinc butanoate, zinc stearate, zinc acrylate, and malein. Fatty acid zinc such as acid zinc, zinc white and the like can be mentioned.

The blending amounts of the raw rubber, the petroleum-based aromatic-containing oil according to the present invention, and the compounding agent may be general blending amounts as long as they do not contradict the object of the present invention.

As an example, with respect to 100 parts by mass of the elastomeric polymer, filler: 30 to 100 parts by mass, petroleum aromatic-containing oil: 80 parts by mass or less, antioxidant: 0.5 to 5 parts by mass, cross-linking agent: 1 Up to 10 parts by mass, resin: 0 to 20 parts by mass, vulcanization accelerator: 0.5 to 5 parts by mass, vulcanization accelerator aid: 1 to 10 parts by mass.
When silica and/or a silane coupling agent is used as a filler, the silica and/or the silane coupling agent is preferably blended in an amount of 10 to 300 parts by mass with respect to 100 parts by mass of the elastomeric polymer. More preferably 50 to 150 parts by mass, more preferably 70 to 100 parts by mass. The content of the silane compound (silane coupling agent) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the elastomeric polymer.
The petroleum-based aromatic-containing oil is preferably blended in an amount of 0.5 to 80 parts by mass, more preferably 10 to 50 parts by mass, and 20 to 40 parts by mass with respect to 100 parts by mass of the elastomeric polymer. It is more preferable that it is blended in parts by mass.

According to the rubber composition of the embodiment, it is possible to provide a rubber composition excellent in rolling resistance performance and wet grip performance.

<<Manufacturing method of tires and tires>>
A tire of an embodiment contains the petroleum-based aromatic-containing oil according to the above embodiment.
The tire of the embodiment can be produced by blending and vulcanizing the rubber and the petroleum-based aromatic-containing oil of the embodiment.
In other words, the tire of the embodiment may contain the above tire composition (rubber composition) and can be produced by vulcanizing the tire composition. Specifically, for example, the tire composition can be vulcanized to produce a tire. More specifically, for example, the tire composition is heated and melted, the heated and melted tire composition is extruded, then molded using a tire molding machine, and then heated and pressurized using a vulcanizer. , can manufacture tires.

A tire, for example, is composed of tire parts such as a tread, carcass, sidewall, inner liner, undertread, and belt. The tire of the embodiment preferably contains the petroleum-based aromatic-containing oil according to the above embodiment in the tread portion. The tire of the embodiment preferably has a tire tread made of the tire composition of the embodiment. By containing the petroleum-based aromatic-containing oil in the tread portion, which serves as a contact surface, rolling resistance performance and wet grip performance are preferably exhibited.

According to the tire and tire manufacturing method of the embodiment, it is possible to provide a tire excellent in rolling resistance performance and wet grip performance.

The reason why the petroleum-based aromatic-containing oil of the embodiment is effective in achieving both wet grip performance and rolling resistance performance of the tire composition (rubber composition) is presumed as follows.
Since the two performances are mutually exclusive, if one can be improved without impairing the other, both can be achieved as a result. Normally, what is called a fuel-saving tire is combined with silica to achieve both, especially fuel-saving performance. It tends to clump together. In that case, when the tire is deformed during running, the silica rubs against each other and generates heat, resulting in unnecessary energy loss. Therefore, the point is how to disperse silica in the rubber polymer. The petroleum-based aromatic-containing oil containing the above-mentioned specific components in specific amounts acts on the dispersion and dissolution of various compounding agents including silica, and their behavior in rubber polymers has a favorable effect on each physical property, resulting in As such, it is considered to lead to compatibility of contradictory performance.

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

1. Manufacture of process oil

<Example 1-1>
The naphthenic crude oil is subjected to an atmospheric distillation apparatus, the obtained atmospheric distillation residue is subjected to a vacuum distillation apparatus, and the obtained vacuum distillation fraction equivalent to 500N is subjected to the first furfural extraction apparatus (operating conditions: tower top temperature 70 ~ 100 ° C., tower bottom temperature 40 to 70 ° C., solvent ratio adjusted in the range of 1.0 to 2.0), and the obtained raffinate fraction is subjected to the second furfural extraction device (operating conditions: tower top temperature 100 to 130° C., bottom temperature of 70 to 90° C., solvent ratio of ^2.0 to 3.0; The resulting extract fraction was used as the process oil of Example 1.

<Example 2-1>
The Middle East crude oil is subjected to an atmospheric distillation apparatus, the obtained atmospheric distillation residue is subjected to a vacuum distillation apparatus, and the obtained vacuum distillation fraction equivalent to 500N is subjected to the first furfural extraction apparatus (operating conditions: tower top temperature 100 ~ 130 ° C., tower bottom temperature 70 to 100 ° C., solvent ratio adjusted in the range of 1.6 to 3.0), and the obtained extract fraction is subjected to the second furfural extraction device (operating conditions: tower top temperature 70 ~ 100 ° C., bottom temperature 40 to 70 ° C., solvent ratio ^1.0 to 2.0. The raffinate fraction was used as the process oil of Example 2.

<Example 3-1>
The Middle East crude oil is subjected to an atmospheric distillation apparatus, the obtained atmospheric distillation residue is subjected to a vacuum distillation apparatus, and the obtained vacuum distillation fraction equivalent to 350N is subjected to the first furfural extraction apparatus (operating conditions: tower top temperature 80 ~ 100 ° C., tower bottom temperature 50 to 70 ° C., solvent ratio adjusted in the range of 1.0 to 1.5), and the obtained raffinate fraction is subjected to the second furfural extraction device (operating conditions: tower top temperature 105 to 125° C., bottom temperature 75 to 95° C., solvent ratio adjusted in the range of 2.0 to 3.0), and the resulting extract fraction was designated as extract (M).
The Middle East crude oil is subjected to an atmospheric distillation apparatus, the obtained atmospheric distillation residue is subjected to a vacuum distillation apparatus, and the obtained vacuum distillation fraction equivalent to 900N is subjected to the first furfural extraction apparatus (operating conditions: tower top temperature 80 ~ 100 ° C., tower bottom temperature 50 to 70 ° C., solvent ratio adjusted in the range of 0.8 to 1.4), and the obtained raffinate fraction is subjected to the second furfural extraction device (operating conditions: tower top temperature 110 to 130° C., bottom temperature of 80 to 100° C., solvent ratio adjusted in the range of 2.0 to 3.0), and the resulting extract fraction was designated as extract (N).
The Middle East crude oil is subjected to an atmospheric distillation apparatus, the obtained atmospheric distillation residue is subjected to a vacuum distillation apparatus, and the obtained vacuum distillation fraction equivalent to 900N is subjected to a furfural extraction apparatus (operating conditions: tower top temperature 105 to 125 ° C., The bottom temperature is 65 to 85 ° C., the solvent ratio is adjusted in the range of 1.0 to 3.0), and the obtained raffinate fraction is hydrorefined (operating conditions: using a noble metal catalyst, the liquid hourly space velocity 1.0 to 2.0 h ⁻¹ , reaction temperature 270 to 330° C., hydrogen oil ratio 1400 to 2800 NL/L, hydrogen partial pressure 4.0 to 6.0 MPa), and obtained hydrorefining Solvent dewaxing equipment for oil (operating conditions: mixed solvent of methyl ethyl ketone and toluene, primary solvent ratio 0.7 to 2.0, secondary solvent ratio 0.7 to 2.0, dewaxing temperature -15 to -25 ° C The dewaxed oil obtained was used as the dewaxed oil (O).
Extract (M)/Extract (N)/Dewaxed oil (O) were mixed in a weight ratio of 25/50/25 to obtain the process oil of Example 3.

<Example 4-1>
The Middle East crude oil is subjected to an atmospheric distillation apparatus, the obtained atmospheric distillation residue is subjected to a vacuum distillation apparatus, and the obtained vacuum distillation residue is compressed and liquefied. ° C., bottom temperature of 45 to 75 ° C., solvent ratio adjusted in the range of 1.0 to 4.0), and the obtained deasphalted oil is subjected to a furfural extraction device (operating conditions: top temperature of 110 to 130 ° C., tower The bottom temperature was adjusted to 60 to 80° C. and the solvent ratio was adjusted to 3.0 to 4.0), and the obtained extract fraction was designated as extract (E).
The above extract (E)/dewaxed oil (F) described below were mixed at a weight ratio of 40/60 to obtain the process oil of Example 4.

<Comparative Example 1-1>
The Middle East crude oil is subjected to an atmospheric distillation apparatus, the obtained atmospheric distillation residue is subjected to a vacuum distillation apparatus, and the obtained vacuum distillation fraction equivalent to 500N is subjected to a furfural extraction apparatus (operating conditions: column top temperature 100 to 130 ° C., The bottom temperature is 50 to 80 ° C., the solvent ratio is adjusted in the range of 1.0 to 3.0), and the obtained raffinate fraction is hydrorefined (operating conditions: using a noble metal catalyst, liquid hourly space velocity 1.0 to 3.0 h ⁻¹ , reaction temperature of 280 to 340° C., hydrogen oil ratio of 1500 to 2500 NL/L, and hydrogen partial pressure of 6.0 to 10.0 MPa). Solvent dewaxing equipment for oil (operating conditions: mixed solvent of methyl ethyl ketone and toluene, primary solvent ratio 1.0 to 2.0, secondary solvent ratio 0.5 to 1.4, dewaxing temperature -15 to -25 ° C The dewaxed oil obtained was used as the dewaxed oil (G).
The Middle East crude oil was subjected to an atmospheric distillation apparatus, the obtained atmospheric distillation residue was subjected to a vacuum distillation apparatus, and the obtained vacuum distillation residue was used as a vacuum distillation residue (H).
Naphthenic crude oil is supplied to an atmospheric distillation unit, the obtained atmospheric distillation residue is supplied to a vacuum distillation unit, and the obtained vacuum distillation fraction equivalent to 1000N is subjected to a hydrorefining unit (operating conditions: using a noble metal catalyst, Liquid hourly space velocity 1.0 to 3.0 h ^-1 , reaction temperature 270 ° C to 340 ° C, hydrogen oil ratio 1400 to 2800 NL / L, hydrogen partial pressure 3.0 to 9.0 MPa), obtained The obtained hydrorefined oil was designated as hydrorefined oil (I).
Naphthenic crude oil was subjected to an atmospheric distillation apparatus, the obtained atmospheric distillation residue was subjected to a vacuum distillation apparatus, and the obtained vacuum distillation residue was used as a vacuum distillation residue (J).
The dewaxed oil (G)/vacuum distillation residue (H) is mixed at a weight ratio of 50/50, and the hydrorefined oil (I)/vacuum distillation residue (J) is mixed at a weight ratio of 50/50. were mixed so that the kinematic viscosity at 100° C. was about 30 mm ² /s, and a process oil of Comparative Example 1 was obtained.

<Comparative Example 2-1>
Naphthenic crude oil is supplied to an atmospheric distillation unit, the obtained atmospheric distillation residue is supplied to a vacuum distillation unit, and the obtained vacuum distillation fraction equivalent to 2000N is subjected to a hydrorefining unit (operating conditions: using a noble metal catalyst, Liquid hourly space velocity 1.0 to 3.0 h ^-1 , reaction temperature 270 ° C to 340 ° C, hydrogen oil ratio 1400 to 2800 NL / L, hydrogen partial pressure 3.0 to 9.0 MPa), obtained The resulting hydrorefined oil was used as the process oil of Comparative Example 2.

<Comparative Example 3-1>
The Middle East crude oil is subjected to an atmospheric distillation apparatus, the obtained atmospheric distillation residue is subjected to a vacuum distillation apparatus, and the obtained vacuum distillation fraction equivalent to 500N is subjected to a furfural extraction apparatus (operating conditions: tower top temperature 105 to 125 ° C., The bottom temperature is 55 to 75 ° C., the solvent ratio is adjusted in the range of 1.2 to 2.8), and the obtained raffinate fraction is subjected to a hydrorefining unit (operating conditions: using a noble metal catalyst, liquid hourly space velocity 2.0 to 3.0 h ⁻¹ , reaction temperature 310 to 360° C., hydrogen oil ratio 1500 to 2500 NL/L, hydrogen partial pressure 8.5 to 12.0 MPa), and obtained hydrorefining Solvent dewaxing equipment for oil (operating conditions: mixed solvent of methyl ethyl ketone and toluene, primary solvent ratio 1.0 to 2.0, secondary solvent ratio 0.5 to 1.4, dewaxing temperature -15 to -25 ° C The dewaxed oil obtained was used as the dewaxed oil (F). The dewaxed oil (F) was used as the process oil of Comparative Example 3.

<Comparative Example 4-1>
The extract (E)/dewaxed oil (F) were mixed at a weight ratio of 80/20 to obtain a process oil of Comparative Example 4.

2. Measurement of Properties of Process Oil Using the process oils obtained in the above Examples and Comparative Examples as samples, the following items were measured.

[Clay gel method]
Clay-gel method (Clay-gel column chromatography): ASTM D2007-11 Standard Test Method for Characteristic Groups in Rubber Extender and Processing Oils and Other Petroleum-Derived Oils by the Clay-Gel Absorption Chromatographic Method, aromatic content, saturate content, polar component (% by mass) was obtained.

[Aromatic fractionation using HPLC]
Aromatic fractionation using HPLC (high pressure liquid chromatography) is described in "Separation of aromatic and polar compounds in fossil fuel liquids by Liquid Chromatography” was used as a reference, and the procedure was as follows.
Pretreatment was performed by diluting the sample 5-fold with hexane. A Waters Spherisorb A5Y 250×4.6 mm column was used, the flow rate was 2.5 mL/min, a UV detector was used as the detector, and measurements were made at a wavelength of 270 nm. As the eluent, hexane is used from 0 to 10.0 minutes after sample introduction, and from 100% by mass of hexane to a mixed solution of 40% by mass of dichloromethane and 60% by mass of hexane from 10.0 to 30.0 minutes. Dichloromethane content increased linearly. A mixed solution of 40% by mass of dichloromethane and 60% by mass of hexane was changed to 100% by mass of dichloromethane during the time from 30.0 to 30.1 minutes after sample introduction, and 100% by mass of dichloromethane was used after 30.1 minutes. board.
From the obtained peak area, the aromatic hydrocarbon content (% by mass) for each ring was determined according to the following formula. Here, the 1 ring area is the sum of the peak areas from the benzene peak to the peak immediately preceding naphthalene, the 2 ring area is the sum of the peak areas from the naphthalene peak to the peak immediately preceding anthracene, and , the three or more ring area is the sum of the peak areas after the anthracene peak.
1 ring aromatic content (mass%) = (1 ring area / (1 ring area + 0.1 x 2 ring areas + 0.025 x 3 or more ring areas)) x 100;
2-ring aromatic content (% by mass) = (0.1 x 2 ring areas/(1 ring area + 0.1 x 2 ring areas + 0.025 x 3 or more ring areas)) x 100;
Aromatic content of 3 or more rings (% by mass) = (0.025 x 3 ring areas/(1 ring area + 0.1 x 2 ring areas + 0.025 x 3 or more ring areas)) x 100

[Kinematic viscosity (100°C)]
Measured according to JIS K2283:2000.

[Aniline point]
Measured in accordance with ASTM D611-12 Standard Test Methods for Aniline Point and Mixed Aniline Point of Petroleum Products and Hydrocarbon Solvents.

[Glass transition point (Tg)]
The glass transition point was obtained from the calorie change peak in the glass transition region measured when the temperature was raised at a constant heating rate with a DSC (differential scanning calorimeter). The initial temperature was usually about 30° C. to 50° C. or lower than the expected glass transition point, and after the initial temperature was maintained for a certain period of time, the temperature was started to rise. Specifically, it was measured under the following conditions.
Apparatus: DSC7020 manufactured by Hitachi High-Tech Science
Initial temperature: −90° C., held for 10 minutes Heating rate: 10° C./min End temperature: 30° C., held for 5 minutes

[Viscosity specific gravity constant (VGC)]
Measured in accordance with ASTM D2140-08 Standard Practice for Calculating Carbon-Type Composition of Insulating Oils of Petroleum Origin.

[%CA]
Measured in accordance with ASTM D2140-08 Standard Practice for Calculating Carbon-Type Composition of Insulating Oils of Petroleum Origin.

[Contents of benzo (a) pyrene and specific aromatic compounds (PAHs)]
European Standard EN 16143: 2013 Petroleum products - Determination of content of Benzo(a)pyrene (BaP) and selected polycyclic aromatic hydrocarbons (PAH) in extender oils - Procedure using double LC cleaning and GC/MS analysis.
In addition, PAHs are shown below.
1) Benzo(a)pyrene (BaP)
2) Benzo(e)pyrene (BeP)
3) Benzo(a)anthracene (BaA)
4) Chrysene (CHR)
5) benzo(b)fluoranthene (BbFA)
6) benzo(j)fluoranthene (BjFA)
7) Benzo(k)fluoranthene (BkFA)
8) Dibenzo(a,h)anthracene (DBAhA)

3. Production of rubber composition <Example 1-2 to Example 4-2>
The rubber polymer, the process oil produced in Examples 1-1 to 4-1 above, and other compounding agents (silica, silane coupling agent, anti-aging agent, vulcanizing aid, zinc oxide, sulfur, vulcanizing agent, A vulcanization accelerator) was prepared according to the following formulation and kneaded to obtain an unvulcanized rubber composition, which was press-vulcanized at 160°C.

<Comparative Examples 1-2 to 4-2>
The rubber polymer, the process oils produced in Comparative Examples 1-1 to 4-1 above, and other compounding agents (same as above) were prepared according to the following formulations, and then kneaded to form an unvulcanized product. After the rubber composition was obtained, it was press-vulcanized at 160°C.

The formulation of the tire composition is shown in Table 1 below. phr in the table represents parts by mass of various compounding agents with respect to 100 parts by mass of the rubber polymer.

・Rubber polymer (SBR): LANXESS BunaVSL4526
・Silica: Evonik ULTRASIL7000GR
・Silane coupling agent: Evonik Si75
・Anti-aging agent: Nocrac 6C manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.
・Vulcanizing aid: NOF stearic acid ・Zinc oxide: Toho Zinc zinc oxide No. 3 ・Process oil: Each process oil produced in Examples and Comparative examples ・Sulfur: Commercial vulcanizing sulfur ・Vulcanization accelerator A: Noxeller cz manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.
・Vulcanization accelerator B: Noxcella d manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.

Rubber kneading method: Two-stage kneading as shown below.
(first stage)
・Testing machine: Laboplastomill B-600 manufactured by Toyo Seiki Seisakusho
・Testing machine capacity: 600cc
・Filling rate: 70% (mass ratio)
・Number of revolutions: 100rpm
・Temperature: Start at 100℃ and set the upper limit to 155℃ ・Kneading time: About 9 minutes (second stage)
・Testing machine: Electric heating high temperature roll machine manufactured by Ikeda Kikai Kogyo Co., Ltd. ・Size: 6 inches φ x 16 inches ・Number of rotations: Front roll 25 rpm
・Rotation ratio: Front-to-rear ratio 1:1.22
・Temperature: 23±10℃

4. Measurement of Physical Properties of Rubber Composition Test pieces of 8 mmφ×10 mm were prepared from rubber kneaded pieces after press vulcanization molding in the above examples and comparative examples, and the following items were measured on the test pieces.

[tan δ (0°C)]
Using a viscoelasticity measuring device ARES manufactured by TAINSTRUMENTS, measurement was performed in torsion mode at a frequency of 10 Hz, a measurement temperature range of -50°C to 100°C, a heating rate of 2°C/min, and a dynamic strain of 0.1%. The value at 0°C was extracted from the obtained temperature variable tan δ.
Tan δ (0°C) is an index of wet grip performance, and a larger value means better wet grip performance.

[tan δ (50°C)]
Using a viscoelasticity measuring device ARES manufactured by TAINSTRUMENTS, measurement was performed in torsion mode at a frequency of 10 Hz, a measurement temperature range of -50°C to 100°C, a heating rate of 2°C/min, and a dynamic strain of 0.1%. A value of 50°C was extracted from the obtained temperature variable tan δ.
Tan δ (50°C) is an index of rolling resistance performance, and a smaller value means better rolling resistance performance.

5. Results The results of the above measurements are shown below. The above Examples 1-1 and 1-2 are abbreviated as Example 1. Other examples and comparative examples are also abbreviated in the same manner.

The measurement results for each item are shown in Table 2 below. The values of tan δ (0° C.) and tan δ (50° C.) are expressed as relative values with 1 being the real value of Example 4 (0.594 and 0.105, respectively).

The process oils of Examples 1 to 4 satisfy the ranges of "percentage of saturates by Claygel method" and "percentage of bicyclic aromatics fractionated using HPLC" specified in the embodiments. The rubber compositions of Examples 1 to 4 obtained by blending the procell oil were extremely excellent in both wet grip performance and rolling resistance performance.
In particular, the rubber compositions of Examples 1 to 3, which were obtained by blending process oils that satisfy the range specified in the embodiment for the "proportion of aromatic content according to the clay gel method", had wet grip performance and rolling resistance performance of It can be seen that they are compatible with each other with good numerical values.
Moreover, it was confirmed that the contents of benzo(a)pyrene and specific aromatic compounds (PAHs) in both the process oils of Examples and Comparative Examples satisfy the REACH regulations.

As described above, each configuration and combination thereof in each embodiment are examples, and addition, omission, replacement, and other modifications of the configuration are possible without departing from the scope of the present invention. Moreover, the present invention is not limited by each embodiment, but is limited only by the scope of the claims.

DESCRIPTION OF SYMBOLS 10... Vacuum distillation apparatus, 11... Vacuum distillation fraction, 30a, 30b... Solvent extractor, 31a, 31b... Raffinate, 33a, 33b... Extract, 40... Hydrorefining apparatus, 41... Hydrorefined oil, 50... Dewaxing apparatus, 51 Dewaxing oil, 62 Petroleum aromatic-containing oil

Claims (9)

The percentage of saturated content by the clay gel method is 45% by mass or less,
The ratio of bicyclic aromatics fractionated using HPLC is 16% by mass or more and 29% by mass or less with respect to 100% by mass of aromatics by the clay gel method ,
The ratio of 1-ring aromatics fractionated using HPLC is 48% by mass or more and 80% by mass or less with respect to 100% by mass of aromatics by the clay gel method,
The proportion of aromatics with three or more rings fractionated using HPLC is 4% by mass or more and 20% by mass or less with respect to 100% by mass of aromatics by the clay gel method,
The content of benzo(a)pyrene is 1 mass ppm or less,
A petroleum-based aromatic-containing oil having a total content of specific aromatic compounds of 1) to 8) below of 10 ppm by mass or less.
1) Benzo(a)pyrene (BaP)
2) Benzo(e)pyrene (BeP)
3) Benzo(a)anthracene (BaA)
4) Chrysene (CHR)
5) benzo(b)fluoranthene (BbFA)
6) benzo(j)fluoranthene (BjFA)
7) Benzo(k)fluoranthene (BkFA)
8) Dibenzo(a,h)anthracene (DBAhA). 2. The petroleum-based aromatic-containing oil according to claim 1, wherein the ratio of saturates by the clay gel method is 22% by mass or more. 3. The petroleum-based aromatic according to claim 1 or 2, wherein the ratio of the bicyclic aromatic fraction fractionated using the HPLC is less than 23% by mass with respect to 100% by mass of the aromatic content by the clay gel method. contained oil. The petroleum-based aromatic-containing oil according to any one of claims 1 to 3, wherein the ratio of saturated content by the clay gel method is 36% by mass or less. The ratio of the bicyclic aromatic fraction fractionated using the HPLC is 22% by mass or less with respect to 100% by mass of the aromatic content by the clay gel method , according to any one of claims 1 to 4. of petroleum-based aromatic-containing oils. Extender oil or process oil used by being mixed with rubber ,
The petroleum aromatic-containing oil according to any one of claims 1 to 5 , wherein the rubber is at least one selected from the group consisting of natural rubber, isoprene rubber, styrene-butadiene rubber and butadiene rubber. A rubber composition containing the petroleum-based aromatic-containing oil according to any one of claims 1 to 6 and a rubber ,
The rubber composition, wherein the rubber is at least one selected from the group consisting of natural rubber, isoprene rubber, styrene-butadiene rubber and butadiene rubber. A tire containing the petroleum aromatic-containing oil according to any one of claims 1 to 6. A method for manufacturing a tire according to claim 8, comprising blending and vulcanizing the rubber and the petroleum-based aromatic-containing oil according to any one of claims 1 to 6 ,
The tire manufacturing method, wherein the rubber is at least one selected from the group consisting of natural rubber, isoprene rubber, styrene-butadiene rubber and butadiene rubber.

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