WO2020175512A1 - Petroleum-based aromatics-containing oil, rubber composition, tire, and method for producing tire - Google Patents

Abstract

Provided is a petroleum-based aromatics-containing oil having a saturates content by the clay-gel method of not more than 40 mass%, a proportion for a bicyclic aromatics fraction, as fractionated using HPLC, of 10 mass% to 30 mass% with reference to 100 mass% for an aromatics fraction, a benzo(a)pyrene content of not more than 1 mass-ppm, and a total content of following specific aromatic compounds 1) through 8) of not more 10 mass-ppm: 1) benzo(a)pyrene, 2) benzo(e)pyrene, 3) benzo(a)anthracene, 4) chrysene, 5) benzo(b)fluoranthene, 6) benzo(j)fluoranthene, 7) benzo(k)fluoranthene, and 8) dibenzo(a, h)anthracene.

Description

\¥0 2020/175 512 1 ?＜: 17 2020 /007603

Title of invention:

Petroleum-based aromatic-containing oil, rubber composition, tire, and method for manufacturing tire

Technical field

[0001] The present invention relates to a petroleum-based aromatic-containing oil, a rubber composition, a tire, and a method for producing a tire.

The present application claims priority on the basis of Japanese Patent Application No. 2019-9-03583836 filed in Japan on February 28, 2019, the content of which is incorporated herein by reference.

Background technology

[0002] Generally, a rubber product is often blended with a process oil in order to improve the processability and softening property of the rubber composition. For example, 3

Synthetic rubbers such as (styrene-butadiene copolymer rubber) are blended with extender oil (extender oil) during synthesis (rubber compounding oil). In addition, rubber processed products such as tires contain processing oil (process oil) to improve the processability and the quality of the rubber processed products. Although the expression oil is divided into the expression oil and the processing oil here, they may be collectively referred to as process oil.

On the other hand, in Europe, it is regulated that rubber compounded oils containing a specific amount of a carcinogenic polycyclic aromatic compound in a specific amount or more must not be used in the manufacture of tires or tire parts ([[ ¾ 801 ^~ 1 rule) has been applied since 2010. for that reason,

Rubber compounding oils that meet the snake eighty ^1-1 rule is demanded.

[0003] The trend of fuel saving in the automobile field has received a great deal of attention, and further improvement is required for the fuel saving of tires. With the start of the tire labeling system in January 2010, tires are strongly required to have improved "rolling resistance performance," which indicates fuel efficiency, and "wet grip performance," which indicates braking performance. ing. However, in general, rolling resistance performance and wet grip performance are in a trade-off relationship, and it is an issue to achieve both of these at a high level. [0004] In order to improve the rolling resistance performance of tires, air resistance is reduced and 〇 2020/175 512 卩 (: 170? 2020 /007603

There is a method to control the rubber composition, that is, the hysteresis loss of the tread compound itself, in addition to the device design. In recent years, compounds containing silica as a reinforcing material, which is one of tire prescriptions, have become popular. If silica is simply compounded, silica particles will agglomerate in the compound, and silica molecules will rub against each other during rubber deformation, resulting in energy loss. On the other hand, for the purpose of improving the rolling resistance performance while maintaining the wet grip performance, a method of controlling the existing 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, hydrous calcium carbonate, and a silane coupling agent, and a kneaded material obtained by the first base kneading step and kneading silica. A rubber composition for a tire obtained by a production method including a second base kneading step is disclosed. According to this, it is possible to obtain a rubber composition for a tire which has excellent dispersibility of silica and can improve fuel economy, wet grip performance, and wear resistance with good balance.

Prior art documents

Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 20 1 2-1 5 3 7 8 7

Summary of the invention

Problems to be Solved by the Invention

[0006] However, tires are required to further improve "rolling resistance performance" and "wet grip performance" and to achieve both of them. In response to such requirements, various approaches from rubber members other than silica and silane coupling agents are expected.

[0007] The present invention has been made to solve the above problems, and makes it possible to produce a rubber composition having excellent rolling resistance performance and wet grip performance,

And to provide a petroleum-based aromatic containing oils satisfying only 〇 ^1-1 rule.

Further, the present invention is

〇 2020/175 512 3 boxes (: 170? 2020 /007603

It is an object of the present invention to provide a rubber composition having excellent 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 manufacturing the tire.

Means for solving the problem

[0008] As a result of intensive studies to solve the above problems, the present inventors have formulated an oil containing a saturated component and, in particular, a two-ring aromatic component among aromatic components, in the following specific amounts. As a result, they have found that it is possible to produce a rubber composition having excellent rolling 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 method for producing a tire.

[0009] (1) The proportion of saturated components by the Clay gel method is 40% by mass or less,

!! !_ (The proportion of the two-ring aromatics fractionated using 3 is 10 mass% or more and 30 mass% or less with respect to 100 mass% of the aromatic content,

The benzo (8) pyrene content is 1 mass 111 or less,

A petroleum-containing aromatic-containing oil, wherein the total content of the specific aromatic compounds of 1) to 8) below is 10 mass 111 or less.

1) Benzo (3) Pyrene (Mimi 3)

2) Benzo (6) Pyrene (Minami 6)

3) Benzo (3) Anthracene (Mitsuhachihachi)

4) Chrysene (〇 1 ^~ 1 [¾)

5) Benzo (匕) Fluoranthene (Minami Yahachi)

6) Benzo) Fluoranthene (Mimi "8)

7) Benzo (1<) Fluoranthene (Mitsu 1<8)

8) Dibenzo (3,) Anthracene (0,8,8).

(2) The petroleum-containing aromatic oil according to (1) above, wherein the proportion of the saturated component by the clay gel method is 20% by mass or more.

(3) The proportion of the two-ring aromatics fractionated using !! !_(3 above is 〇 2020/175 512 4 (: 170? 2020 /007603

The petroleum-containing aromatic-containing oil described in (1) or (2) above is 28% by mass or less based on 100% by mass.

(4) The petroleum-based aromatic-containing oil according to any one of the above (1) to (3), wherein the ratio of saturated components by the Clay gel method is 35% by mass or less.

(5) The proportion of the two-ring aromatics fractionated by using !! !_(3 is 20% by mass or more based on 100% by mass of the aromatics, (1) ~ A petroleum-based aromatic-containing oil according to any one of (4).

(6) The petroleum-based aromatic-containing oil according to any one of (1) to (5) above, wherein the proportion of the saturated component by the Clay gel method is 30% by mass or less.

(7) The proportion of the bicyclic aromatic fraction fractionated by using !! !_(3 is 25 mass% or less with respect to 100 mass% of the aromatic content, (1) ~ A petroleum-based aromatic-containing oil according to any one of (6).

(8) The proportion of the bicyclic aromatic fraction fractionated by using !! !_(3 is 24.5 mass% or less with respect to 100 mass% of the aromatic content. The petroleum-based aromatic-containing oil according to any one of 1) to 7).

(9) A petroleum-based aromatic-containing oil according to any one of (1) to (8) above, which is an extender oil or a process oil used by being mixed with rubber.

(10) A rubber composition containing the petroleum-based aromatic-containing oil according to any one of (1) to (9) above and a rubber.

(11) A tire containing the petroleum-based aromatic-containing oil according to any one of (1) to (9) above.

(12) A rubber, and the petroleum-based aromatic-containing oil according to any one of (1) to (9) above, which is compounded and vulcanized. Tire manufacturing method.

Effect of the invention

[0010] According to the present invention, it is possible to produce a rubber composition having excellent rolling resistance performance and wet grip performance,

it can.

Further, according to the present invention, it is possible to provide a rubber composition containing a petroleum-based aromatic-containing oil satisfying the R EACH rule and being excellent in rolling resistance performance and wet grip performance.

Further, according to the present invention, it is possible to provide a tire containing the petroleum-based aromatic-containing oil, and a method for manufacturing the tire.

Brief description of the drawings

[0011] [Fig. 1] Fig. 1 is a process chart explaining an example of a method for producing a petroleum-based aromatic oil according to an embodiment of the present invention.

FIG. 2A is a process chart illustrating an example of the process of preparing the tire composition according to the embodiment of the present invention.

FIG. 2B is a process chart illustrating an example of the process of preparing the tire composition according to the embodiment of the present invention.

MODE FOR CARRYING OUT THE INVENTION

[0012] Hereinafter, embodiments of the petroleum-based aromatic-containing oil, the rubber composition, the tire, and the method for manufacturing a tire according to the present invention will be described.

[0013] <<Oil-containing aromatic oil>>

In the petroleum-based aromatic-containing oil of the embodiment, the ratio of the saturated component by the clay gel method, the ratio of the 2-ring aromatics fractionated by using HP LC, the content of benzo(a)pyrene, and the specific aromatic The content of the group compound satisfies a specific numerical range. For rubber compositions or tires containing petroleum-based aromatic-containing oils that satisfy the following numerical ranges for these items, the values of tan 5 (50 ^° C) and tan S (0 ^° C) are preferable, and the wet grip performance and Both rolling resistance performance is compatible. [0014] Here, the "wet grip performance" is so-called braking performance, and tan S (0 ^° C) obtained by the dynamic viscoelasticity test is an index thereof. “Rolling resistance performance” is so-called fuel-saving performance, and its index is tan 5 (50 ^° C) obtained by a dynamic viscoelasticity test.

[0015] The above "petroleum-based" includes petroleum-derived (Petroleum-Derived) hydrocarbon oils. 〇 2020/175 512 6 boxes (: 170? 2020 /007603

Means to do. The above-mentioned "aromatic-containing oil" means that the ratio of the saturated content by the Clay-gel method and the ratio of the 2-ring aromatics fractionated by using 1 1 1_(3 satisfy the following numerical value range. ..

The petroleum-based aromatic-containing oil of the embodiment is not particularly limited in its production method and classification as long as it satisfies the numerical ranges of the above-mentioned items, and includes, for example, atmospheric distillation residue, atmospheric distillation fraction, reduced pressure distillation fraction, Examples include vacuum distillation residue, deasphalted oil, solvent-extracted raffinate, hydrorefined oil, dewaxed oil, solvent-extracted extract, etc., and contain the oil produced by the petroleum-based aromatic-containing oil production method described below. Is preferred. The content ratio 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, and 95% by mass or more.

[0016] Each item relating to the properties of the petroleum-based aromatic-containing oil of the embodiment will be described below.

[0017] The components of petroleum-based oils can be classified into saturated components, aromatic components, and polar components (mass %) by the Clay gel method. The values of saturated content, aromatic content, or polar component (mass %) by the Clay gel method below are values based on 100 mass% of the total amount of saturated content, aromatic content, and polar component.

[0018] In the petroleum-based aromatic-containing oil of the embodiment, the proportion of the saturated component by the clay gel method is 40% by mass or less, preferably 35% by mass or less, and 30% by mass or less. Is more preferable. In the petroleum-based aromatic-containing oil of the embodiment, the ratio of the saturated component by the clay gel method is preferably 5% by mass or more, more preferably 20% by mass or more, and 22% by mass or more. It is even better to have it. As an example of the numerical range of the above numerical values, in the petroleum-based aromatic-containing oil of the embodiment, the proportion of the saturated component by the clay gel method may be 5% by mass or more and 40% by mass or less, and 20% by mass or more. It may be 35 mass% or less, or 22 mass% or more and 30 mass% or less.

When the ratio of the above-mentioned saturated component satisfies the above-mentioned value, the values of tan 5 (50 ° 〇) and tan S (0 ° 〇) of the rubber composition or tire containing the oil become preferable, and the wet grip Both performance and rolling resistance performance are compatible. 〇 2020/175 512 7 (: 170? 2020 /007603

This is because the saturated content has a proper balance as the polarity of hydrocarbons and has a certain affinity with rubber and a certain affinity with the compounding agent of rubber. It is considered that when the content is within the range, the physical properties of the rubber composition or the tire to be manufactured become suitable.

[0019] In the petroleum-based aromatic-containing oil of the embodiment, the proportion of the aromatic component 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 is more preferable. In the petroleum-based aromatic-containing oil according to the embodiment, the proportion of the aromatic component by the Clay gel method is preferably 74% by mass or less, more preferably 70% by mass or less, and 66% by mass or less. It is more preferable that there is. As an example of the numerical range of the above numerical values, the petroleum-based aromatic-containing oil of the embodiment,

It may be 50 mass% or more and 74 mass% or less, 51 mass% or more and 70 mass% or less, and 58 mass% or more and 66 mass% or less. When the ratio of the above aromatic content satisfies the above value, the values of 1 an 8 (50° 〇) and I 3 n 5 (0° 〇) of the rubber composition or tire containing the oil are preferable. Therefore, the wet grip performance and the rolling resistance performance are compatible.

This is because the aromatic component has a high affinity for rubber, so that the ratio of the above aromatic component is within the above range, the physical properties of the rubber composition or the tire to be manufactured are preferable. it is conceivable that.

[0020] The petroleum-containing aromatic-containing oil of the embodiment has a ratio of polar components measured by the clay gel method,

It is preferably 3% by mass or more, more preferably 4% by mass or more, and further preferably 5% by mass or more. In the petroleum-containing aromatic oil of the embodiment, the proportion of the polar component by the clay gel method is preferably 12% by mass or less, more preferably 11% by mass or less, and 10% by mass or less. It is more preferable that there is. As an example of the numerical range of the above numerical values, in the petroleum-based aromatic-containing oil of the embodiment, the proportion of polar components by the clay gel method may be 3% by mass or more and 12% by mass or less, and 4% by mass or more 1 It may be 1 mass% or less, or 5 mass% or more and 10 mass% or less. The proportion of the polar component has a reciprocal relation with the proportion of the saturated component and the aromatic component, and when the proportion of the polar component satisfies the above numerical value, the rubber composition containing the oil or The tan 5 (50°C) and tan S (0°C) values of the tire are preferred, and both wet grip performance and rolling resistance performance are compatible.

[0021] The ratio (mass %) of the saturated component, aromatic component, and polar component by the Clay gel method is

ASTM D 2007 — 1 1 Standard Test Method for Characteristic Grups in Rubber Extender and Processing Oils and Other Petroleum-Derived Oi Is by the Clay-Gel Absorption Chromatographic Method.

[0022] In the petroleum-based aromatic-containing oil of the embodiment, when the proportion of the 2-ring aromatics fractionated by using HP LC is 10% by mass or more based on 100% by mass of the aromatic content. %, preferably 16% by mass or more, more preferably 20% by mass or more, further preferably 22% by mass or more, and particularly preferably 23% by mass or more. In the petroleum-based aromatic-containing oil according to the embodiment, the proportion of the 2-ring aromatics fractionated by using HP LC is 30 mass% or less with respect to 100 mass% of the aromatic content, and 28 mass% % Or less, more preferably 26% by mass or less, further preferably 25% by mass or less, particularly preferably 24.5% by mass or less. As an example of the numerical range of the above numerical values, in the petroleum-based aromatic-containing oil of the embodiment, the proportion of the 2-ring aromatics fractionated by using HP LC is 100% by mass of the aromatic content. On the other hand, it may be 10% by mass or more and 30% by mass or less, 16% by mass or more and 28% by mass or less, 20% by mass or more and 26% by mass or less, and 22% by mass. It may be 25 mass% or more and 25 mass% or less, or 23 mass% or more and 24.5 mass% or less. Here, the values of tan 5 (50 °C) and tan 5 (○ ^° C) of the rubber composition or the tire containing the oil described above are satisfied when the ratio of the above two-ring aromatic content satisfies the above numerical values. This is preferable, and both wet grip performance and rolling resistance performance are supported.

The fact that the aromatic content in the aromatic content 〇 2020/175 512 9 (: 170? 2020 /007603

However, the ratio of aromatics having two or more rings greatly contributes to achieving both wet grip performance and rolling resistance performance. Among them, the bicyclic aromatic content, in addition to improving Yuck Toguri' flops performance and rolling resistance, also have good properties further terms of satisfying only 0 1 ^to 1 rule.

[0023] The petroleum-based aromatic-containing oil of the embodiment has a ratio of 1-ring aromatics fractionated using 1 ^to 1 !_(3 to 4% of the aromatic content of 100% by mass. preferably the this is 8 mass% or more, more preferably 5 0 mass% or more, 5 2 it is mass% or more is more preferred. petroleum aromatic-containing oils embodiments, ^1-1! _ The proportion of 1-ring aromatics fractionated using ◯ is preferably 64% by mass or less, and 62% by mass or less, based on 100% by mass of the aromatic content. More preferably, it is still more preferably 60% by mass or less.. As an example of the numerical range of the above numerical values, the petroleum-based aromatic-containing oil of the embodiment is

The ratio of the 1-ring aromatics fractionated by using may be 48% by mass or more and 64% by mass or less, or 50% by mass or more and 6% by mass or less, based on 100% by mass of the aromatic content. It may be 2% by mass or less, or 52% by mass or more and 60% by mass or less.

The proportion of the above-mentioned 1-ring aromatic content has a reciprocal relationship with the proportion of the above-mentioned 2 or more-ring aromatic content, and the proportion of the above-mentioned 1-ring aromatic content satisfies the above numerical values, so that the oil content is The values of 1 an 8 (50° ◯) and I 3 n 5 (0° 〇) of the rubber composition or tire to be used become preferable, and the wet grip performance and the rolling resistance performance are compatible with each other.

[0024] In the petroleum-based aromatic-containing oil of the embodiment, the ratio of the aromatic content of 3 or more rings fractionated by using 1 ^to 11_(3 is relative to 100% by mass of the aromatic content, The content is preferably 10% by mass or more, more preferably 12% by mass or more, further preferably 14% by mass or more, and particularly preferably 16% by mass or more. In the petroleum-based aromatic-containing oil, the proportion of aromatics having 3 or more rings fractionated using 1 ^to 1 !_(3 is 28% by mass relative to 100% by mass of the aromatics. It is preferably below, more preferably at most 26% by mass, further preferably at most 24% by mass, particularly preferably at most 23% by mass. 〇 2020/175 512 10 boxes (: 170? 2020 /007603

preferable. As an example of the numerical range of the above numerical values, the petroleum-based aromatic oil of the embodiment has a ratio of aromatics of 3 or more rings fractionated using 1 ^to 11_(3, Min. 10% by mass to 28% by mass, 12% to 26% by mass, 14% to 24% by mass It may be the following, or may be 16% by mass or more and 23% by mass or less: The rubber composition containing the oil when the ratio of the aromatic component having 3 or more rings is satisfying the above numerical values. The values of I an 8 (50° 〇) and I 3 n 5 (0° 〇) of the object or tire are preferable, and both the wet grip performance and the rolling resistance performance are compatible, and it is also good from the viewpoint of meeting the ACH rule. Become.

[0025] Fractionation of aromatic components using !!?!_(3 can be determined under the measurement conditions described in Examples below.

[0026] The petroleum-based aromatic-containing oil of the embodiment is

The benzo (8) pyrene content is 1 mass 111 or less,

Following 1) to 8 specific aromatic compound) (? 1 ^- 1 ₃₎ Total is 1 0 mass 01 following content.

1) Benzo (3) Pyrene (Mimi 3)

2) Benzo (6) Pyrene (Minami 6)

3) Benzo (3) Anthracene (Mitsuhachihachi)

4) Chrysene (〇 1 ^~ 1 [¾)

5) Benzo (匕) Fluoranthene (Minami Yahachi)

6) Benzo) Fluoranthene (Mimi) eight)

7) Benzo (1<) Fluoranthene (Mitsu 1<8)

8) Dibenzo (3,) Anthracene (0,8,8).

[0027] When the content of these base down zone ₍₃₎ pyrene and the specific aromatic compound ^(1-1 ₃₎ is within the above range,

And compliance with content regulation of extender for oil in snake eighty ^1-1 rule, Ru can be a more secure rubber compounding oil.

[0028] The content of these compounds is determined by separating and concentrating the target components, It can be obtained by preparing a sample to which is added and quantitatively analyzing by GC_MS analysis.

The content of benzo (a) pyrene and specific aromatic compounds (PAH s) is determined by the European standard EN 1 6 1 43: 201 3 Petroleum products-Determination of content of Benzo(a) pyrene (BaPJ and selected polycyclic aromatic hydrocarbons ( PAH) in extender oils -Procedure using double LC cleaning a nd GC/MS ana lysis.

[0029] The petroleum-containing aromatic-containing oil of the embodiment has a kinematic viscosity ^at 100 ^° C of preferably 25 mm ² /s or more, more preferably 27 mmVs or more, and 28 mmVs or more. More preferably, The petroleum-based aromatic-containing oil of the embodiment has a kinematic viscosity at 100°C of preferably 75 mm Vs or less, more preferably 58 mm ² /s or less, and 50 mm ² /s or less. Is more 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 kinematic viscosity at 100 ^° C of 25 mm V s or more and 75 mm ² /s or less, It may be in the range of 27 mm ² /s or more and 58 mm ² /s or less, or in the range of 28 mm ² /s or more and 50 mm ² /s or less. When the value of the kinematic viscosity satisfies the above value, the viscosity of the rubber composition or the tire containing the petroleum-based aromatic-containing oil becomes preferable, so that tan 5 (50 ^° C) and tan S (0 ^° C) Is even more preferable, and compatibility of wet grip performance and rolling resistance performance is even more desirable. Further, when the value of the kinematic viscosity is less than or equal to the upper limit value, the transfer and workability for blending the petroleum-based aromatic-containing oil with the rubber become good.

[0030] The kinematic viscosity at 100 °C can be determined according to the regulations of J I S K 2283 :2000.

The petroleum-based aromatic-containing oil of the embodiment preferably has an aniline point of 60 ^° C. or higher, more preferably 65° C. or higher, even more preferably 70° C. or higher. Petroleum aromatic-containing oils embodiment is preferably an aniline point of less than 1 00 ^° C, more preferably not more than 95 ^° C, 90 ^° C The following is more preferable. 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 of 60 ^° C or higher and 100 ^° C or lower, and 65 ^° C or higher and 95 ^° C or higher ^. It may be in the following range, or in the range of 70 ^° C or higher and 90°C or lower. The aniline point is the temperature at which an equal amount of aniline and oil mix, and is an indicator of rubber compatibility. When the aniline point is at most the above upper limit value, the oil will dissolve with aniline without excessive heating, which is preferable because of high rubber compatibility. That is, when the value of the aniline point satisfies the above-mentioned value, the affinity of the petroleum-based aromatic-containing oil for rubber becomes good, and the physical properties of the rubber composition or tire produced become even more preferable.

[0032] The aniline point can be determined according to the rules of ASTM D 6 1 1 -1 2 Standard Test Methods for Ani line Point and Mixed Am line Point of Petroleum Products and Hydrocarbon So Ivents.

[0033] petroleum aromatic-containing oils embodiment, the glass transition point (T g), preferably from the _58 ^° C or more, more preferably _ 56 ^° C or higher, one 54 ° C It is more preferable that the above is satisfied. The petroleum-containing aromatic oil of the embodiment has a glass transition point (T g) of preferably 44 ^° C or lower, more preferably 46 ^° C or lower, and _ 48 ^° C or lower. It is more preferable that there is. 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 (T g) in the range of _58°C or more and 1 44°C or less. It may be in the range of 56°C or higher and 1°C or lower and 46°C or lower, or may be in the range of 54°C or higher and 1°C or lower and 48°C or lower. When the glass transition point satisfies the above numerical values, the physical properties of the rubber composition or tire to be produced become more preferable, and it becomes important for improving the wet grip performance and rolling resistance performance.

[0034] The glass transition point can be determined under the measurement conditions described in Examples below.

[0035] The petroleum-containing aromatic-containing oil of the embodiment has a viscosity specific gravity constant (VGC) of preferably 0.84 or more, more preferably 0.85 or more, and 0.8.

It is more preferably 86 or more. The petroleum-based aromatic-containing oil of the embodiment, The viscosity specific gravity constant (VGC) is preferably 0.92 or less, more preferably 0.90 or less, and further preferably 0.89 or less. As an example of the numerical range of the above numerical values, the petroleum-based aromatic-containing oil of the embodiment may have a viscosity specific gravity (VGC) of 0.84 or more and 0.92 or less, and 0.85 or more and 0.90 or less. It may be less than or equal to 0.86 and less than or equal to 0.89. The viscosity specific gravity constant is an index expressing the composition of oil. Generally, the higher the paraffinicity, the lower the value, and the higher the aromaticity, the higher the value. When the value of the viscosity specific gravity constant satisfies the above value, the physical properties of the rubber composition or the tire containing the petroleum-based aromatic-containing oil become favorable, so that tan 8 (50°C) tan 5 (0° 〇 The value becomes even more preferable, and the compatibility of the wet grip performance and the rolling resistance performance becomes even more preferable.

[0036] The viscosity specific gravity constant (VGC) can be determined in accordance with the provisions of ASTM D 2 40-08 08 Standard Prac 11 ce for Calculating Carbon-Type Composition of Insulating 01 Is of Petroleum Origin.

[0037] The petroleum-containing aromatic-containing oil of the embodiment has a% CA by ring analysis of preferably 12 or more, more preferably 14 or more, and further preferably 16 or more. The petroleum-containing aromatic-containing oil of the embodiment has a% C A by ring analysis of preferably 30 or less, more preferably 28 or less, and further preferably 26 or less. As an example of the numerical range of the above numerical values, the petroleum-based aromatic-containing oil of the embodiment may have% CA by ring analysis of 12 or more and 30 or less, or 14 or more and 28 or less, It may be 16 or more and 26 or less.

When the above% CA satisfies the above value, the amount of polycyclic aromatic compounds having high carcinogenicity is suppressed, and at the same time, the aromatic compound tends to have an aroma improving the compatibility with the rubber. The values of tan 5 (50 °C) and tan 5 (○ ^° C) of the composition or the tire become preferable, and the compatibility of the wet grip performance and the rolling resistance performance becomes more preferable.

[0038] %CA is ASTM D 2 1 40 -08 Standard Practice for Calcula ti ng Carbon-Type Compositi on of Insu Lat i ng O i Ls of Pet ro Leum Or igin

[0039] The petroleum-containing aromatic-containing oil of the embodiment is preferably used as an extender oil or a process oil used by being mixed with rubber.

[Method for producing petroleum-based aromatic-containing oil]

Hereinafter, a method for producing a petroleum-based aromatic-containing oil according to the embodiment will be described. According to the above method, the petroleum-based aromatic-containing oil of the present invention can be produced. The petroleum-based aromatic-containing oil of the present invention is not limited to those produced by the method for producing a petroleum-based aromatic-containing oil of the following embodiments.

[0041] The method for producing a petroleum-containing aromatic-containing oil according to the embodiment is

A step of obtaining an extract by solvent extraction, or

The method includes a step of mixing the extract obtained by solvent extraction with a raffinate or a refined base oil of raffinate.

Solvent extraction targets include deasphalted oil fraction obtained by degassing the residue obtained by distilling crude oil under atmospheric pressure under reduced pressure, and depressurized distillation fraction obtained by distilling the residue obtained by distilling crude oil under atmospheric pressure under reduced pressure. Minutes. In solvent extraction, the extract is obtained by subjecting the object of solvent extraction to extraction treatment with a solvent that has an affinity for aromatic hydrocarbons, and separating and recovering the solvent and extract (extract). .. As the starting crude oil, various crude oils such as paraffinic crude oil and naphthenic crude oil can be used alone or in combination, but paraffinic crude oil is particularly preferably used.

[0042] Fig. 1 is a process chart illustrating an example of a method for producing a petroleum-based aromatic-containing oil according to an embodiment. The crude oil is first processed in an atmospheric distillation device (not shown) to obtain an atmospheric distillation residue. The atmospheric distillation residue is sent to the vacuum distillation apparatus 10 and vacuum distilled to obtain a vacuum distillation residue 12. The vacuum distillation residue 1 2 is treated in the deasphalting extraction device 20 to become the deasphalted oil 22. Thereafter, the deasphalted oil 22 is sent to the solvent extraction device 30. The solvent extractor 30 separates the deasphalted oil 22 into a raffine extract 32 and an extract 34. Raffinate 32 is hydrogenated 〇 2020/175 512 15 boxes (: 170? 2020 /007603

It is hydrorefined in the production unit 40 to be hydrorefined oil 42, and then dewaxed in the dewaxing unit 50 to obtain dewaxed oil 52. The dewaxed oil 52 obtained and the extract 34 can be mixed to obtain a petroleum-based aromatic-containing oil 62.

Here, the case where the dewaxed oil 52 and the extract 34 are mixed to obtain the petroleum-based aromatic-containing oil 62 is explained, but instead of the dewaxed oil 52, the raffinate 32 or The hydrorefined oil 42 may be mixed with the extract 34.

[0044] Separately, the vacuum distillation fraction 11 separately fractionated from the vacuum distillation apparatus 10 is treated by a solvent extraction apparatus 30 and separated into raffinate 31 and extract 33. The raffinate 3 1 is hydrorefined in the hydrorefining unit 40 to be hydrorefined oil 41, and is further dewaxed in the dewaxing unit 50 to obtain dewaxed oil 5 1. The dewaxed oil 51 and the extract 34 thus obtained can be mixed to obtain a petroleum-based aromatic oil-containing oil 62.

Here, the case where the dewaxed oil 5 1 and the extract 34 are mixed to obtain the petroleum-based aromatic-containing oil 62 is explained, but instead of the dewaxed oil 51, the raffinate 31 or hydrorefining is used. The oil 41 may be mixed with the extract 34.

[0045] Further, here, the case where the dewaxed oils 51, 52 and the like and the extract 34 are mixed to obtain the petroleum-containing aromatic-containing oil 62 is described, but instead of the extract 34, , Dewaxed oil 51, 52, etc. may be mixed with extract 33

[0046] Further, the extracts 3 3 and 3 4 may be petroleum-based aromatic-containing oil 62.

[0047] It is possible to obtain the vacuum distillation under the condition that the end point of the distillate oil is 580 ° 〇 or more in terms of atmospheric pressure or the initial distillation point of the residue is 450 ° 〇 or more. It is preferable because the aromatic content in the extract can be easily adjusted within a predetermined range. Debris removal is carried out at a tower top temperature: preferably 40 to 120 ^° 〇, more preferably 50 to 100 ^° 〇, tower bottom temperature: preferably 30 to 100 ^° 〇, more preferably 4 It can be carried out under the conditions of 0 to 90 ^° and solvent ratio: preferably 1 to 10 and more preferably 1 to 9. 20/175512 16 卩 (: 170? 2020 /007603

The solvent extraction is preferably performed by extracting the obtained deasphalted oil with a solvent having a selective affinity for aromatic hydrocarbons in order to obtain the extracts 33 and 34. As the solvent having a selective affinity for aromatic hydrocarbon, a polar solvent may be used, and one or more selected from the group consisting of furfural, phenol and 1\1-methyl-2-pyrrolidone is used. be able to. The specific extraction conditions for controlling the extract yield within the above range cannot be uniquely determined because it depends on the composition of the deasphalted oil, but by appropriately selecting the solvent ratio, pressure, temperature, etc. It is possible. In general, the column top temperature: preferably 100 to 155°°, more preferably 100 to 140°°, the column bottom temperature: preferably 40 to 120°°, The solvent is preferably contacted at a ratio of 50 to 110° and a ratio of solvent to oil 1: 2 to 5, more preferably 3 to 4.5. On the other hand, in order to obtain the raffinates 31 and 32, a solvent refining process is carried out in which a vacuum distillation fraction having a boiling point at atmospheric pressure of 300 to 700° is extracted with a solvent having an affinity for aromatic hydrocarbons. It is preferable. As a solvent having a selective affinity for aromatic hydrocarbons, one or more selected from furfural, phenol and 1\]-methyl-2-pyrrolidone can be used. In this solvent purification step, the conditions for purifying conventional lubricating base oils, for example, the case of using furfural as citrus out solvent, column top temperature: preferably 9 0 to 1 5 0 ^° 〇, more preferred properly 1 0 0 to 140° 〇, tower bottom temperature: preferably 40 to 90° 〇, more preferably 50 to 80 ^° 〇, solvent ratio to oil 1: preferably 0.5 to 4 It is preferable to contact with the solvent at 1 to 3.

If desired, a more preferable base oil can be obtained by dewaxing the raffinate by hydrorefining and/or solvent dewaxing or hydrodewaxing treatment. The hydrorefining is carried out in the presence of a catalyst in which one or more kinds of active metals such as nickel, cobalt and molybdenum are supported on a carrier such as alumina or silica-alumina under hydrogen pressure.

It is advisable to perform the test at a temperature of 250 to 400° and liquid space velocity (!_ 1 ^to 13) 1 to 5 1^ ^-1 . The solvent dewaxing can be performed, for example, in a mixed solvent of methyl ethyl ketone/toluene with a solvent/oil ratio (volume ratio) = 1/1 〇 2020/175 512 17 boxes (: 170? 2020 /007603

It is recommended to carry out the reaction at a temperature of ~5/1 at a temperature of 110-1 to 40 ^° 〇, and hydrodewaxing should be carried out at a hydrogen pressure in the presence of a zeolite catalyst.

Temperature 300 to 400 ^° 〇, LHSV 1 to 5 H “It is recommended to carry out under the conditions of 1.

Hydrorefining involves contacting hydrogen at high temperature and high pressure with feedstock oil in the presence of a catalyst to remove impurities, such as sulfur and nitrogen, that can adversely affect the use and storage of process oil as hydrogenated light reactants. It can be removed, and as a result, stability and hue can be improved. For solvent dewaxing, one or more solvents selected from the group consisting of acetone, methylethylketone, benzene, and toluene are used to mix with the feedstock, and then a cooling process is performed to start with normal paraffin. It is possible to improve the low temperature fluidity by precipitating a wax fraction and separating it by filtration with a filter.

By mixing the extract and the base oil obtained as described above in a mass ratio of 9 5/5 to 5/95, and particularly preferably in a ratio of 80/20 to 20/80. The petroleum-based aromatic-containing oil of the embodiment can be produced.

[0048] <<Rubber composition>>

Hereinafter, the rubber composition of the embodiment will be described. The rubber composition of the present invention is not limited to the following rubber composition.

FIG. 2 and FIG. 2 are process drawings illustrating an example of a process of preparing a tire composition from a raw rubber. The tire composition used as a tire raw material contains raw rubber and various compounding agents. Synthetic rubber may be blended with extender oil during its synthesis, and a rubber composition containing an extender oil in advance (also referred to as oil-extended rubber) may be used as a raw rubber (see Fig. 2-8). See). Alternatively, raw rubber (also called non-oil extended rubber) containing no extender oil may be used (see Fig. 2). Process oil and various compounding agents are added to the raw rubber (see Fig. 2 and Mitsumi).

A raw rubber (rubber composition) that is an oil-extended rubber can be obtained by subjecting a monomer to a polymerization reaction, and can be produced by adding an extender oil in the process. For example, the monomer and extender that are the raw materials for the raw rubber 〇 2020/175 512 18 卩 (: 170? 2020 /007603

Oil extension can be carried out by subjecting a reaction liquid containing oil to a polymerization reaction, or by adding a extender oil to the polymer solution after polymerizing a reaction liquid containing a monomer which is a rubber raw material of the raw rubber. Rubber can be manufactured (Fig. 28). A tire composition (rubber composition) includes the above-mentioned raw material rubber, the petroleum-based aromatic-containing oil according to the present invention, and a compounding agent, for example, known kneaders for rubber, for example, mouth rolls, mixers, and kneaders. It can be manufactured by kneading. The tire composition can be vulcanized under any conditions.

In the present specification, a rubber composition containing a raw material rubber and a 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 used for manufacturing a tire. It is suitable as a rubber composition for a tire. As one embodiment, the present invention provides a tire composition containing a raw material rubber, a petroleum-based aromatic-containing oil according to the present invention, and a compounding agent. The evening composition is a concept included in the rubber composition of the embodiment. The tire composition (rubber composition) may be vulcanized or unvulcanized.

Here, the expression is divided into the extruder oil and the process oil, but these are sometimes collectively referred to as the process oil.

[0049] Hereinafter, the compositions of the rubber composition and the tire composition will be described.

[0050] As the raw material rubber, an elastomeric polymer can be used. Gen rubber, ethylene-propylene-gen rubber, halogenated butyl rubber, halogenated isoprene rubber, halogenated isoprene copolymer, chloroprene rubber, butyl rubber and halogenated isoptylene-genyl rubber such as methylstyrene rubber, nitrile rubber, chloroprene rubber, Butyl rubber, Ethylene-Propylene-based rubber (Mimi 0 1\/1, Mimi 1\/1), Ethylene-Butene rubber (Mimi Mimi 1\/1), Chlorosulfonated polyethylene, Acrylic rubber, Fluorine rubber and other olefins System rubber, epichlorohydrin rubber, polysulfide rubber, 〇 2020/175 512 19 boxes (: 170? 2020 /007603

Silicone rubber, urethane rubber, etc. can be mentioned. In addition, polystyrene-based elastomeric polymer that may be hydrogenated (3, 3, 3 1, 3, 3, £ 3, 3), polyolefin-based elastomeric polymer, polyvinyl chloride It may be a thermoplastic elastomer such as elastomeric polymer, polyurethane elastomeric polymer, polyester elastomeric polymer or polyamide elastomeric polymer. These can be used alone or in any blend.

From the viewpoint of compatibility with petroleum-based 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. It is preferably at least one of Furthermore, from the viewpoint that it can be suitably used for a tire that exhibits rolling resistance and water-grip performance as tire performance, elastomeric polymers include natural rubber, isoprene rubber, styrene-butadiene rubber, and butadiene. It is preferably at least one selected from the group consisting of rubber.

[0051] As the extender oil or the process oil, the petroleum-based aromatic-containing oil according to the embodiment can be used.

[0052] Compounding agents include fillers, antioxidants, antioxidants, cross-linking agents (vulcanizing agents), cross-linking accelerators, resins, plasticizers, vulcanization accelerators, vulcanization accelerating aids (vulcanization aids). Agents).

[0053] Examples of the filler include carbon black, silica, silane compounds (silane coupling agents) and the like, and silica and/or silane coupling agents are preferable.

Carbon black is classified into hard carbon and soft carbon based on particle size. Soft carbon has low reinforcement to rubber, and hard carbon has high reinforcement to rubber. When the rubber composition of the embodiment contains force-bonded black, it is preferable to use hard carbon having a particularly strong reinforcing property. Carbon black is based on 100 parts by weight of the elastomeric polymer. 〇 2020/175 512 20 units (: 170? 2020 /007603

It is preferably mixed in an amount of 10 to 250 parts by mass, more preferably in an amount of 20 to 200 parts by mass, and even more preferably in an amount of 30 to 50 parts by mass.

The silica is not particularly limited, and examples thereof include dry method white carbon, wet method white carbon, colloidal silica, and precipitated silica. Among these, wet method 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 is usually 10 to 40 in terms of nitrogen adsorption specific surface area (Mitsumi method).

It is suitable for improvement of reinforcing property, abrasion resistance, heat generation property, etc. when it is in the range of preferably ^{20 to} 300! ² /, more preferably 120 to 1900 ¹² /. Is. Here, the nitrogen adsorption specific surface area is a value measured by the Mitsumi method in accordance with 8 3 1\/1 0 3 0 3 7-81.

The silane compound is not particularly limited, but a sulfur-containing silane coupling agent is preferable, and bis(3-triethoxysilylpropyl)disulfide is more preferable.

[0054] Examples of the crosslinking agent (vulcanizing agent) include powdered sulfur, precipitated sulfur, highly dispersible sulfur, surface-treated sulfur, and insoluble sulfur.

[0055] Examples of the vulcanization accelerator include tetramethylthiuram disulfide (Cho 1\/1C 0), tetraethyl thiuram disulfide (Chomi Cho), and other thiuram-based compounds, and aldehydes such as hexamethylenetetramine. Ammonia type, guanidine type such as diphenylguanidine, thiazole type such as dibenzothiazyl disulfide (Mouth IV!), cyclohexyl ether such as 1\1-cyclohexyl-2-benzothiazolyl sulfenamide. Examples include Nzothiazyl sulfenamide type.

[0056] Examples of the vulcanization accelerator 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, acryl. Examples thereof include zinc acid, fatty acid zinc such as zinc maleate, and zinc white. 〇 2020/175 512 21 box (: 170? 2020 /007603

[0057] The amounts of these raw material rubbers, the petroleum-based aromatic-containing oil according to the present invention, and the compounding agent can be set to general amounts unless it is against the object of the present invention.

[0058] As an example, with respect to 100 parts by mass of the elastomeric polymer, a filler: 30 to 100 parts by mass, a petroleum-based aromatic-containing oil: 80 parts by mass or less, an antiaging agent: 0.5 ~ 5 parts by mass, cross-linking agent: 1 to 10 parts by mass, resin: 〇 to 20 parts by mass, vulcanization accelerator: 0.5 to 5 parts by mass, vulcanization accelerator aid: 1 to 10 parts by mass Can be exemplified.

When a silica and/or silane coupling agent is used as a filler, the silica and/or silane coupling agent is mixed in an amount of 10 to 300 parts by mass with respect to 100 parts by mass of the elastomeric polymer. It is preferable that it is contained, more preferably 50 to 150 parts by mass, further 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, and more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the elastomeric polymer. The petroleum-based aromatic-containing oil is preferably 0.5 to 80 parts by mass with respect to 100 parts by mass of the elastomeric polymer, and more preferably 10 to 50 parts by mass. It is more preferably 20 to 40 parts by mass.

[0059] According to the rubber composition of the embodiment, it is possible to provide a rubber composition having excellent rolling resistance performance and wet grip performance.

[0060] <<Tire-Method for manufacturing tire>>

The tire of the embodiment contains the petroleum-based aromatic-containing oil according to the above embodiment.

The tire of the embodiment can be manufactured by blending rubber and the petroleum-based aromatic-containing oil of the embodiment and vulcanizing.

In other words, the tire according to the embodiment may include the above tire composition (rubber composition), and can be produced by vulcanizing the tire composition. 〇 2020/175512 22 (: 170? 2020/007603) Specifically, for example, the above tire composition can be vulcanized to produce a tire. More specifically, for example, A tire is manufactured by heat-melting the above tire composition, extruding the heat-melted tire composition, then molding using a tire molding machine, and then heating and pressurizing using a vulcanizer. You can

[0061] A tire is composed of, for example, a tire, a tire, a carcass, a side wall, an inner liner, an undertread, and a belt portion. The tire according to the embodiment preferably contains the petroleum-based aromatic-containing oil according to the above-described embodiment in the tred portion. The tire of the embodiment preferably has a tire tread made of the tire composition of the embodiment. Since the petroleum-based aromatic-containing oil is contained in the tread portion that serves as the ground contact surface, rolling resistance performance and wet grip performance are suitably exhibited.

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

[0063] The reason why the petroleum-containing aromatic-containing oil of the embodiment exerts the effect of achieving both the wet grip performance and the rolling resistance performance of the tire composition (rubber composition) is estimated as follows. ..

Since both performances are trade-offs, if one is improved without compromising the other, they can be compatible as a result. Normally, it is compatible with what is called a fuel-efficient tire by blending silica, and it is especially aimed at fuel-saving performance, but since the siliency has many hydrophilic groups on the surface and it is difficult to fit with rubber polymers, Silicas tend to agglomerate. In that case, when the tire is deformed during driving, heat will be generated due to friction between the silica particles, resulting in extra 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 component in a specific amount acts on the dispersion or dissolution of various compounding agents including silica, and their behavior in the rubber polymer has a favorable influence on each physical property. As a result, it is considered that the anti-performance is compatible. 〇 2020/175 512 23 卩 (: 170? 2020 /007603

Example

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.

[0065] 1. Manufacturing of process oil

<Example 1 _ 1>

Middle Eastern 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 subjected to compression liquefaction propane deasphalting extraction apparatus (operating conditions: overhead temperature 60 to 90 ^° 0, tower bottom temperature 50 to 80 ^° 0, solvent ratio adjusted to within the range of 1.5 to 6.0), and the obtained deasphalted oil was extracted with a furfural extractor (operating conditions: tower top temperature 1 30 to 1 40 ^° 0, column bottom temperature 80 to 100 ^° 0, solvent ratio adjusted to within the range of 3.0 to 4.0), and the obtained extract fraction was used as extract (8).

The Middle Eastern crude oil was subjected to an atmospheric distillation apparatus, the obtained atmospheric distillation residue was subjected to a vacuum distillation apparatus, and the obtained 500!\1 equivalent vacuum distillation fraction was converted to a furfural extraction apparatus (operating conditions: column top temperature 1 1 0 to 1 30 ^° 0, column bottom temperature 60 to 80 ^° 0, solvent ratio adjusted to 1.0 to 3.0), and the resulting raffinate fraction is hydrorefining equipment (operating conditions: precious metal system). Using a catalyst, liquid space velocity 1. 〇 to 2.0 _ ¹ , reaction temperature 27 〇 to 330 ° 0, hydrogen oil ratio 1 500 to 2500 !_/!_, hydrogen partial pressure 4. 〇 to 6.

The hydrogenated refined oil obtained is subjected to solvent dewaxing equipment (operating conditions: mixed solvent of methyl ethyl ketone and toluene, primary solvent ratio 2.0, secondary solvent ratio 0.8, dewaxing). The dewaxed oil obtained was used as dewaxed oil (Mitsumi).

Extract (8)/dewaxed oil (Mitsumi) were mixed at a mass ratio of 60/40 to obtain the process oil of Example 1.

[0066] <Example 2-1>

Middle Eastern 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 subjected to compression liquefaction propane deasphalting extraction apparatus (operating conditions: tower top temperature 50 to 80 °0, bottom temperature 40-70°0, solvent ratio 5.0 〇 2020/175 512 24 boxes (: 170? 2020 /007603

The obtained deasphalted oil is subjected to a furfural extraction device (operating conditions: column top temperature 100 to 120 ^° 0, column bottom temperature 50 to 70 ^° 0, solvent ratio 3. The extract fraction thus obtained was used as extract (○).

The Middle Eastern crude oil was subjected to an atmospheric distillation apparatus, the obtained atmospheric distillation residue was subjected to a vacuum distillation apparatus, and the obtained 500!\1 equivalent vacuum distillation fraction was converted to a furfural extraction apparatus (operating conditions: column top temperature 10 °C). ◯ to 120 ^° 0, column bottom temperature 50 to 70 ^° 0, solvent ratio adjusted to 1.0 to 3.0), and the resulting raffinate fraction is hydrorefining equipment (operating conditions: precious metal system). Using a catalyst, the liquid space velocity is 1.0 to 2.0 _ ¹ , the reaction temperature is 32 〇 to 370°0, the hydrogen oil ratio is 1 500 to 2500 !_/!_, and the hydrogen partial pressure is 8.0 〜 10.

The hydrogenated refined oil obtained is subjected to a solvent dewaxing apparatus (operating conditions: a mixed solvent of methyl ethyl ketone and toluene, a primary solvent ratio of 1.3, a secondary solvent ratio of 1.3, and a dewaxing temperature of 1). The dewaxed oil obtained was used as dewaxed oil (mouth).

The extract (◯/dewaxed oil (mouth)) was mixed at a mass ratio of 70/30 to obtain the process oil of Example 2.

[0067] <Example 3_1>

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 subjected to deliquescent extraction with propane (operating conditions: column top temperature 55 to 85 ^° 0, tower bottom temperature 45 to 75 ^° 0, solvent ratio adjusted to 1.0 to 4.0), and the resulting deasphalted oil was extracted with a furfural extractor (operating conditions: tower top temperature 110 ~ 1 30 ^° 0, column bottom temperature 60 to 80 ^° 0, solvent ratio adjusted to within the range of 3.0 to 4.0), and the obtained extract fraction was used as extract (norm).

The Middle Eastern crude oil was subjected to an atmospheric distillation apparatus, the obtained atmospheric distillation residue was subjected to a vacuum distillation apparatus, and the obtained 500!\1 equivalent vacuum distillation fraction was converted to a furfural extraction apparatus (operating conditions: column top temperature 10 °C). 5 to 125 ^° 0, column bottom temperature 55 to 75 ^° 0, solvent ratio adjusted to 1.2 to 2.8), and the resulting raffinate fraction is hydrorefining equipment. 〇 2020/175 512 25 units (: 170? 2020 /007603

(Operating conditions: using a precious metal catalyst, liquid space velocity 2. 〇 to 3.0 _ ¹ , reaction temperature 3 1 〇 to 360 ° 0, hydrogen oil ratio 1 500 to 2500 !_/!_, hydrogen partial pressure 8.5-1 2.

The hydrogenated refined oil obtained is subjected to a solvent dewaxing device (operating conditions: mixed solvent of methyl ethyl ketone and toluene, primary solvent ratio of 1.0 to 2.0, secondary solvent ratio of 0.5 to 1.4, dewaxing temperature—adjusted within the range of −15 to −25° ◯), and the resulting dewaxed oil was used as dewaxed oil ().

The extract (Minami)/dewaxed oil () was mixed in a mass ratio of 62/38 to obtain the process oil of Example 3.

[0068] <Example 4_1>

The naphthene crude oil was subjected to an atmospheric distillation device, the obtained atmospheric distillation residue was subjected to a vacuum distillation device, and the resulting vacuum distillation fraction equivalent to 1 000!\1 was hydrorefined (operating conditions: precious metal system). using a catalyst, the liquid hourly space velocity 1. 〇_～ 3. 011 ^1, reaction temperature 2 70 ° 〇_～340 ° 0, hydrogen oil ratio 1 400-2800! _ /! _, hydrogen partial pressure of 3. 〇_～ 9 .

The hydrogenated refined oil obtained was used as the hydrogenated refined oil (<).

The naphthene 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 (!_).

The hydrorefined oil (<) and the vacuum distillation residue (!_) were mixed so that the kinematic viscosity at 100°° would be around 5500^ /, and the process oil of Example 4 was obtained.

[0069] <Example 5-1>

The extract (Mitsumi) was used as the process oil of Example 5.

[0070] <Example 6-1>

The extract (◯) was used as the process oil of Example 6.

[0071] <Comparative Example 1 _ 1>

The Middle Eastern crude oil was subjected to an atmospheric distillation apparatus, the obtained atmospheric distillation residue was subjected to a vacuum distillation apparatus, and the obtained 500!\1 equivalent vacuum distillation fraction was converted to a furfural extraction apparatus (operating conditions: column top temperature 10 °C). ◯ to 1 30°0, tower bottom temperature 50 to 80°0, solvent ratio adjusted to 1.0 to 3.0), and the resulting raffinate fraction is hydrorefining equipment. 〇 2020/175 512 26 boxes (: 170? 2020 /007603

(Operating conditions:! Using a noble metal catalyst, the liquid hourly space velocity 1. 〇_～ 3. 011 ^1, reaction temperature 280 to 340 ° 0, hydrogen oil ratio 1 500-25001 \ 1 _ / _, hydrogen partial pressure 6.〇〜10.

The hydrogenated refined oil obtained is subjected to a solvent dewaxing device (operating conditions: mixed solvent of methyl ethyl ketone and toluene, primary solvent ratio of 1.0 to 2.0, secondary solvent ratio of 0.5 to 1.4, dewaxing temperature — adjusted to within the range of 15 to 25 °C), and the dewaxed oil obtained was used as dewaxed oil (◦).

The Middle Eastern 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 (!!).

The naphthene crude oil was subjected to an atmospheric distillation device, the obtained atmospheric distillation residue was subjected to a vacuum distillation device, and the resulting vacuum distillation fraction equivalent to 1 000!\1 was hydrorefined (operating conditions: precious metal system). Using a catalyst, liquid hourly space velocity of 1.0 〜 3.01^ ^-1 , reaction temperature of 2 70° 〇 to 340° 0, hydrogen oil ratio of 1 400 to 2800 !_/!_, hydrogen partial pressure of 3.0 〜 9.

The resulting hydrogenated refined oil was used as a hydrogenated refined oil (丨).

The naphthene 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 (").

Dewaxed oil (◦)/vacuum distillation residue (!!) are mixed in a mass ratio of 50/50, and hydrorefined oil (丨)/vacuum distillation residue (”) is mixed in a mass ratio of 50/50. were mixed so that the kinematic viscosity of the 1 00 ° 〇 both a 30 〇 _{1 ^2/3} near to give up Rosesuoiru of Comparative example 1.

[0072] <Comparative Example 2-1>

The naphthene crude oil was subjected to an atmospheric distillation apparatus, the obtained atmospheric distillation residue was subjected to a vacuum distillation apparatus, and the obtained 2000!\1 equivalent vacuum distillation fraction was subjected to a hydrorefining apparatus (operating condition: precious metal catalyst). Liquid space velocity of 1.0 to 3.01^ ^-1 , reaction temperature of 2 70° to 340° 0, hydrogen oil ratio of 1 400 to 2800 !_/!_, hydrogen partial pressure of 3.0 to 9 .

The hydrogenated refined oil obtained was used as the process oil of Comparative Example 2.

[0073] <Comparative Example 3-1> The dewaxed oil (F) was used as the process oil of Comparative Example 3.

[0074] <Comparative Example 41-1>

The above extract (E)/dewaxed oil (F) was mixed in a mass ratio of 80/20 to obtain a process oil of Comparative Example 4.

[0075] 2. Measurement of properties of process oil

The process oils obtained in the above Examples and Comparative Examples were used as samples, and the following items were measured.

[0076] [Craigel method]

Clay gel method (Clay gel column chromatography): ASTM D 2007— 1 1 StandardTest Method for Characteristic Groups m Rubber Extender and Processing Oils and Other Petroleum-Derived Oils by the Clay-Gel A bsorpt ion Chromatographic Method. Minutes and polar components (mass%) were calculated.

[0077] [Aromatic fractionation using HPLC]

Fractionation of aromatics using HP LC (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 following procedure was performed.

Pretreatment was performed by diluting the sample 5 times with hexane. The column used was Spherisorb A5 Y 250X4.6 mm manufactured by Waters Co., the flow rate was 2.5 mL/min, the UV detector was used as the detector, and the wavelength was measured at 270 nm. Hexane was used as the eluent from the time of sample introduction to 0 to 10.0 minutes, and from 100 to 30.0 minutes from 100% by mass of hexane to 40% by mass of dichloromethane and 60% by mass of hexane. %, the dichloromethane content was increased linearly in the mixed solution. Change the mixed solution of 40% by mass of dichloromethane and 60% by mass of hexane to 100% by mass of dichloromethane within the time of 30.0 to 30.1 minutes after introduction of the sample, and after 30.1 minutes, 100% by mass of dichloromethane. % Was used. From the obtained peak area, the content (% by mass) of aromatic hydrocarbon by ring was determined by the following formula. Here, 1-ring area is the total peak area from the peak of benzene to the peak immediately before naphthalene, and 2-ring area is the total peak area from the peak of naphthalene to the peak immediately before anthracene. The area of 3 or more rings is the sum of the peak areas after the anthracene peak.

1-ring aromatic content (mass %) = (1 ring area / (1 ring area + 0.1 X2 ring area + 0.025 X3 or more ring area)) X 100

2-ring aromatic content (mass %) = (0.1 X2 ring area / (1 ring area + 0.1 X2 ring area + 0.025 X3 or more ring area)) X 100

Aromatic content of 3 or more rings (mass %) = (0.025 X3 ring area / (1 ring area + 0.1 X2 ring area + 0.025 X3 ring or more area)) X 100

[0078] [Kinematic viscosity (100 °C)]

Measured according to J I S K 2283:2000.

[0079] [Aniline point]

ASTM D 611 — 1 2 Standard Test Methods for Aniline Point and Mixed Amline Point of Petroleum Products and Hydrocarbon Solvents.

[0080] [Glass transition point (T g)]

The glass transition point was obtained from the calorific value change peak in the glass transition region, which was 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 the temperature was started after the initial temperature was maintained for a certain period of time. Specifically, the measurement was performed under the following conditions.

Equipment: Hitachi High-Tech Science DSC 7020

Initial temperature: _ 90 ^° C, hold for 10 minutes

Rate of temperature rise: 10 ^° C/min

End temperature: 30 ^° C, hold for 5 minutes [0081] [Viscosity Specific Gravity Constant (VGC)]

A S T M D 2 1 40—08 Standard Practice for Cal Leu lat i ng Carbon-Type Composition of Insulating Oi Is of Petroleum Origin.

[0082] [%C A]

A S T M D 2 1 40—08 Standard Practice for Cal Leu lat Ing Carbon-Type Composition of Insulating Oi Is of Petroleum Origin.

[0083] [Content of Benzo (a) Pyrene and Specific Aromatic Compound (P A H s)]

European Standard EN 1 6 1 43 :20 1 3 Petroleum products-Determi nat i on of content of Benzo (a) pyrene (BaP) and selected po lycyc lic aromat ic hydrocarbons (PAH) in extender oi ls-Procedure using double LC c The measurement was performed according to the rules of Leaning and GC/MS analysis.

P A H s means the following:

1) Benzo (a) Pyrene (B a P)

2) Benzo (e) Pyrene (B e P)

3) Benzo (a) Anthracene (B a A)

4) Chrysene (C H R)

5) Benzo (b) Fluoranthene (B b F A)

6) Benzo (j) fluoranthene (B j F A)

7) Benzo (k) fluoranthene (B k F A)

8) Dibenzo (a, h) anthracene (D BA h A)

[0084] 3. Production of rubber composition

<Example 1_2 to Example 6_2>

The rubber polymer, the process oil produced in the above Examples 1-1 to 6-1 and other compounding agents (silica, silane coupling agent, antioxidant, vulcanization aid, zinc oxide, sulfur, addition of (Vulcanization accelerator) was prepared in the following composition, and then kneaded to obtain an unvulcanized rubber composition, which was then press-vulcanized and molded at 160°C. 〇 2020/175 512 30 units (: 170? 2020 /007603

[0085] <Comparative Example 1 _ 2 ~ Comparative Example 4-2>

A rubber polymer, the process oil produced in Comparative Examples 1-1 to 4-1 above, and other compounding agents (same as above) were prepared in the following composition, and then kneaded to obtain an unvulcanized product. After obtaining the rubber composition (1), press vulcanization molding was performed at 160 ^° .

[0086] The composition of the tire composition is shown in Table 1 below. "II" in the table represents parts by mass of various compounding agents based on 100 parts by mass of the rubber polymer.

[0087] [Table 1]

[0088] Rubber polymer

LANXESS 31_4526

Silica: Evonik 1]1_Ding (^311_7000 〇 [¾

Silane coupling agent: Evonik _175

-Anti-aging agent: Ouchi Shinko Chemical Industry Nocrac 6 (: Vulcanization aid: NOF stearic acid

Zinc Oxide: Toho Zinc's Zinc Oxide No. 3

Process oil: Each process oil produced in Examples and Comparative Examples Sulfur: Commercial sulfur for vulcanization

Vulcanization accelerator 8: Noxera manufactured by Ouchi Shinko Chemical Industry

Ouchi Shinko Chemical Industry Nox Cellar

[0089] Rubber kneading method: The following two-stage kneading was performed.

(-Step) 〇 2020/175 512 卩 (: 170? 2020 /007603

Testing machine: Labo Plastomill 600 manufactured by Toyo Seiki Seisakusho

Testing machine volume: 600 〇 〇

Filling ratio: 70% (mass ratio)

Number of revolutions: 100"

Temperature: 100° 〇 and the upper limit was 155° 〇

Kneading time: About 9 minutes

(Step)

-Testing machine: Ikeda Machinery's electric heating type high temperature machine, size: 6 inch ø 16 inch

-Number of revolutions: Front mouth 25 "Lord 111

-Rotation ratio: Front-to-back ratio 1:1 .22

Temperature: 23 ± 10 ^° 〇

[0090] 4. Measurement of physical properties of rubber composition

Test pieces of 8111111 ø X 10111111 were prepared from the rubber kneaded pieces after press vulcanization molding of the above Examples and Comparative Examples, and the following items were measured on the test pieces.

[0091] [tan 5 (0°○]

Was used in the torsion mode at a frequency of 10, a measurement temperature range of 50° to 100°, a heating rate of 204, and a dynamic strain of 0.1%. From the obtained variable temperature tan 5, the value at 0 ^° is extracted.

A value of 3 (5 ^° 0) is an index of wet grip performance, and the larger this value, the better the wet grip performance.

[0092] [Person 3 5 (50°○]

Was used in the torsion mode at a frequency of 10, a measurement temperature range of 50° to 100°, a heating rate of 204, and a dynamic strain of 0.1%. The value at 50 ^° was extracted from the obtained temperature variable tan 5.

Tan S (50 ^° C) is an index of rolling resistance performance, and the smaller this value is, the better the rolling resistance performance is.

[0093] 5. Result 〇 2020/175 512 32 units (: 170? 2020 /007603

The above measurement results are shown below. The above Examples 1 — 1 and Examples 1 — 2 are abbreviated as Example 1. The same applies to other examples and comparative examples.

The measurement results of each item are shown in Table 2 below. The values of tanS (0 °C) and tanS (50 °C) are expressed as relative values with the real value of Example 6 (0.814 and 0.118, respectively) as 1.

[0095]

Each item of process oil: The underline indicates that it is outside the range specified in the embodiment.

1¾ _{60 [8]} : ◯ means that the content is less than 1111 (within the 1/81 01 regulation standard value).

Total of eight substances: ◯ means that the content is less than 10 111 (1^ (: within the 11 standard values)).

3 _1! 6 (0° ◯: Underline means that the value is less than 1 (wet grip performance is inferior).

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Saturated ratio”, and “1 ^to 1!_(Ratio of two-ring aromatic fraction fractionated using 3)”, and the results obtained by blending the above-mentioned Procel oil The rubber composition of 6 had both wet grip performance and rolling resistance performance, and was extremely excellent.

In particular, the rubber compositions of Examples 1 to 3 obtained by blending the process oils in which the “ratio of aromatics by the Clay gel method” satisfies the range specified in the embodiment have wet grip performance and rolling resistance performance. It can be seen that good values are compatible.

Moreover, the content of benzo (3) pyrene and the specific aromatic compound (1 ^to | ₃ ) in each of the process oils of Examples and Comparative Examples is

It was confirmed that the rule was satisfied.

As described above, each configuration and the combination thereof in each embodiment are examples, and the configuration can be added, omitted, replaced, and other changes without departing from the spirit of the present invention. Further, the present invention is not limited by each embodiment, but is limited only by the scope of the claims.

Industrial availability

[0098] It is possible to manufacture a rubber composition having excellent rolling resistance performance and wet grip performance.

Explanation of symbols

[0099] 10 Vacuum distillation apparatus

1 1 Vacuum distillation fraction

1 2 Vacuum distillation residue

20 Debris extraction device

2 2 Deasphalted oil

30 solvent extractor

3 1, 3 2 roughinate

3 3, 3 4 extract 5512 35 卩 (: 170? 2020 /007603

Hydrorefining equipment

1, 42 Hydrogenated refined oil

Dewaxing device

1, 52 Dewaxed oil

Oil containing petroleum-based aromatics

Claims

〇 2020/175 512 36 (: 170? 2020/007603 Claims

[Claim 1] The proportion of the saturated component by the clay gel method is 40% by mass or less,

!! !_ (The proportion of the two-ring aromatics fractionated using 3 is 10% by mass or more and 30% by mass or less based on 100% by mass of the aromatic content by the Cragel method.

A petroleum-based aromatic-containing oil having a benzo(8)pyrene content of 1 mass 111 or less and a total content of the specific aromatic compounds of 1) to 8) below is 10 mass or less.

1) Benzo (3) Pyrene

2) Benzo (6) Pyrene

3) Benzo (3) Anthracene

4) Chrysene

5) Benzo (13) Fluoranthene

6) Benzo (") fluoranthene

7) Benzo (1<) Fluoranthene

8) Dibenzo (3, 11) Anthracene.

[Claim 2] The petroleum-containing aromatic-containing oil according to claim 1, wherein a ratio of a saturated component by the clay gel method is 20% by mass or more.

[Claim 3] The proportion of the bicyclic aromatic fraction fractionated by using !!? 1_(3 is 28 mass% or less with respect to 100 mass% of the aromatic content. The petroleum-containing aromatic-containing oil according to 1 or 2.

[Claim 4] The petroleum-containing aromatic-containing oil according to any one of claims 1 to 3, wherein a ratio of a saturated component by the clay gel method is 35% by mass or less.

[Claim 5] The proportion of the two-ring aromatics fractionated by using !!? 1_(3 is 20% by mass or more based on 100% by mass of the aromatics. The petroleum-based aromatic-containing oil according to any one of 1 to 4.

6. The petroleum-containing aromatic-containing oil according to any one of claims 1 to 5, wherein a ratio of a saturated component by the clay gel method is 30% by mass or less. 〇 2020/175 512 37 卩(: 170? 2020/007603

[Claim 7] The proportion of the bicyclic aromatic fraction fractionated using 1 ^to 1 to 1_ ⁽ 3 is 25 mass% or less with respect ^to 100 mass% of the aromatic content. Item 7. A petroleum-based aromatic-containing oil according to any one of items 1 to 6.

[Claim 8] The proportion of the two-ring aromatics fractionated by using !!?!_ ⁽ 3 is 24.5% by mass or less based on 100% by mass of the aromatics. The petroleum-containing aromatic-containing oil according to any one of claims 1 to 7.

[Claim 9] The petroleum-based aromatic-containing oil according to any one of claims 1 to 8, which is an extender oil or a process oil used by being mixed with rubber.

[Claim 10] A rubber composition containing the petroleum-based aromatic-containing oil according to any one of claims 1 to 9 and a rubber.

[Claim 11] A tire containing the petroleum-containing aromatic-containing oil according to any one of claims 1 to 9.

[Claim 12] A method for producing the tire according to claim 11, which comprises compounding rubber and the petroleum-based aromatic-containing oil according to any one of claims 1 to 9 and vulcanizing the compound. Build method.