TW202037581A - 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

Containing petroleum-based aromatic oil, rubber composition, tire and tire manufacturing method

The present invention relates to a method for manufacturing a rubber composition, a tire, and a tire containing petroleum-based aromatic oil. This application claims priority based on Japanese Patent Application No. 2019-035836 filed in Japan on February 28, 2019, and the content is cited here.

In most cases, processing oil is generally blended into rubber products to improve the processability or softening properties of the rubber composition. For example, in synthetic rubbers such as SBR (styrene butadiene copolymer rubber), extension oil (extending oil) is blended in it (rubber blending oil) during its synthesis. In addition, in rubber processed products such as tires, processing oil (processing oil) is blended to improve the processability or the quality of rubber processed products. Here, extended oil and processing oil are distinguished and shown, but they are sometimes collectively referred to as processing oil. On the other hand, in Europe, the following restrictions have been applied since 2010, that is, rubber compounding oil containing more than a specific amount of specific carcinogenic polycyclic aromatic compounds cannot be used to manufacture tires or tire parts (REACH (Registration, Evaluation, Authorisation and Restriction of Chemicals, chemical registration, evaluation, licensing and restriction) regulations). Therefore, rubber blending oils that comply with REACH regulations are required.

The trend of fuel consumption saving in the automobile field has attracted much attention, and further improvements are required for fuel consumption saving of tires. With the launch of the tire labeling system in January 2010, there is a strong demand for tires to improve the "rolling resistance performance" that represents fuel economy and the "wet grip performance" that represents braking performance. However, generally speaking, the rolling resistance performance and the wet grip performance are in a contradictory relationship, and the combination of these high standards becomes a problem.

In order to improve the rolling resistance of tires, in addition to reducing air resistance, or researching and designing tread patterns, there are methods to suppress the hysteresis loss of the rubber composition, that is, the tread rubber itself. In recent years, it has become popular to formulate silica composites as one of the reinforcing materials for tire formulations. If only silica is blended, silica agglomerates with each other in the composite, and the silica molecules are likely to rub against each other to cause energy loss when the rubber is deformed. In view of this, in terms of maintaining wet grip performance and improving rolling resistance performance, a method for controlling the existence of silica by applying terminal modified silica or silane coupling agent is proposed. According to Patent Document 1, there is disclosed a rubber composition for tires obtained by a manufacturing method including the following steps: a first basic kneading step of kneading a rubber component, a water-containing calcium carbonate, and a silane coupling agent; and a second The basic kneading step involves kneading the kneaded product obtained by the above-mentioned first basic kneading step and silica. Thereby, it is possible to obtain a rubber composition for tires that has excellent dispersibility of silicon dioxide and can improve fuel economy, wet grip performance, and abrasion resistance in a balanced manner. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2012-153787

[The problem to be solved by the invention]

However, the tires are required to further improve the "rolling resistance performance" and "wet grip performance", and so on. In response to this requirement, various methods are expected from consideration of rubber components other than silica or silane coupling agents.

The present invention was completed to eliminate the above-mentioned problems, and its purpose is to provide a petroleum-based aromatic oil that can produce a rubber composition with excellent rolling resistance and wet grip performance, and meets REACH regulations. In addition, the object of the present invention is to provide a rubber composition that contains petroleum-based aromatic oil that meets REACH regulations and has excellent rolling resistance performance and wet grip performance. Furthermore, an object of the present invention is to provide a tire containing the above-mentioned petroleum-based aromatic oil, and a method of manufacturing the above-mentioned tire. [Technical means to solve the problem]

The inventors of the present invention have conducted intensive research to solve the above-mentioned problems, and found that by blending oils containing saturated components and aromatic components in the following specific amounts, particularly bicyclic aromatic components, rolling resistance performance and The rubber composition with excellent wet grip performance has completed the present invention. That is, one aspect of the present invention is the following petroleum-based aromatic oil, rubber composition, tire, and tire manufacturing method.

(1) An oil containing petroleum-based aromatics whose saturation ratio obtained by the clay gel method is 40% by mass or less, The ratio of the bicyclic aromatic components separated by HPLC (high performance liquid chromatography) is 10% by mass to 30% by mass relative to 100% by mass of the above-mentioned aromatic components, The content of benzo(a)pyrene is 1 mass ppm or less, and The total content of the specific aromatic compounds in the following 1) to 8) is 10 mass ppm or less. 1) Benzo(a)pyrene (BaP) 2) Benzo(e)pyrene (BeP) 3) Benzo(a)anthracene (BaA) 4) 哛 (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 oil described in (1) above, wherein the saturated content obtained by the clay gel method is 20% by mass or more. (3) The petroleum-based aromatic oil as described in (1) or (2) above, wherein the ratio of the bicyclic aromatic fraction separated by HPLC is 28% by mass or less with respect to 100% by mass of the aromatic fraction. (4) The petroleum-based aromatic oil according to any one of (1) to (3) above, wherein the saturated content obtained by the clay gel method is 35% by mass or less. (5) The petroleum-based aromatic oil according to any one of (1) to (4) above, wherein the ratio of the above-mentioned bicyclic aromatic components separated by HPLC to 100% by mass of the above-mentioned aromatic components is 20 Above mass%. (6) The petroleum-based aromatic oil according to any one of (1) to (5) above, wherein the saturated content obtained by the clay gel method is 30% by mass or less. (7) The petroleum-based aromatic oil according to any one of (1) to (6) above, wherein the ratio of the above-mentioned bicyclic aromatic components separated by HPLC to 100% by mass of the above-mentioned aromatic components is 25 Less than mass%. (8) The petroleum-based aromatic oil according to any one of the above (1) to (7), wherein the ratio of the bicyclic aromatic fraction separated by HPLC is 24.5 relative to 100% by mass of the aromatic fraction Less than mass%. (9) The petroleum-based aromatic oil as described in any one of (1) to (8) above, which is an extender oil or processing oil used by mixing with rubber. (10) A rubber composition containing the petroleum-based aromatic oil as described in any one of (1) to (9) above, and rubber. (11) A tire containing the petroleum-based aromatic oil as described in any one of (1) to (9) above. (12) A method for manufacturing a tire as described in (11) above, which comprises compounding rubber and vulcanizing the petroleum-based aromatic oil as described in any one of (1) to (9) above. [Effects of Invention]

According to the present invention, it is possible to provide a petroleum-based aromatic oil, which can produce a rubber composition with excellent rolling resistance performance and wet grip performance, and meets REACH regulations. Furthermore, according to the present invention, it is possible to provide a rubber composition that contains petroleum-based aromatic oils that meet the REACH regulations and has excellent rolling resistance performance and wet grip performance. Furthermore, according to the present invention, it is possible to provide a tire containing the above-mentioned petroleum-based aromatic oil and a method of manufacturing the above-mentioned tire.

Hereinafter, embodiments of the petroleum-based aromatic oil, rubber composition, tire, and tire manufacturing method of the present invention will be described.

"Containing petroleum-based aromatic oil" In the petroleum-based aromatic oil of the embodiment, the ratio of the saturated content obtained by the clay gel method, the ratio of the bicyclic aromatic content separated by HPLC, the content of benzo(a)pyrene, and the specific aroma The content of the group compound satisfies a specific numerical range. The tanδ (50°C) and tanδ (0°C) values of rubber compositions or tires containing petroleum-based aromatic oils that satisfy the following numerical ranges of these items become good, thereby having both wet grip performance and Rolling resistance performance.

Here, "wet grip performance" is the so-called braking performance, and the tanδ (0°C) obtained by the dynamic viscoelasticity test becomes its index. "Rolling resistance performance" is the so-called fuel economy performance, and the tanδ (50°C) obtained by the dynamic viscoelasticity test becomes its index.

The above-mentioned "petroleum series" means hydrocarbon oil containing petroleum (Petroleum-Derived). The above-mentioned "aromatic oil" means that the ratio of the saturated fraction obtained by the clay gel method and the ratio of the bicyclic aromatic fraction separated by HPLC satisfy the following numerical range. If the petroleum-based aromatic oil of the embodiment satisfies the numerical range of the above items, the preparation method or classification is not particularly limited, for example: atmospheric distillation residue, atmospheric distillation fraction, vacuum distillation fraction, vacuum distillation The residue, deasphalted oil, solvent extraction raffinate, hydrorefined oil, dewaxed oil, solvent extraction extract, etc., preferably contain oil produced by the following production method of petroleum-based aromatic oil. The content ratio of the petroleum-derived hydrocarbon oil in the petroleum-based aromatic oil may be 50% by mass or more, 80% by mass or more, or 95% by mass or more.

Hereinafter, each item of the properties of the petroleum-based aromatic oil contained in the embodiment will be described.

The components of petroleum-based oils can be classified into saturated components, aromatic components, and polar components (mass%) by the clay gel method. The following values of saturation, aromatic, or polar components (mass%) obtained by the clay gel method are relative to 100% by mass of the total amount of saturated, aromatic, and polar components.

The saturated content ratio of the petroleum-based aromatic oil of the embodiment obtained by the clay gel method is 40% by mass or less, preferably 35% by mass or less, and more preferably 30% by mass or less. The ratio of the saturated content obtained by the clay gel method of the petroleum-based aromatic oil of the embodiment is preferably 5% by mass or more, more preferably 20% by mass or more, and still more preferably 22% by mass or more. As an example of the numerical range of the above-mentioned numerical value, the ratio of the saturated content obtained by the clay gel method of the petroleum-based aromatic oil of the embodiment can be 5 mass% or more and 40 mass% or less, and can be 20 mass% or more and 35 mass% % Or less, and may be 22% by mass to 30% by mass. By making the ratio of the above-mentioned saturation content meet the above-mentioned value, the tanδ (50°C) and tanδ (0°C) values of the rubber composition or tire containing the above-mentioned oil become good, thereby having both wet grip performance and Rolling resistance performance. It is believed that the reason is that the polarity of the saturated component as a hydrocarbon is appropriately balanced, shows a certain affinity for rubber, and also shows a certain affinity for rubber compounding agents. Therefore, by making the ratio of the saturated component within the above range, The physical properties of the manufactured rubber composition or tire become suitable.

The ratio of the aromatic content obtained by the clay gel method of the petroleum-based aromatic oil of the embodiment is preferably 50% by mass or more, more preferably 51% by mass or more, and still more preferably 58% by mass or more. The ratio of the aromatic content obtained by the clay gel method of the petroleum-based aromatic oil of the embodiment is preferably 74% by mass or less, more preferably 70% by mass or less, and still more preferably 66% by mass or less. As an example of the numerical range of the above-mentioned numerical value, the ratio of the aromatic content obtained by the clay gel method containing the petroleum-based aromatic oil of the embodiment can be 50% by mass or more and 74% by mass or less, and can be 51% by mass or more and 70 The mass% or less may be 58 mass% or more and 66 mass% or less. By making the ratio of the above-mentioned aromatic components meet the above-mentioned value, the tanδ (50°C) and tanδ (0°C) values of the rubber composition or tire containing the above-mentioned oil become good, thereby achieving both wet grip performance And rolling resistance performance. The reason for this is thought to be that the aromatic component shows a high affinity for rubber. Therefore, by making the ratio of the aromatic component within the above range, the physical properties of the manufactured rubber composition or tire can be made suitable.

The ratio of the polar component obtained by the clay gel method containing the petroleum-based aromatic oil of the embodiment is preferably 3% by mass or more, more preferably 4% by mass or more, and still more preferably 5% by mass or more. The ratio of the polar component obtained by the clay gel method containing the petroleum-based aromatic oil of the embodiment is preferably 12% by mass or less, more preferably 11% by mass or less, and still more preferably 10% by mass or less. As an example of the numerical range of the above-mentioned numerical values, the ratio of polar components obtained by the clay gel method containing petroleum-based aromatic oils of the embodiment can be 3% by mass to 12% by mass, and can be 4% by mass to 11% by mass % Or less, and may be 5 mass% or more and 10 mass% or less. The ratio of the above-mentioned polar component and the ratio of the above-mentioned saturated component and aromatic component are in an inverse relationship. By making the ratio of the above-mentioned polar component meet the above-mentioned value, the tanδ (50°C) and tanδ of the rubber composition or tire containing the above oil The value of (0°C) becomes better, so that it has both wet grip performance and rolling resistance performance.

The ratio of saturated, aromatic, and polar components (mass%) obtained by the clay-gel method can be used in accordance with ASTM D2007-11 to apply the clay-gel absorption chromatography method to rubber extenders, processing oils and other petroleum The characteristic bases in the derived oil are determined by the standard test method (Standard Test Method for Characteristic Groups in Rubber Extender and Processing Oils and Other Petroleum-Derived Oils by the Clay-Gel Absorption Chromatographic Method).

The ratio of the bicyclic aromatic component separated by HPLC of the petroleum-based aromatic oil of the embodiment is 10% by mass or more, preferably 16% by mass or more, and more preferably 20 relative to 100% by mass of the above-mentioned aromatic component. % By mass or more, more preferably 22% by mass or more, particularly preferably 23% by mass or more. The ratio of the bicyclic aromatic component separated by HPLC of the petroleum-based aromatic oil of the embodiment is 30% by mass or less, preferably 28% by mass or less, and more preferably 26, relative to 100% by mass of the above-mentioned aromatic component % By mass or less, more preferably 25% by mass or less, particularly preferably 24.5% by mass or less. As an example of the numerical range of the above-mentioned numerical value, the ratio of the bicyclic aromatic component separated by HPLC using the petroleum-based aromatic oil of the embodiment can be 10% by mass or more and 30% by mass relative to 100% by mass of the above-mentioned aromatic component. % Or less, may be 16 mass% or 28 mass% or less, 20 mass% or more and 26 mass% or less, 22 mass% or more and 25 mass% or less, or 23 mass% or more and 24.5 mass% or less. Here, by making the ratio of the above-mentioned bicyclic aromatic component meet the above-mentioned value, the tanδ (50°C) and tanδ (0°C) values of the rubber composition or tire containing the above-mentioned oil become good, thereby achieving both Wet grip performance and rolling resistance performance. According to the data shown in the following examples, the ratio of aromatic components with more than two rings in the aromatic components greatly contributes to both wet grip performance and rolling resistance performance. Among them, the bicyclic aromatic component not only improves wet grip performance and rolling resistance performance, but also has good properties from the viewpoint of meeting REACH regulations.

The ratio of the one-ring aromatic component separated by HPLC of the petroleum-based aromatic oil of the embodiment to 100% by mass of the above-mentioned aromatic component is preferably 48% by mass or more, more preferably 50% by mass or more, and more Preferably, it is 52% by mass or more. The ratio of the one-ring aromatic component separated by HPLC of the petroleum-based aromatic oil of the embodiment is relative to 100% by mass of the above-mentioned aromatic component, preferably 64% by mass or less, more preferably 62% by mass or less, and more Preferably, it is 60% by mass or less. As an example of the numerical range of the above-mentioned numerical value, the ratio of the one-ring aromatic component separated by HPLC using the petroleum-based aromatic oil of the embodiment may be 48% by mass or more and 64% by mass relative to 100% by mass of the above-mentioned aromatic component. Below, it may be 50% by mass or more and 62% by mass or less, and may be 52% by mass or more and 60% by mass or less. The ratio of the above-mentioned one-ring aromatic component and the ratio of the above-mentioned two-ring or more aromatic component are in an inverse relationship. By making the ratio of the above-mentioned one-ring aromatic component meet the above value, the tanδ( 50°C) and tanδ (0°C) values become better, so that it has both wet grip performance and rolling resistance performance.

The ratio of the aromatics of three or more rings separated by HPLC of the oil-containing aromatic oil of the embodiment relative to 100% by mass of the above-mentioned aromatics, preferably 10% by mass or more, more preferably 12% by mass or more , More preferably 14% by mass or more, particularly preferably 16% by mass or more. The ratio of the aromatic components with three or more rings separated by HPLC in the embodiment of the petroleum-based aromatic oil is relative to 100% by mass of the above-mentioned aromatic components, preferably 28% by mass or less, more preferably 26% by mass or less , More preferably 24% by mass or less, particularly preferably 23% by mass or less. As an example of the numerical range of the above-mentioned numerical value, the ratio of aromatic components with three or more rings separated by HPLC in the petroleum-based aromatic oil of the embodiment may be 10% by mass or more with respect to 100% by mass of the above-mentioned aromatic components 28 mass% or less, 12 mass% or more and 26 mass% or less, 14 mass% or more and 24 mass% or less, and 16 mass% or more and 23 mass% or less. By making the ratio of the aromatic components of the above three rings or more meet the above value, the rubber composition or tire containing the above oil has good tanδ (50°C) and tanδ (0°C) values, thereby achieving both moisture Ground grip performance and rolling resistance performance are also good in terms of meeting REACH regulations.

The separation of the aromatic components by HPLC can be determined by the measurement conditions described in the following examples.

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

By making the content of the benzo(a)pyrene and the above-mentioned specific aromatic compounds (PAHs) within the above-mentioned range, a safer rubber compound can be made that complies with the REACH regulations on the content of extender oil. oil.

The content of these compounds can be obtained by the following method, that is, after the components of the object are separated and concentrated, a sample with internal standard substances is prepared, and by GC-MS (Gas chromatography-mass spectrometry, gas chromatography Analysis-mass spectrometry) analysis for quantitative analysis. The content of benzo(a)pyrene and specific aromatic compounds (PAHs) can be based on the European standard EN 16143: 2013 Petroleum Products-Benzo(a) pyrene (BaP) and selected polycyclic aromatic hydrocarbons ( (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).

The dynamic viscosity of the petroleum-based aromatic oil of the embodiment at 100°C is preferably 25 mm ² /s or more, more preferably 27 mm ² /s or more, and still more preferably 28 mm ² /s or more. The dynamic viscosity of the petroleum-based aromatic oil of the embodiment at 100°C is preferably 75 mm ² /s or less, more preferably 58 mm ² /s or less, and still more preferably 50 mm ² /s or less. As an example of the numerical range of the above values, the dynamic viscosity of the petroleum-based aromatic oil of the embodiment at 100°C can be in the range from 25 mm ² /s to 75 mm ² /s, and can be 27 mm ² /s The range above 58 mm ² /s can be above 28 mm ² /s and below 50 mm ² /s. If the value of the above-mentioned dynamic viscosity satisfies the above-mentioned value, the viscosity of the rubber composition or tire containing the petroleum-based aromatic oil becomes better, so the values of tanδ (50°C) and tanδ (0°C) become better. As a result, both wet grip performance and rolling resistance performance become better. Furthermore, if the value of the above-mentioned dynamic viscosity is equal to or less than the above-mentioned upper limit value, the migration or workability for blending the petroleum-based aromatic oil into rubber becomes good.

The kinematic viscosity at 100°C can be calculated according to JIS K2283:2000.

The aniline point of the petroleum-based aromatic oil of the embodiment is preferably 60°C or higher, more preferably 65°C or higher, and still more preferably 70°C or higher. The aniline point of the petroleum-based aromatic oil of the embodiment is preferably 100°C or lower, more preferably 95°C or lower, and still more preferably 90°C or lower. As an example of the numerical range of the above-mentioned values, the aniline point of the petroleum-based aromatic oil of the embodiment can be in the range of 60°C to 100°C, 65°C to 95°C, and 70°C to 90°C. The range below ℃. The aniline point is the temperature at which equal amounts of aniline and oil are mixed, which is an indicator of rubber compatibility. If the aniline point is less than the above upper limit, the oil will melt with aniline even without excessive heating, and the rubber compatibility is higher, which is preferable. That is, if the value of the aniline point satisfies the above-mentioned value, the affinity of the petroleum-based aromatic oil for rubber becomes better, and the physical properties of the manufactured rubber composition or tire become better.

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

The glass transition point (Tg) of the petroleum-based aromatic oil of the embodiment is preferably -58°C or higher, more preferably -56°C or higher, and still more preferably -54°C or higher. The glass transition point (Tg) of the petroleum-based aromatic oil of the embodiment is preferably -44°C or lower, more preferably -46°C or lower, and still more preferably -48°C or lower. As an example of the numerical range of the above-mentioned numerical value, the glass transition point (Tg) of the petroleum-based aromatic oil of the embodiment can be in the range of -58℃ to 44℃, and it can be in the range of -56℃ to 46℃. The range can be above -54°C and below 48°C. If the glass transition point satisfies the above-mentioned value, the physical properties of the manufactured rubber composition or tire become better, which is important for improving wet grip performance and rolling resistance performance.

The glass transition point can be determined by the measurement conditions described in the following examples.

The viscosity specific gravity constant (VGC) of the petroleum-based aromatic oil of the embodiment is preferably 0.84 or more, more preferably 0.85 or more, and still more preferably 0.86 or more. The viscosity specific gravity constant (VGC) of the petroleum-based aromatic oil of the embodiment is preferably 0.92 or less, more preferably 0.90 or less, and still more preferably 0.89 or less. As an example of the numerical range of the above numerical value, the viscosity specific gravity constant (VGC) of the petroleum-based aromatic oil of the embodiment can be 0.84 or more and 0.92 or less, 0.85 or more and 0.90 or less, and can be 0.86 or more and 0.89 or less. The viscosity specific gravity constant is an index indicating the composition of the oil. Generally speaking, if the paraffinicity becomes higher, the value becomes lower, and if the aromaticity becomes higher, the value becomes higher. If the value of the above-mentioned viscosity specific gravity constant satisfies the above-mentioned value, the physical properties of the rubber composition or tire containing the petroleum-based aromatic oil will become better, so the values of tanδ (50°C) and tanδ (0°C) become even higher. Good, so that both wet grip performance and rolling resistance performance become better.

Viscosity specific gravity constant (VGC) can be calculated according to ASTM D2140-08 Standard Practice for Calculating Carbon-Type Composition of Insulating Oils of Petroleum Origin (Standard Practice for Calculating Carbon-Type Composition of Insulating Oils of Petroleum Origin).

The %CA obtained by ring analysis of the petroleum-based aromatic oil of the embodiment is preferably 12 or more, more preferably 14 or more, and still more preferably 16 or more. The %CA obtained by ring analysis of the petroleum-based aromatic oil of the embodiment is preferably 30 or less, more preferably 28 or less, and still more preferably 26 or less. As an example of the numerical range of the above numerical value, the %CA obtained by ring analysis of the petroleum-based aromatic oil of the embodiment can be 12 or more and 30 or less, 14 or more and 28 or less, and 16 or more and 26 or less. If the above %CA satisfies the above value, it will suppress the carcinogenicity of the polycyclic aromatic content, and at the same time have the tendency to improve the compatibility with rubber, so that the tanδ of the rubber composition or tire containing the above oil (50°C) and tanδ (0°C) values become better, so that both wet grip performance and rolling resistance performance become better.

%CA can be calculated according to ASTM D2140-08 standard operating regulations for calculating the carbon-type composition of petroleum-derived insulating oil.

The petroleum-based aromatic oil of the embodiment is suitable for use as an extender oil or processing oil that is mixed with rubber and used.

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

The manufacturing method of the petroleum-based aromatic oil of the embodiment includes: The step of obtaining an extract by solvent extraction; or The step of mixing the extract obtained by solvent extraction with the raffinate or the base oil obtained by refining the raffinate. Examples of the solvent extraction target include: vacuum distillation residue obtained by vacuum distillation of the residue obtained by atmospheric distillation of crude oil, deasphalted oil fraction obtained by deasphalting, or atmospheric distillation of crude oil The distillation residue is a vacuum distillation fraction obtained by vacuum distillation. In the solvent extraction, the extract can be obtained in the following way, that is, the solvent and the extract are separated and recovered by the solvent having affinity for aromatic hydrocarbons. The crude oil as the starting material can be used alone or in combination with various crude oils such as paraffinic crude oil and naphthenic crude oil, and paraffinic crude oil is particularly preferred.

Fig. 1 is a process chart explaining an example of a method for producing petroleum-based aromatic oil according to the embodiment. The crude oil is first processed by an atmospheric distillation device (not shown) to obtain an atmospheric distillation residue. The atmospheric distillation residue is sent to a vacuum distillation apparatus 10 to perform vacuum distillation, and a vacuum distillation residue 12 is obtained. The vacuum distillation residue 12 is processed by the deasphalting extraction device 20 to become deasphalted oil 22. After that, the deasphalted oil 22 is sent to the solvent extraction device 30. In the solvent extraction device 30, the deasphalted oil 22 is separated into a raffinate 32 and an extract 34. The raffinate 32 is hydrorefined by the hydrorefining device 40 to become a hydrorefined oil 42, and then dewaxed by the dewaxing device 50 to obtain a dewaxed oil 52. The obtained dewaxed oil 52 and the extract 34 can be mixed to obtain a petroleum-based aromatic oil 62.

Here, the case where the dewaxed oil 52 and the extract 34 are mixed to obtain the petroleum-based aromatic oil 62 is described, but the raffinate 32 or the hydrorefined oil 42 may be substituted for the dewaxed oil 52 and The extract 34 is mixed.

In addition, the vacuum distillation fraction 11 fractionated by the vacuum distillation device 10 is processed by the solvent extraction device 30 and separated into a raffinate 31 and an extract 33. The raffinate 31 is hydrorefined by the hydrorefining device 40 to become a hydrorefined oil 41, and then dewaxed by the dewaxing device 50 to obtain a dewaxed oil 51. The obtained dewaxed oil 51 and the extract 34 are mixed to obtain a petroleum-based aromatic oil 62. Here, the case where the dewaxed oil 51 and the extract 34 are mixed to obtain the petroleum-based aromatic oil 62 is described, but the raffinate 31 or the hydrorefined oil 41 may be substituted for the dewaxed oil 51 and The extract 34 is mixed.

Also, here, the case where the dewaxed oils 51, 52, etc., and the extract 34 are mixed to obtain the petroleum-based aromatic oil 62 is described, but the dewaxed oils 51, 52, etc., and the extract 33 mix instead of extract 34.

In addition, the extracts 33 and 34 may be the oil 62 containing petroleum-based aromatics.

Vacuum distillation is carried out under the condition that the final boiling point of the distilled oil is converted to normal pressure at 580°C or higher, or the initial boiling point of the residue is 450°C or higher, because the aromatic content of the obtained extract can be easily adjusted to A specific range is preferred. Deasphalting can be performed at tower top temperature: preferably 40-120°C, more preferably 50-100°C, tower bottom temperature: preferably 30-100°C, more preferably 40-90°C, solvent ratio: preferably Carry out under the conditions of 1-10, more preferably 1-9. Solvent extraction In order to obtain the extracts 33 and 34, it is preferable to perform a process of extracting the obtained deasphalted oil by a solvent having a selective affinity for aromatic hydrocarbons. As a solvent having selective affinity for aromatic hydrocarbons, a polar solvent may be used, and one or more selected from the group consisting of furfural, phenol, and N-methyl-2-pyrrolidone may be used. Since the specific extraction conditions for bringing the yield of the extract into the above-mentioned range also depend on the composition of the deasphalted oil, it cannot be determined singly, and can be performed by appropriately selecting the solvent ratio, pressure, temperature, etc. Generally speaking, the temperature at the top of the tower: preferably 100 to 155°C, more preferably 100 to 140°C, and the temperature at the bottom of the tower: preferably 40 to 120°C, more preferably 50 to 110°C, relative to oil 1 Solvent ratio: preferably 2 to 5, more preferably 3 to 4.5, contact with the solvent. On the other hand, in order to obtain the raffinates 31 and 32, it is preferable to perform a solvent purification treatment by extracting a vacuum distillation fraction with a boiling point of 300 to 700°C in terms of normal pressure by a solvent having affinity for aromatic hydrocarbons. As a solvent having selective affinity for aromatic hydrocarbons, one or more of furfural, phenol, and N-methyl-2-pyrrolidone can be selected and used. In the solvent refining step, under the usual conditions of refining lubricating oil base oil, for example, when furfural is used as the extraction solvent, the temperature at the top of the tower: preferably 90-150°C, more preferably 100-140°C , Tower bottom temperature: preferably 40～90℃, more preferably 50～80℃, relative to oil 1 solvent ratio: preferably 0.5～4, more preferably 1～3, contact with solvent . According to other requirements, the raffinate is dewaxed by hydrofining and/or solvent dewaxing or hydrodewaxing treatment to obtain a better base oil. The above-mentioned hydrogenation purification 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 5-15 MPa and a temperature of 250- It can be carried out under the conditions of 400℃ and liquid space velocity (LHSV) 1～5 h ^-1 . In addition, the above-mentioned solvent dewaxing is carried out, for example, in a mixed solvent of methyl ethyl ketone/toluene, under the conditions of solvent/oil ratio (volume ratio) = 1/1 to 5/1, and a temperature of -10 to -40°C. In addition, the hydrogenation dewaxing can be carried out in the presence of a zeolite catalyst under the 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 involves contacting high-temperature and high-pressure hydrogen with the feedstock oil in the presence of a catalyst, so that impurities such as sulfur and nitrogen that have adverse effects on the use and storage of processed oil can be used as hydrogenated light reactants. Removal, the result can be improved stability or color equality. Solvent dewaxing uses one or more solvents selected from the group consisting of acetone, methyl ethyl ketone, benzene, and toluene mixed with the raw oil, and then passes through a cooling step to make it represented by normal alkane The wax distillation analysis found that it was separated and removed by filtering it by a screening program, thereby improving the low-temperature fluidity. By mixing the extract obtained in the above manner with the base oil in a mass ratio of 95/5 to 5/95, particularly preferably 80/20 to 20/80, it is possible to manufacture the petroleum-containing aromatics of the embodiment Of oil.

"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. 2A and B are step diagrams illustrating an example of the process of preparing a tire composition from raw rubber. The tire composition that becomes the tire raw material is blended with raw rubber and various blending agents. Synthetic rubber is sometimes blended with extender oil when it is synthesized, and a rubber composition containing extender oil in advance (also called oil-extended rubber) can be used as the raw rubber (see FIG. 2A). Or raw rubber that does not contain extender oil (also known as non-oil-extended rubber) (refer to Figure 2B). Add processing oil and various blending agents to the raw rubber (see Figure 2A and B). The rubber (rubber composition) as the raw material of the oil-extended rubber can be obtained by supplying monomers to the polymerization reaction, and an extender oil can be added during the process. For example, by supplying the reaction liquid containing the rubber raw material monomer and extender oil as the raw rubber to the polymerization reaction, or after the reaction liquid containing the rubber raw material monomer as the raw rubber is polymerized, The method of adding extender oil to the polymer solution can produce oil-extended rubber (Figure 2A). The tire composition (rubber composition) can be kneaded with the above-mentioned raw rubber, the petroleum-based aromatic oil of the present invention, and the compounding agent by, for example, a well-known rubber kneader such as a roller press, a mixer, a kneader, etc. And manufacturing. The tire composition can be vulcanized under any conditions. In this specification, the one containing the raw rubber and the petroleum-based aromatic oil (extender oil or processing 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 in the manufacture of tires. As one embodiment, the present invention provides a tire composition containing raw rubber, the petroleum-based aromatic oil of the present invention, and a compounding agent. The tire composition is regarded as a concept included in the rubber composition of the embodiment. The tire composition (rubber composition) may be vulcanized or unvulcanized. Here, the extender oil and the processed oil are shown separately, but they may be collectively referred to as processed oil.

Hereinafter, the composition of the rubber composition and the tire composition will be described.

As the raw material rubber, elastomeric polymers can be used. Examples include natural rubber, isoprene rubber, butadiene rubber, 1,2-butadiene rubber, styrene-butadiene rubber, and isoprene rubber. Ene-butadiene rubber, styrene-isoprene-butadiene rubber, ethylene-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 and other diene rubbers, butyl rubber, ethylene-propylene rubber (EPDM, EPM), ethylene-butene rubber ( BBM), chlorosulfonated polyethylene, acrylic rubber, fluorine rubber and other olefin rubbers, epichlorohydrin rubber, polysulfide rubber, silicone rubber, urethane rubber, etc., and can also be hydrogenated Polystyrene elastomeric polymer (SBS, SIS, SEBS), polyolefin elastomeric polymer, polyvinyl chloride elastomeric polymer, polyurethane elastomeric polymer, polyolefin elastomer Thermoplastic elastomers such as ester-based elastomeric polymers or polyamide-based elastomeric polymers. These can be used alone or as arbitrary blends. From the viewpoint of compatibility with petroleum-based aromatic oils, the elastomeric polymer is preferably selected from natural rubber, isoprene rubber, styrene-butadiene rubber, butadiene rubber, At least one of the group consisting of butyl rubber, chloroprene rubber, and acrylonitrile rubber. Furthermore, from the viewpoint that it can be suitably used in a tread portion that exhibits rolling resistance performance and wet grip performance as tire performance, the elastomeric polymer is preferably selected from natural rubber, isoprene rubber, and styrene. At least one of the group consisting of butadiene rubber and butadiene rubber.

As the extender oil or the processing oil, the petroleum-based aromatic oil of the embodiment can be used.

Examples of compounding agents include fillers, anti-aging agents, antioxidants, crosslinking agents (vulcanizing agents), crosslinking accelerators, resins, plasticizing materials, vulcanization accelerators, vulcanization accelerators (vulcanization aids), etc. .

Examples of the filler include carbon black, silicon dioxide, silane compounds (silane coupling agents), and the like, and silicon dioxide and/or silane coupling agents are preferred. Carbon black is classified into hard carbon and soft carbon based on particle size. Soft carbon has lower reinforcement for rubber, and hard carbon has stronger reinforcement for rubber. When the rubber composition of the embodiment contains carbon black, it is particularly preferable to use hard carbon with stronger reinforcement. With respect to 100 parts by mass of the elastomeric polymer, the carbon black is preferably blended in 10 to 250 parts by mass, more preferably 20 to 200 parts by mass, and still more preferably 30 to 50 parts by mass. The silicon dioxide is not particularly limited, and examples thereof include dry-process white carbon, wet-process white carbon, colloidal silica, and precipitated silica. Among them, wet process white carbon with hydrous silicic acid as the main component is preferred. These silicas can be used alone or in combination of two or more kinds. The specific surface area of the silicon dioxide is not particularly limited, but it is usually 10 to 400 m ² /g, preferably 20 to 300 m ² /g, and more preferably 120 to the nitrogen adsorption specific surface area (BET method). The range of 190 m ² /g is suitable for improving reinforcement, abrasion resistance, and heat generation properties. Here, the nitrogen adsorption specific surface area is a value measured by the BET method in accordance with ASTM D3037-81. The silane compound is not particularly limited, but a sulfur-containing silane coupling agent is preferred, and bis(3-triethoxysilylpropyl) disulfide is more preferred.

As a crosslinking agent (vulcanizing agent), powder sulfur, precipitation sulfur, highly dispersible sulfur, surface-treated sulfur, insoluble sulfur, etc. are mentioned.

Examples of vulcanization accelerators include thiuram series such as tetramethylthiuram disulfide (TMTD) and tetraethylthiuram disulfide (TETD), aldehyde-ammonia series such as hexamethylenetetramine, and disulfide Guanidine series such as benzoguanidine, thiazole series such as dibenzothiazole disulfide (DM), cyclohexylbenzothiazole sulfenamide series such as N-cyclohexyl-2-benzothiazole sulfenamide, etc.

Examples of vulcanization accelerators include fatty acids such as acetic acid, propionic acid, butyric acid, stearic acid, acrylic acid, and maleic acid, zinc acetate, zinc propionate, zinc butyrate, zinc stearate, zinc acrylate, Fatty acid zinc such as zinc maleate, zinc white, etc.

The compounding amounts of the raw rubber, the petroleum-based aromatic oil of the present invention, and the compounding agent may be general compounding amounts as long as they do not violate the purpose of the present invention.

As an example, it can be exemplified: with respect to 100 parts by mass of the elastomeric polymer, a filler: 30-100 parts by mass, petroleum-based aromatic oil: 80 parts by mass or less, anti-aging agent: 0.5-5 parts by mass, Crosslinking agent: 1-10 parts by mass, resin: 0-20 parts by mass, vulcanization accelerator: 0.5-5 parts by mass, and vulcanization accelerator: 1-10 parts by mass. In the case of using silica and/or silane coupling agent as a filler, relative to 100 parts by mass of the elastomeric polymer, the silica and/or silane coupling agent is preferably blended with 10 to 300 parts by mass, more The blending is preferably 50 to 150 parts by mass, and 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, and more preferably 1 to 20 parts by mass relative to 100 parts by mass of the elastomeric polymer. With respect to 100 parts by mass of the elastomeric polymer, the petroleum-based aromatic oil is preferably blended in 0.5 to 80 parts by mass, more preferably 10 to 50 parts by mass, and still more preferably 20 to 40 parts by mass. Copies.

According to the rubber composition of the embodiment, a rubber composition having excellent rolling resistance performance and wet grip performance can be provided.

"Tire, Tire Manufacturing Method" The tire of the embodiment contains the petroleum-based aromatic oil of the above embodiment. The tire of the embodiment can be manufactured by blending rubber with the petroleum-based aromatic oil of the embodiment and vulcanizing it. In other words, the tire of the embodiment may include the above-mentioned tire composition (rubber composition), and may be manufactured by vulcanizing the tire composition. Specifically, for example, the tire composition can be vulcanized and molded to produce a tire. More specifically, for example, the above-mentioned tire composition is heated and melted, and the heated and melted tire composition is extruded. Then, after molding using a tire building machine, it is heated and pressurized using a vulcanizer to manufacture a tire.

As an example, a tire includes various parts of the tire such as a tread, a carcass, a side wall, an inner liner, an under tread, and a belt. The tire of the embodiment preferably contains the petroleum-based aromatic oil of the above embodiment in the tread portion. The tire of the embodiment preferably has a tire surface including the tire composition of the embodiment. Since the tread portion used as the ground contact surface contains petroleum-based aromatic oil, the rolling resistance performance and wet grip performance can be exerted well.

According to the tire and tire manufacturing method of the embodiment, a tire with excellent rolling resistance performance and wet grip performance can be provided.

As to why the petroleum-based aromatic oil of the embodiment exerts an effect on both the wet grip performance and the rolling resistance performance of the tire composition (rubber composition), it is estimated as follows. Since the two properties are self-contradictory, if one is not damaged and the other is improved, the result is both. Usually, it is attempted to have both, especially fuel economy performance, by blending silicon dioxide due to the so-called fuel-saving tires. However, silicon dioxide has many hydrophilic groups on the surface and is difficult to be compatible with rubber polymers. The tendency of silica to aggregate with each other. In this case, when the tire is deformed during driving, the silicon dioxide rubs against each other and generates heat, resulting in excess energy loss. Therefore, how to disperse silica in the rubber polymer becomes an important point. It is believed that the petroleum-based aromatic oil containing the above-mentioned specific components in a specific amount contains silica, which plays a role in the dispersion or dissolution of various formulations. This is equivalent to the behavior in the rubber polymer having a better effect on the physical properties. As a result, a combination of contradictory performance is achieved. [Example]

Next, examples are shown to explain the present invention in further detail, but the present invention is not limited to the following examples.

1. Production of processed oil <Example 1-1> The Middle East crude oil was supplied to the atmospheric distillation device, the obtained atmospheric distillation residue was supplied to the vacuum distillation device, and the vacuum distillation residue obtained was supplied to the utilization Compressed and liquefied propane deasphalting extraction device (adjusted under operating conditions: tower top temperature 60～90℃, tower bottom temperature 50～80℃, solvent ratio 1.5～6.0), and the obtained deasphalted oil Supply to the furfural extraction device (adjust under operating conditions: top temperature of 130 to 140°C, bottom temperature of 80 to 100°C, solvent ratio 3.0 to 4.0), and set the obtained extract fraction as extract ( A). The Middle East crude oil is supplied to the atmospheric distillation unit, the obtained atmospheric distillation residue is supplied to the vacuum distillation unit, and the obtained vacuum distillation fraction equivalent to 500 N is supplied to the furfural extraction unit (at the top of the tower) The temperature is 110～130℃, the bottom temperature of the tower is 60～80℃, and the solvent ratio is adjusted within the range of 1.0～3.0), and the obtained raffinate fraction is supplied to the hydrorefining device (under operating conditions: noble metal catalyst, Liquid space velocity 1.0～2.0 h ^-1 , reaction temperature 270～330℃, hydrogen-to-oil ratio 1500～2500 NL/L, hydrogen partial pressure 4.0～6.0 MPa), supply the obtained hydrogenated refined oil to Solvent dewaxing device (adjust the operating conditions: mixed solvent of methyl ethyl ketone and toluene, primary solvent ratio 2.0, secondary solvent ratio 0.8, and dewaxing temperature within the range of -15～-25℃) to obtain The dewaxing oil is set as dewaxing oil (B). The extract (A)/dewaxed oil (B) was mixed to 60/40 in a mass ratio to obtain the processed oil of Example 1.

<Example 2-1> The Middle East crude oil was supplied to an atmospheric distillation device, the obtained atmospheric distillation residue was supplied to the vacuum distillation device, and the obtained vacuum distillation residue was supplied to the decompression of propane by compressed liquefaction Asphalt extraction device (adjusted under operating conditions: tower top temperature 50～80℃, tower bottom temperature 40～70℃, solvent ratio 5.0～8.0), the obtained deasphalted oil is supplied to furfural extraction unit (at Operating conditions: the temperature at the top of the tower is 100-120°C, the temperature at the bottom of the tower is 50-70°C, and the solvent ratio is adjusted within the range of 3.5-4.5), and the obtained extract fraction is referred to as extract (C). The Middle East crude oil is supplied to the atmospheric distillation unit, the obtained atmospheric distillation residue is supplied to the vacuum distillation unit, and the obtained vacuum distillation fraction equivalent to 500 N is supplied to the furfural extraction unit (at the top of the tower) The temperature is 100～120℃, the bottom temperature of the tower is 50～70℃, and the solvent ratio is adjusted within the range of 1.0～3.0), and the obtained raffinate fraction is supplied to the hydrorefining unit (under operating conditions: noble metal catalyst, Liquid space velocity 1.0～2.0 h ^-1 , reaction temperature 320～370℃, hydrogen-to-oil ratio 1500～2500NL/L, hydrogen partial pressure 8.0～10.0 MPa to adjust), supply the obtained hydrogenated refined oil to the solvent Dewaxing device (adjust under operating conditions: mixed solvent of methyl ethyl ketone and toluene, primary solvent ratio 1.3, secondary solvent ratio 1.3, dewaxing temperature -15～-25℃), and the obtained The dewaxing oil is referred to as dewaxing oil (D). The extract (C)/dewaxed oil (D) was mixed to 70/30 in a mass ratio to obtain the processed oil of Example 2.

<Example 3-1> The Middle East crude oil was supplied to an atmospheric distillation device, the obtained atmospheric distillation residue was supplied to the vacuum distillation device, and the obtained vacuum distillation residue was supplied to the decompression of propane by compressed liquefaction. Asphalt extraction device (adjusted under operating conditions: tower top temperature 55-85°C, tower bottom temperature 45-75°C, solvent ratio 1.0-4.0), the obtained deasphalted oil is supplied to the furfural extraction device (at Operating conditions: the temperature at the top of the tower is 110-130°C, the temperature at the bottom of the tower is 60-80°C, and the solvent ratio is adjusted within the range of 3.0-4.0), and the obtained extract fraction is referred to as extract (E). The Middle East crude oil is supplied to the atmospheric distillation unit, the obtained atmospheric distillation residue is supplied to the vacuum distillation unit, and the obtained vacuum distillation fraction equivalent to 500 N is supplied to the furfural extraction unit (at the top of the tower) The temperature is 105～125℃, the bottom temperature of the tower is 55～75℃, and the solvent ratio is 1.2～2.8. The obtained raffinate fraction is supplied to the hydrorefining device (under operating conditions: noble metal catalyst, Liquid space velocity 2.0～3.0 h ^-1 , reaction temperature 310～360℃, hydrogen-oil ratio 1500～2500 NL/L, hydrogen partial pressure 8.5～12.0 MPa adjusted within the range), the obtained hydrogenated refined oil is supplied to Solvent dewaxing device (adjust under operating conditions: mixed solvent of methyl ethyl ketone and toluene, primary solvent ratio 1.0～2.0, secondary solvent ratio 0.5～1.4, dewaxing temperature -15～-25℃) , Set the obtained dewaxing oil as dewaxing oil (F). The extract (E)/dewaxed oil (F) was mixed to 62/38 in a mass ratio to obtain the processed oil of Example 3.

<Example 4-1> Naphthenic crude oil was supplied to the atmospheric distillation device, the obtained atmospheric distillation residue was supplied to the vacuum distillation device, and the obtained vacuum distillation fraction equivalent to 1000 N was supplied to the hydrorefining Device (under operating conditions: use precious metal catalyst, liquid space velocity 1.0～3.0 h ^-1 , reaction temperature 270℃～340℃, hydrogen oil ratio 1400～2800 NL/L, hydrogen partial pressure within the range of 3.0～9.0 MPa Adjust), and set the obtained hydrorefined oil as hydrorefined oil (K). The naphthenic crude oil is supplied to the atmospheric distillation apparatus, the obtained atmospheric distillation residue is supplied to the vacuum distillation apparatus, and the obtained vacuum distillation residue is referred to as the vacuum distillation residue (L). The hydrorefined oil (K) and the vacuum distillation residue (L) were mixed so that the kinematic viscosity at 100° C. became about 55 mm ² /s to obtain the processed oil of Example 4.

<Example 5-1> The above extract (E) was used as the processed oil of Example 5.

<Example 6-1> The above-mentioned extract (C) was used as the processed oil of Example 6.

<Comparative Example 1-1> The Middle East crude oil was supplied to the atmospheric distillation device, the obtained atmospheric distillation residue was supplied to the vacuum distillation device, and the obtained vacuum distillation fraction equivalent to 500 N was supplied to the furfural extraction device (Adjust within the range of operating conditions: tower top temperature 100-130°C, tower bottom temperature 50-80°C, solvent ratio 1.0-3.0), and supply the obtained raffinate fraction to the hydrorefining unit (under operating conditions ：Use precious metal catalyst, liquid space velocity 1.0～3.0 h ^-1 , reaction temperature 280～340℃, hydrogen-oil ratio 1500～2500 NL/L, hydrogen partial pressure 6.0～10.0 MPa to adjust), The obtained hydrogenated refined oil is supplied to the solvent dewaxing device (under operating conditions: mixed solvent of methyl ethyl ketone and toluene, primary solvent ratio 1.0～2.0, secondary solvent ratio 0.5～1.4, dewaxing temperature -15～-25 Adjust within the range of ℃), and set the obtained dewaxing oil as dewaxing oil (G). The Middle East crude oil is supplied to the atmospheric distillation apparatus, the obtained atmospheric distillation residue is supplied to the vacuum distillation apparatus, and the obtained vacuum distillation residue is referred to as the vacuum distillation residue (H). The naphthenic crude oil is supplied to the atmospheric distillation unit, the obtained atmospheric distillation residue is supplied to the vacuum distillation unit, and the obtained vacuum distillation fraction equivalent to 1000 N is supplied to the hydrorefining unit (under operating conditions: use Precious metal catalyst, liquid space velocity 1.0～3.0 h ^-1 , reaction temperature 270℃～340℃, hydrogen-to-oil ratio 1400～2800 NL/L, hydrogen partial pressure 3.0～9.0 MPa), the obtained The hydrogenated refined oil is referred to as hydrogenated refined oil (I). The naphthenic crude oil is supplied to an atmospheric distillation apparatus, the obtained atmospheric distillation residue is supplied to a vacuum distillation apparatus, and the obtained vacuum distillation residue is referred to as a vacuum distillation residue (J). Mix the dewaxed oil (G)/vacuum distillation residue (H) in a mass ratio to 50/50, and mix the hydrorefined oil (I)/vacuum distillation residue (J) in a mass ratio to 50/50, The two were mixed so that the dynamic viscosity at 100°C became about 30 mm ² /s to obtain the processed oil of Comparative Example 1.

<Comparative Example 2-1> Naphthenic crude oil was supplied to the atmospheric distillation device, the obtained atmospheric distillation residue was supplied to the vacuum distillation device, and the obtained vacuum distillation fraction equivalent to 2000 N was supplied to the hydrorefining Device (under operating conditions: use precious metal catalyst, liquid space velocity 1.0～3.0 h ^-1 , reaction temperature 270℃～340℃, hydrogen oil ratio 1400～2800 NL/L, hydrogen partial pressure within the range of 3.0～9.0 MPa (Adjustment), the obtained hydrorefined oil was used as the processed oil of Comparative Example 2.

<Comparative Example 3-1> The dewaxing oil (F) described above was used as the processing oil of Comparative Example 3.

<Comparative Example 4-1> The above-mentioned extract (E)/dewaxed oil (F) was mixed into 80/20 by mass ratio, thereby obtaining the processed oil of Comparative Example 4.

2. Determination of properties of processed oil The processing oils obtained in the above-mentioned Examples and Comparative Examples were used as samples, and the following items were measured.

[Clay Gel Method] According to the clay gel method (clay gel column chromatography): ASTM D2007-11 uses clay-gel absorption chromatography to standardize the characteristic bases in rubber extenders, processing oils and other petroleum-derived oils The method of testing is to determine the aromatic content, saturated content, and polar content (mass%).

[Separation of aromatics by HPLC] The separation of aromatics using HPLC (High Pressure Liquid Chromatography) is based on the "Separation of aromatic and polar compounds in fossil fuel liquids" published in (Previous Report: Analytical Chemistry, 1983, 55, p.1375-1379) "by liquid chromatography" is used as a reference and implemented by the following procedures. The pretreatment was performed by diluting the sample 5 times with hexane. The column used Spherisorb A5Y 250×4.6 mm manufactured by Waters Company, the flow rate was set to 2.5 mL/min, and the detector used a UV (ultraviolet) detector, and the measurement was performed at a wavelength of 270 nm. Regarding the eluent, hexane is used from 0 to 10.0 minutes from the introduction of the sample, and the dichloromethane content is linearly increased from 10.0 to 30.0 minutes from 100% by mass of hexane to become 40% by mass of dichloromethane and 60% by mass of hexane. The mixed solution. The time from the introduction of the sample was 30.0 to 30.1 minutes, the mixed solution of 40% by mass of dichloromethane and 60% by mass of hexane was changed to 100% by mass of dichloromethane, and 100% by mass of dichloromethane was used after 30.1 minutes. Calculate the content (mass%) of aromatic hydrocarbons in different rings from the peak areas obtained according to the following formula. Here, the area of the first ring is the total of the peak areas from the peak of benzene to the peak directly in front of naphthalene, and the area of the second ring is the total of the peak areas from the peak of naphthalene to the peak directly in front of anthracene. The above area is the sum of the peak areas after the anthracene peak. One-ring aromatic content (mass%)=(first-ring area/(first-ring area+0.1×second-ring area+0.025×three-ring above area))×100; Dicyclic aromatic content (mass%)=(0.1×area of the second ring/(area of the first ring+0.1×area of the second ring+0.025×area above the third ring))×100; Aromatic content above three rings (mass%)=(0.025×area of three rings/(area of one ring+0.1×area of two rings+0.025×area of more than three rings))×100

[Kinetic viscosity (100℃)] Measure according to JIS K2283:2000.

[Aniline point] Measure according to ASTM D611-12 Standard Test Method for Aniline Point and Mixed Aniline Point of Petroleum Products and Hydrocarbon Solvents.

[Glass transition point (Tg)] It is set as the glass transition point obtained from the heat change peak in the glass transition area measured by DSC (differential scanning calorimeter) when the temperature is raised at a certain temperature rise rate. The initial temperature is usually set to a temperature lower than the expected glass transition point by about 30°C to 50°C or lower. After the initial temperature is maintained for a certain period of time, the temperature rises. Specifically, the measurement is performed under the following conditions. Device: DSC7020 manufactured by Hitachi High-Tech Science Initial temperature: -90℃, keep for 10 minutes Heating rate: 10℃/min End temperature: 30℃, keep for 5 minutes

[Viscosity Specific Gravity Constant (VGC)] According to ASTM D2140-08, the standard operation of calculating the carbon component of petroleum-derived insulating oil is determined.

[%CA] According to ASTM D2140-08, the standard operation of calculating the carbon component of petroleum-derived insulating oil is determined.

[The content of benzo(a)pyrene and specific aromatic compounds (PAHs)] According to European Standard EN 16143:2013 Petroleum Products-Determination of Benzo (a) Pyrene (BaP) and Selected Polycyclic Aromatic Hydrocarbons (PAH) Content in Extender Oil-Procedures for Dual LC Cleaning and GC/MS Analysis The regulations are determined. PAHs means the following. 1) Benzo(a)pyrene (BaP) 2) Benzo(e)pyrene (BeP) 3) Benzo(a)anthracene (BaA) 4) 哛 (CHR) 5) Benzo(b)fluoranthene (BbFA) 6) Benzo(j)fluoranthene (BjFA) 7) Benzo(k)fluoranthene (BkFA) 8) Dibenzo(a,h)anthracene (DBAhA)

3. Manufacturing of rubber composition <Example 1-2～Example 6-2> The rubber polymer, the processing oil produced in the above Examples 1-1 to 6-1, and other formulations (silicon dioxide, silane coupling agent, anti-aging agent, vulcanization aid, zinc oxide) were prepared according to the following composition , Sulfur, vulcanization accelerator), kneading to obtain an unvulcanized rubber composition, press vulcanization molding at 160 ℃.

<Comparative example 1-2～Comparative example 4-2> The rubber polymer, the processing oil produced in the above-mentioned Comparative Examples 1-1 to 4-1, and other formulations (same as above) were prepared according to the following composition, and then kneaded to obtain an unvulcanized rubber composition. Press vulcanization molding at ℃.

The composition of the tire composition is shown in Table 1 below. The phr in the table represents the mass parts of various formulations relative to 100 parts by mass of the rubber polymer.

[Table 1] Allocation amount (phr) Rubber polymer (SBR) 100 Silicon dioxide 80 Silane coupling agent 6.4 Anti-aging agent 2 Vulcanization aid 1 Zinc oxide 3 Processing oil 37.5 sulfur 2.2 Vulcanization accelerator A 1.7 Vulcanization accelerator B 2.0

・Rubber polymer (SBR): BunaVSL4526 manufactured by Lanxess ・Silicon dioxide: ULTRASIL7000GR manufactured by Evonik ・Silicane coupling agent: Si75 manufactured by Evonik ・Anti-aging agent: Nocrack 6C manufactured by Ouchi Xinxing Chemical Industry ・Vulcanization additives: Stearic acid manufactured by NOF ・Zinc oxide: Toho Asia Lead Manufacturing Zinc Oxide No. 3 ・Processing oil: each processing oil produced in the examples and comparative examples ・Sulfur: Commercially available sulfur for sulfur ・Vulcanization accelerator A: Ouchi Xinxing Chemical Industry Manufacturing Nocceler cz ・Vulcanization accelerator B: Nocceler d manufactured by Ouchi Xinxing Chemical Industry

Rubber kneading method: set as the two-stage kneading shown below. (The first stage) ・Testing machine: Laboplastomill B-600 manufactured by Toyo Seiki Manufacturing Co., Ltd. ・Testing machine volume: 600 cc ・Filling rate: 70% (quality ratio) ・Speed: 100 rpm ・Temperature: Starting from 100℃, the upper limit is set to 155℃ ・Mixing time: about 9 minutes (second stage) ・Testing machine: Electric heating type high temperature rolling machine manufactured by Ikeda Machinery Industry ・Size: 6 inches ϕ×16 inches ・Rotation speed: front roller 25 rpm ・Speed ratio: Front-to-rear ratio 1:1.22 ・Temperature: 23±10℃

4. Determination of physical properties of rubber composition 8 mmφ×10 mm test pieces were produced from the rubber kneaded sheets after compression vulcanization molding of the above-mentioned Examples and Comparative Examples, and the following items were measured on the above-mentioned test pieces.

[tanδ(0℃)] Use ARES, a viscoelasticity measuring device manufactured by TAINSTRUMENTS, in torsion mode, under the conditions of frequency 10 Hz, measuring temperature range -50℃～100℃, heating rate 2℃/min, and dynamic strain 0.1%. Choose a value of 0°C from the obtained variable temperature tanδ. tanδ (0℃) is an index of wet grip performance. The larger the value, the better the wet grip performance.

[tanδ(50℃)] Use ARES, a viscoelasticity measuring device manufactured by TAINSTRUMENTS, in torsion mode, under the conditions of frequency 10 Hz, measuring temperature range -50℃～100℃, heating rate 2℃/min, and dynamic strain 0.1%. Choose a value of 50°C from the obtained variable temperature tanδ. tanδ (50°C) is an index of rolling resistance performance. The smaller the value, the better the rolling resistance performance.

5. Results The above measurement results are shown below. The foregoing embodiment 1-1 and embodiment 1-2 are referred to as embodiment 1 for short. For other embodiments and comparative examples, they are also abbreviated in the same manner.

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

[Table 2] Example Comparative example 1 2 3 4 5 6 1 2 3 4 Processing oil Separation of aromatics by HPLC One-ring aromatic quality% 55.0 58.9 53.6 63.9 44.9 50.8 67.0 71.5 87.9 46.8 Bicyclic aromatics quality% 24.5 24.8 25.6 15.5 29.7 29.9 18.5 18.8 9.1 30.8 Aromatic components with three or more rings quality% 20.5 16.3 20.8 20.6 25.4 19.3 14.5 9.7 3.0 22.4 Clay gel column chromatography Aromatic quality% 61.7 63.4 60.9 45.5 81.9 74.2 39.5 41.2 34.6 70.8 Saturation quality% 28.8 28.1 32.5 36.3 9.8 16.8 45.4 55.3 64.9 21.4 Polarity quality% 9.5 8.5 6.6 18.2 8.3 9.0 15.1 3.5 0.5 7.8 Dynamic viscosity (100℃) mm ² /s 31.10 32.00 28.35 56.64 71.09 58.55 29.40 20.01 10.91 43.54 Aniline point °C 80.9 89.2 85.0 82.8 67.1 79.1 90.4 97.6 110.0 76.4 Glass transfer point °C -50.2 -50.5 -52.9 -39.8 -34.6 -39.1 -54.1 -53.6 -69.1 -44.1 Ring analysis (ASTM D2140) VGC 0.882 0.868 0.874 0.889 0.917 0.895 0.861 0.849 0.815 0.896 %CA 22.8 18.9 21.2 29.1 29.9 23.9 22.4 13.2 5.7 25.8 Benzo[a]pyrene ppm 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 Total PAHs 8 substances ppm 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 Rubber composition tanδ(0℃): Wetland grip performance 1.13 1.12 1.08 1.03 1.16 1.00 0.80 0.68 0.51 0.96 tanδ(50℃): rolling resistance performance 0.89 0.94 0.92 0.98 0.99 1.00 0.91 0.88 0.83 0.97 Each item of processing oil: The underline indicates that it is outside the scope specified in the implementation form. Benzo[a]pyrene: ○ means that the content is less than 1 ppm (within the REACH regulatory standard value). The total of PAHs 8 substances: ○ means that the content is less than 10 ppm (within the REACH standard value). tanδ (0°C): Underlined means the index value is lower than 1 (wet grip performance is poor).

The processed oil of Examples 1 to 6 satisfies the "ratio of saturated fraction obtained by the clay gel method" and "ratio of bicyclic aromatic fraction separated by HPLC" specified in the embodiment, and the above processing is formulated The rubber compositions of Examples 1 to 6 obtained by treating the oil have both wet grip performance and rolling resistance performance and are very excellent. It can be seen that, in particular, the rubber composition of Examples 1 to 3 obtained by blending the "ratio of the aromatic content obtained by the clay gel method" to meet the range specified in the embodiment form can have good values and moisture. Ground grip performance and rolling resistance performance. In addition, it can be confirmed that the contents of benzo(a)pyrene and specific aromatic compounds (PAHs) in all processed oils in the examples and comparative examples meet the REACH regulations.

The above, each configuration in each embodiment and the combination thereof and the like are just an example, and addition, omission, substitution, and other changes of the configuration can be made without departing from the scope of the spirit of the present invention. In addition, the present invention is not limited by each embodiment, but is limited only by the scope of a claim. [Industrial availability]

The present invention can provide a petroleum-based aromatic oil, which can produce a rubber composition with excellent rolling resistance performance and wet grip performance, and meets REACH regulations.

10: Vacuum distillation device 11: Vacuum distillation fraction 12: Vacuum distillation residue 20: Deasphalting extraction device 22: Deasphalted oil 30: Solvent extraction device 31: raffinate 32: raffinate 33: Extract 34: Extract 40: Hydrogenation Refining Unit 41: Hydrogenated refined oil 42: Hydrogenated refined oil 50: Dewaxing device 51: dewaxing oil 52: dewaxing oil 62: Containing petroleum-based aromatic oil

Fig. 1 is a process diagram illustrating an example of a method for producing petroleum-based aromatic oil according to an embodiment of the present invention. Fig. 2A is a step diagram illustrating an example of a process for preparing a tire composition according to an embodiment of the present invention. Fig. 2B is a step diagram illustrating an example of the process of preparing the tire composition according to one embodiment of the present invention.

Claims (12)

A petroleum-based aromatic oil whose saturation ratio obtained by the clay gel method is 40% by mass or less, The ratio of the bicyclic aromatic components separated by HPLC is 10% by mass to 30% by mass relative to 100% by mass of the aromatic components obtained by the clay gel method, The content of benzo(a)pyrene is 1 mass ppm or less, and The total content of specific aromatic compounds in 1) to 8) below is 10 mass ppm or less; 1) Benzo(a)pyrene 2) Benzo(e)pyrene 3) Benzo(a)anthracene 4) 哛 5) Benzo(b)fluoranthene 6) Benzo(j)fluoranthene 7) Benzo(k)fluoranthene 8) Dibenzo(a,h)anthracene. Such as the petroleum-based aromatic oil of claim 1, wherein the saturated content obtained by the clay gel method is 20% by mass or more. The petroleum-based aromatic oil of claim 1 or 2, wherein the ratio of the bicyclic aromatic component separated by HPLC is 28% by mass or less with respect to 100% by mass of the aromatic component. For the petroleum-based aromatic oil of claim 1 or 2, wherein the saturated content obtained by the clay gel method is 35% by mass or less. The petroleum-based aromatic oil of claim 1 or 2, wherein the ratio of the bicyclic aromatic component separated by HPLC is 20% by mass or more relative to 100% by mass of the aromatic component. Such as the petroleum-based aromatic oil of claim 1 or 2, wherein the saturated content obtained by the clay gel method is 30% by mass or less. The petroleum-based aromatic oil of claim 1 or 2, wherein the ratio of the bicyclic aromatic component separated by HPLC is 25% by mass or less with respect to 100% by mass of the aromatic component. The petroleum-based aromatic oil according to claim 1 or 2, wherein the ratio of the bicyclic aromatic component separated by HPLC is 24.5% by mass or less with respect to 100% by mass of the aromatic component. For example, the petroleum-based aromatic oil in claim 1 or 2 is an extender oil or processing oil used by mixing with rubber. A rubber composition containing the petroleum-based aromatic oil as described in claim 1 or 2 and rubber. A tire containing the petroleum-based aromatic oil as claimed in claim 1 or 2. A method for manufacturing a tire according to claim 11, which includes compounding rubber and vulcanizing the petroleum-based aromatic oil according to claim 1 or 2.

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