TWI753370B - Petroleum-based aromatic-containing oil, rubber composition, tire, and method for producing tire - Google Patents

Petroleum-based aromatic-containing oil, rubber composition, tire, and method for producing tire Download PDF

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TWI753370B
TWI753370B TW109106270A TW109106270A TWI753370B TW I753370 B TWI753370 B TW I753370B TW 109106270 A TW109106270 A TW 109106270A TW 109106270 A TW109106270 A TW 109106270A TW I753370 B TWI753370 B TW I753370B
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oil
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TW202037582A (en
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伊藤岳史
新保紘子
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日商Ｊｘｔｇ能源股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/32—Properties characterising the ingredient of the composition containing low molecular weight liquid component
    • C08L2207/322—Liquid component is processing oil
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

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Abstract

本發明之含有石油系芳香族之油利用黏土凝膠法所得之飽和份之比率為45質量%以下，使用HPLC所分離之二環芳香族份之比率相對於上述芳香族份100質量%為16質量%以上29質量%以下，苯并(a)芘之含量為1質量ppm以下，且下述1)～8)之特定芳香族化合物之含量之合計為10質量ppm以下。1)苯并(a)芘、2)苯并(e)芘、3)苯并(a)蒽、4)䓛、5)苯并(b)螢蒽、6)苯并(j)螢蒽、7)苯并(k)螢蒽、8)二苯并(a,h)蒽。In the present invention, the ratio of the saturated content of the oil containing petroleum-based aromatics obtained by the clay gel method is 45 mass % or less, and the ratio of the bicyclic aromatic content separated by HPLC is 16 relative to 100 mass % of the above-mentioned aromatic content. Mass % or more and 29 mass % or less, the content of benzo(a)pyrene is 1 mass ppm or less, and the total content of the specific aromatic compounds of the following 1) to 8) is 10 mass ppm or less. 1) Benzo(a) pyrene, 2) benzo(e) pyrene, 3) benzo(a) anthracene, 4) fen, 5) benzo(b) fluoranthene, 6) benzo(j) fluoranthene , 7) benzo (k) fluoranthene, 8) dibenzo (a, h) anthracene.

Description

含有石油系芳香族之油、橡膠組合物、輪胎及輪胎之製造方法Petroleum-based aromatic-containing oil, rubber composition, tire, and method for producing tire

本發明係關於一種含有石油系芳香族之油、橡膠組合物、輪胎及輪胎之製造方法。 本申請基於2019年2月28日於日本申請之日本專利特願2019-035837號主張優先權，並將其內容引用於此處。The present invention relates to a petroleum-based aromatic-containing oil, a rubber composition, a tire, and a method for producing the tire. This application claims priority based on Japanese Patent Application No. 2019-035837 filed in Japan on February 28, 2019, the content of which is incorporated herein by reference.

大多情況下，一般於橡膠製品中調配有加工處理油以改善橡膠組合物之加工性或軟化性。例如於SBR(苯乙烯丁二烯共聚物橡膠)等合成橡膠中，於其合成時將延展油(增量油)調配於其中(橡膠調配油)。又，於輪胎等橡膠加工製品中，調配有加工油(加工處理油)以改善其加工性或橡膠加工製品之品質。此處，將延展油與加工油區分表示，但有時其等被統稱為加工處理油。 另一方面，於歐洲，自2010年開始應用如下限制，即，不可將橡膠調配油中含有特定量以上之特定之致癌性多環芳香族化合物者用於製造輪胎或輪胎零件(REACH(Registration ，Evaluation，Authorisation and Restriction of Chemicals，化學品註冊、評估、許可及限制)法規)。因此，要求符合REACH法規之橡膠調配油。In most cases, processing oils are generally prepared in 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), a spreading oil (extender oil) is blended therein (rubber blending oil) during its synthesis. In addition, processing oil (processing oil) is prepared in rubber processed products such as tires to improve the workability or the quality of the rubber processed products. Here, the extension oil and the processing oil are shown separately, but they may be collectively referred to as processing oil in some cases. On the other hand, in Europe, the following restrictions have been applied since 2010, that is, those containing specific carcinogenic polycyclic aromatic compounds in a rubber compounding oil above a specific amount cannot be used in the manufacture of tires or tire parts (REACH (Registration, Evaluation, Authorisation and Restriction of Chemicals, Chemical Registration, Evaluation, Authorisation and Restriction) Regulations). Therefore, rubber compounding oils that comply with REACH regulations are required.

汽車領域中之省燃耗化之動向非常受到關注，對於輪胎之省燃耗化亦要求進一步之改良。隨著自2010年1月開始輪胎貼標制度，對輪胎強烈要求提高表示省燃耗性之「滾動阻力性能」及表示制動性能之「濕地抓地性能」。然而，一般而言，滾動阻力性能與濕地抓地性能處於矛盾之關係，其等高水準之兼具成為課題。The trend of fuel saving in the automotive field has attracted much attention, and further improvements have been demanded for the fuel saving of tires. With the start of the tire labeling system in January 2010, tires have been strongly demanded to improve the "rolling resistance performance" that represents fuel economy and the "wet grip performance" that represents braking performance. However, in general, the rolling resistance performance and the wet grip performance are in a conflicting relationship, and it has become a problem to have both of these high levels.

為了提高輪胎之滾動阻力性能，除了減少空氣阻力、或研究設計胎面花紋等以外，有抑制橡膠組成即胎面膠自身之遲滯損失之方法。近年來，普及調配二氧化矽之複合物作為輪胎配方之一之補強材料。若僅調配二氧化矽，則於複合物中二氧化矽彼此凝集，於橡膠變形時二氧化矽分子彼此容易摩擦產生能量損失。針對於此，就保持濕地抓地性能，且改良滾動阻力性能之目標而言，提出藉由應用末端改性二氧化矽或矽烷偶合劑而控制二氧化矽之存在形態的方法。 根據專利文獻1，揭示有一種藉由包括如下步驟之製造方法所獲得之輪胎用橡膠組合物：第一基礎混練步驟，其將橡膠成分、含水碳酸鈣、及矽烷偶合劑加以混練；及第二基礎混練步驟，其將藉由上述第一基礎混練步驟所獲得之混練物、及二氧化矽加以混練。藉此，可獲得二氧化矽之分散性優異，且可均衡地提高省燃耗性、濕地抓地性能、耐磨耗性之輪胎用橡膠組合物。 [先前技術文獻] [專利文獻]In order to improve the rolling resistance performance of tires, in addition to reducing air resistance, or researching and designing tread patterns, etc., there are methods to suppress the hysteresis loss of the rubber composition, that is, the tread compound itself. In recent years, a compound of silicon dioxide has been popularized as one of the reinforcing materials in tire formulations. If only silicon dioxide is prepared, the silicon dioxide in the compound will agglomerate with each other, and when the rubber is deformed, the silicon dioxide molecules will easily rub against each other, resulting in energy loss. In view of this, for the purpose of maintaining wet grip performance and improving rolling resistance performance, a method of controlling the existence form of silica by applying terminal-modified silica or a silane coupling agent has been proposed. According to Patent Document 1, there is disclosed a rubber composition for tires obtained by a manufacturing method comprising the following steps: a first basic kneading step in which a rubber component, hydrous calcium carbonate, and a silane coupling agent are kneaded; and a second The basic kneading step is to knead the kneaded material obtained by the above-mentioned first basic kneading step and silica. Thereby, the rubber composition for tires which is excellent in dispersibility of silica and can improve fuel efficiency, wet grip performance, and abrasion resistance in a balanced manner can be obtained. [Prior Art Literature] [Patent Literature]

[專利文獻1]日本專利特開2012-153787號公報[Patent Document 1] Japanese Patent Laid-Open No. 2012-153787

然而，對輪胎要求進一步提高「滾動阻力性能」及「濕地抓地性能」、及其等之兼具。針對該要求，期待自除了二氧化矽或矽烷偶合劑以外之橡膠構件考慮之各種方法。However, tires are required to further improve "rolling resistance performance" and "wet grip performance", as well as both. In response to this requirement, various methods considered from the rubber member other than the silica or silane coupling agent are expected.

本發明係用於消除如上所述之問題而完成，目的在於提供一種含有石油系芳香族之油，其可製造滾動阻力性能及濕地抓地性能優異之橡膠組合物，且滿足REACH法規。 又，本發明之目的在於提供一種橡膠組合物，其含有滿足REACH法規之含有石油系芳香族之油，且滾動阻力性能及濕地抓地性能優異。 又，本發明之目的在於提供一種含有上述含有石油系芳香族之油之輪胎、及上述輪胎之製造方法。The present invention has been accomplished in order to solve the above-mentioned problems, and an object of the present invention is to provide a rubber composition containing a petroleum-based aromatic oil, which can produce a rubber composition excellent in rolling resistance performance and wet grip performance, and satisfies REACH regulations. Another object of the present invention is to provide a rubber composition containing a petroleum-based aromatic-containing oil that satisfies REACH regulations, and which is excellent in rolling resistance performance and wet grip performance. Moreover, the objective of this invention is to provide the tire containing the said petroleum-based aromatic-containing oil, and the manufacturing method of the said tire.

本發明者等人為了解決上述課題進行了銳意研究，結果發現，藉由調配以下述特定量包含飽和份、及芳香族份之中特別是二環芳香族份之油，可製造滾動阻力性能及濕地抓地性能優異之橡膠組合物，從而完成了本發明。 即，本發明之一態樣係下述含有石油系芳香族之油、橡膠組合物、輪胎、及輪胎之製造方法。The inventors of the present invention have conducted intensive studies in order to solve the above-mentioned problems, and as a result, they have found that rolling resistance performance and oil can be produced by blending an oil containing a saturated part and an aromatic part, especially a bicyclic aromatic part, in the following specific amounts. The present invention has been completed by a rubber composition excellent in wet grip performance. That is, one aspect of the present invention is the following petroleum-based aromatic-containing oil, a rubber composition, a tire, and a method for producing the tire.

(1)一種含有石油系芳香族之油，其利用黏土凝膠法所得之飽和份之比率為45質量%以下，使用HPLC(high performance liquid chromatography，高效液相層析法)所分離之二環芳香族份之比率相對於利用黏土凝膠法所得之芳香族份100質量%為16質量%以上29質量%以下，苯并(a)芘之含量為1質量ppm以下，且下述1)~8)之特定芳香族化合物之含量之合計為10質量ppm以下。 (1) An oil containing petroleum-based aromatics, the ratio of the saturated fraction obtained by the clay gel method being 45% by mass or less, and the bicyclic ring separated by HPLC (high performance liquid chromatography). The ratio of the aromatic part is 16 mass % or more and 29 mass % or less with respect to 100 mass % of the aromatic part obtained by the clay gel method, the content of benzo(a)pyrene is 1 mass ppm or less, and the following 1)～ 8) The total content of the specific aromatic compound is 10 mass ppm or less.

1)苯并(a)芘(BaP) 1) Benzo(a)pyrene (BaP)

2)苯并(e)芘(BeP) 2) Benzo(e)pyrene (BeP)

3)苯并(a)蒽(BaA) 3) Benzo (a) Anthracene (BaA)

4)

Figure 109106270-A0305-02-0005-2
(CHR) 4)
Figure 109106270-A0305-02-0005-2
(CHR)

5)苯并(b)螢蒽(BbFA) 5) Benzo (b) Fluoranthene (BbFA)

6)苯并(j)螢蒽(BjFA) 6) Benzo (j) Fluoranthene (BjFA)

7)苯并(k)螢蒽(BkFA) 7) Benzo (k) Fluoranthene (BkFA)

8)二苯并(a,h)蒽(DBAhA)。 8) Dibenzo(a,h)anthracene (DBAhA).

(2)如上述(1)之含有石油系芳香族之油，其中上述利用黏土凝膠法所得之飽和份之比率為22質量%以上。 (2) The petroleum-based aromatic-containing oil according to the above (1), wherein the ratio of the saturated content obtained by the above-mentioned clay gel method is 22% by mass or more.

(3)如上述(1)或(2)之含有石油系芳香族之油，其中上述使用HPLC所分離之二環芳香族份之比率相對於上述利用黏土凝膠法所得之芳香族份100質量%未達23質量%。 (3) The petroleum-based aromatic-containing oil according to (1) or (2) above, wherein the ratio of the bicyclic aromatic fraction separated by HPLC is relative to 100 mass of the aromatic fraction obtained by the clay gel method. % is less than 23% by mass.

(4)如上述(1)至(3)中任一項之含有石油系芳香族之油，其中上述利用黏土凝膠法所得之飽和份之比率為36質量%以下。 (4) The petroleum-based aromatic-containing oil according to any one of the above (1) to (3), wherein the ratio of the saturated part obtained by the above-mentioned clay gel method is 36 mass % or less.

(5)如上述(1)至(4)中任一項之含有石油系芳香族之油，其中上述使 用HPLC所分離之二環芳香族份之比率相對於上述利用黏土凝膠法所得之芳香族份100質量%為22質量%以下。 (5) The petroleum-based aromatic-containing oil according to any one of the above (1) to (4), wherein the above uses The ratio of the bicyclic aromatic content separated by HPLC was 22 mass % or less with respect to 100 mass % of the aromatic content obtained by the above-mentioned clay gel method.

(6)如上述(1)至(5)中任一項之含有石油系芳香族之油，其係混合於橡膠中而使用之增量油或加工處理油。 (6) The petroleum-based aromatic-containing oil according to any one of the above (1) to (5), which is an extender oil or a processing oil mixed with rubber and used.

(7)一種橡膠組合物，其含有如上述(1)至(6)中任一項之含有石油系芳香族之油、及橡膠。 (7) A rubber composition comprising the petroleum-based aromatic-containing oil according to any one of (1) to (6) above, and a rubber.

(8)一種輪胎，其含有如上述(1)至(6)中任一項之含有石油系芳香族之油。 (8) A tire containing the petroleum-based aromatic-containing oil according to any one of (1) to (6) above.

(9)一種如上述8之輪胎之製造方法，其包括調配橡膠、及如上述(1)至(6)中任一項之含有石油系芳香族之油進行硫化。 (9) A method for producing a tire according to the above 8, comprising compounding a rubber and vulcanizing the oil containing a petroleum-based aromatic according to any one of the above (1) to (6).

根據本發明，可提供一種含有石油系芳香族之油，其可製造滾動阻力性能及濕地抓地性能優異之橡膠組合物，且滿足REACH法規。 According to the present invention, it is possible to provide a petroleum-based aromatic oil that can produce a rubber composition excellent in rolling resistance performance and wet grip performance, and which satisfies REACH regulations.

又，根據本發明，可提供一種橡膠組合物，其含有滿足REACH法規之含有石油系芳香族之油，且滾動阻力性能及濕地抓地性能優異。 Further, according to the present invention, a rubber composition containing a petroleum-based aromatic-containing oil that satisfies REACH regulations and excellent in rolling resistance performance and wet grip performance can be provided.

又，根據本發明，可提供一種含有上述含有石油系芳香族之油之輪胎、及上述輪胎之製造方法。 Moreover, according to this invention, the tire containing the said petroleum-based aromatic-containing oil, and the manufacturing method of the said tire can be provided.

以下，對本發明之含有石油系芳香族之油、橡膠組合物、輪胎、及輪胎之製造方法之實施形態進行說明。Hereinafter, embodiments of the petroleum-based aromatic-containing oil, rubber composition, tire, and tire manufacturing method of the present invention will be described.

≪含有石油系芳香族之油≫ 於實施形態之含有石油系芳香族之油中，利用黏土凝膠法所得之飽和份之比率、使用HPLC所分離之二環芳香族份之比率、苯并(a)芘之含量、及特定芳香族化合物之含量滿足特定之數值範圍。含有該等項目滿足下述數值範圍之含有石油系芳香族之油的橡膠組合物或輪胎之tanδ(50℃)及tanδ(0℃)之值變得良好，從而兼具濕地抓地性能及滾動阻力性能。≪Contains petroleum-based aromatic oils≫ In the petroleum-based aromatic-containing 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 family compound satisfies a specific numerical range. The values of tanδ (50°C) and tanδ (0°C) of rubber compositions or tires containing petroleum-based aromatic oils that satisfy the following numerical ranges for these items become good, so that they have both wet grip performance and Rolling resistance performance.

此處，「濕地抓地性能」係所謂制動性能，藉由動態黏彈性試驗所獲得之tanδ(0℃)成為其指標。「滾動阻力性能」係所謂省燃耗性能，藉由動態黏彈性試驗所獲得之tanδ(50℃)成為其指標。Here, the "wet grip performance" is the so-called braking performance, and the tan δ (0° C.) obtained by the dynamic viscoelasticity test is used as the index. "Rolling resistance performance" is the so-called fuel saving performance, and the tanδ (50°C) obtained by the dynamic viscoelasticity test is the index.

上述「石油系」意指含有源自石油(Petroleum-Derived)之烴油。上述「含有芳香族之油」意指利用黏土凝膠法所得之飽和份之比率、及使用HPLC所分離之二環芳香族份之比率滿足下述數值範圍。 若實施形態之含有石油系芳香族之油滿足上述各項目之數值範圍，則製法或分類不受特別限制，例如可列舉：常壓蒸餾殘渣、常壓蒸餾餾分、減壓蒸餾餾分、減壓蒸餾殘渣、脫瀝青油、溶劑萃取萃餘物、氫化精製油、脫蠟油、溶劑萃取萃取物等，較佳為含有藉由下述含有石油系芳香族之油之製造方法所製造之油。含有石油系芳香族之油中之源自石油之烴油的含有比率可為50質量%以上，可為80質量%以上，可為95質量%以上。The above-mentioned "petroleum-based" means containing hydrocarbon oil derived from petroleum (Petroleum-Derived). The above-mentioned "aromatic-containing oil" means that the ratio of the saturated part obtained by the clay gel method and the ratio of the bicyclic aromatic part separated by HPLC satisfy the following numerical ranges. As long as the petroleum-based aromatic-containing oil of the embodiment satisfies the numerical ranges of the above items, the production 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-containing oil. 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, or 95% by mass or more.

以下，對於實施形態之含有石油系芳香族之油之性狀的各項目進行說明。Hereinafter, each item of the properties of the petroleum-based aromatic-containing oil according to the embodiment will be described.

石油系油之成分可藉由黏土凝膠法分類成飽和份、芳香族份、極性成分(質量%)。以下之利用黏土凝膠法所得之飽和份、芳香族份、或極性成分(質量%)之值係相對於飽和份、芳香族份、及極性成分之總量100質量%之值。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 saturated content, aromatic content, or polar components (mass %) obtained by the clay gel method are values relative to 100 mass % of the total amount of saturated content, aromatic content, and polar components.

實施形態之含有石油系芳香族之油的利用黏土凝膠法所得之飽和份之比率為45質量%以下，較佳為36質量%以下，更佳為30質量%以下。實施形態之含有石油系芳香族之油的利用黏土凝膠法所得之飽和份之比率較佳為5質量%以上，更佳為20質量%以上，進而較佳為22質量%以上。作為上述數值之數值範圍之一例，實施形態之含有石油系芳香族之油的利用黏土凝膠法所得之飽和份之比率可為5質量%以上45質量%以下，可為20質量%以上36質量%以下，可為22質量%以上30質量%以下。 藉由使上述飽和份之比率滿足上述數值，而使含有上述油之橡膠組合物或輪胎之tanδ(50℃)及tanδ(0℃)之值變得良好，從而兼具濕地抓地性能及滾動阻力性能。 認為其原因在於，飽和份作為烴之極性為適當之平衡，對橡膠顯示一定親和性，且亦對橡膠之調配劑顯示一定親和性，因此藉由使上述飽和份之比率為上述範圍內，可使所製造之橡膠組合物或輪胎之物理特性變得適宜。The ratio of the saturation fraction obtained by the clay gel method of the petroleum-based aromatic-containing oil of the embodiment is 45 mass % or less, preferably 36 mass % or less, and more preferably 30 mass % or less. The ratio of the saturated fraction obtained by the clay gel method of the petroleum-based aromatic-containing 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-containing oil of the embodiment may be 5 mass % or more and 45 mass % or less, and may be 20 mass % or more and 36 mass %. % or less, it may be 22 mass % or more and 30 mass % or less. By making the ratio of the above-mentioned saturated part satisfy the above-mentioned numerical value, the values of tanδ (50°C) and tanδ (0°C) of the rubber composition or tire containing the above-mentioned oil become good, so that both wet grip performance and Rolling resistance performance. The reason for this is considered to be that the saturated part has an appropriate balance as the polarity of the hydrocarbon, and exhibits a certain affinity for rubber and also shows a certain affinity for the rubber compounding agent. The physical properties of the manufactured rubber composition or tire are made suitable.

實施形態之含有石油系芳香族之油的利用黏土凝膠法所得之芳香族份之比率較佳為50質量%以上，更佳為51質量%以上，進而較佳為58質量%以上。實施形態之含有石油系芳香族之油的利用黏土凝膠法所得之芳香族份之比率較佳為74質量%以下，更佳為70質量%以下，進而較佳為69質量%以下。作為上述數值之數值範圍之一例，實施形態之含有石油系芳香族之油的利用黏土凝膠法所得之芳香族份之比率可為50質量%以上74質量%以下，可為51質量%以上70質量%以下，可為58質量%以上69質量%以下。 藉由使上述芳香族份之比率滿足上述數值，而使含有上述油之橡膠組合物或輪胎之tanδ(50℃)及tanδ(0℃)之值變得良好，從而兼具濕地抓地性能及滾動阻力性能。 認為其原因在於，芳香族份對橡膠顯示較高之親和性，因此藉由使上述芳香族份之比率為上述範圍內，可使所製造之橡膠組合物或輪胎之物理特性變得適宜。The ratio of the aromatic content obtained by the clay gel method of the petroleum-based aromatic-containing 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-containing oil of the embodiment is preferably 74% by mass or less, more preferably 70% by mass or less, and still more preferably 69% 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 of the petroleum-based aromatic-containing oil of the embodiment may be 50 mass % or more and 74 mass % or less, and may be 51 mass % or more and 70 mass %. The mass % or less may be 58 mass % or more and 69 mass % or less. By making the ratio of the above-mentioned aromatic part satisfy the above-mentioned numerical value, the values of tan δ (50° C.) and tan δ (0° C.) of the rubber composition or tire containing the above-mentioned oil can be improved, so that both wet grip performance can be achieved. and rolling resistance performance. The reason for this is considered to be that the aromatic part has a high affinity for rubber, and the physical properties of the produced rubber composition or tire can be made suitable by setting the ratio of the above-mentioned aromatic part to be within the above-mentioned range.

實施形態之含有石油系芳香族之油的利用黏土凝膠法所得之極性成分之比率較佳為1質量%以上，更佳為2質量%以上，進而較佳為3質量%以上。實施形態之含有石油系芳香族之油的利用黏土凝膠法所得之極性成分之比率較佳為11質量%以下，更佳為10質量%以下，進而較佳為9質量%以下。作為上述數值之數值範圍之一例，實施形態之含有石油系芳香族之油的利用黏土凝膠法所得之極性成分之比率可為1質量%以上11質量%以下，可為2質量%以上10質量%以下，可為3質量%以上9質量%以下。 上述極性成分之比率與上述飽和份及芳香族份之比率為相反關係，藉由使上述極性成分之比率滿足上述數值，而使含有上述油之橡膠組合物或輪胎之tanδ(50℃)及tanδ(0℃)之值變得良好，從而兼具濕地抓地性能及滾動阻力性能。The ratio of the polar component obtained by the clay gel method of the petroleum-based aromatic-containing oil of the embodiment is preferably 1 mass % or more, more preferably 2 mass % or more, and still more preferably 3 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 11% by mass or less, more preferably 10% by mass or less, and still more preferably 9% by mass or less. As an example of the numerical range of the above-mentioned numerical value, the ratio of the polar component obtained by the clay gel method containing the petroleum-based aromatic oil of the embodiment may be 1 mass % or more and 11 mass % or less, and may be 2 mass % or more and 10 mass % % or less, it may be 3 mass % or more and 9 mass % or less. The ratio of the above-mentioned polar component has an inverse relationship with the ratio of the above-mentioned saturated part and the above-mentioned aromatic part. By making the ratio of the above-mentioned polar component satisfy the above-mentioned numerical value, the tanδ (50°C) and tanδ of the rubber composition or tire containing the above-mentioned oil can be obtained. The value of (0° C.) becomes good, so that both wet grip performance and rolling resistance performance are achieved.

利用黏土凝膠法所得之飽和份、芳香族份、及極性成分之比率(質量%)可根據ASTM D2007-11用黏土-凝膠吸收層析法對橡膠增量劑及加工處理油以及其他石油衍生油中之特徵性基進行標準測試之方法(Standard Test Method for Characteristic Groups in Rubber Extender and Processing Oils and Other Petroleum-Derived Oils by the Clay-Gel Absorption Chromatographic Method)之規定而求出。The ratio (mass %) of saturated, aromatic, and polar components obtained by the clay gel method can be used for rubber extenders, processing oils and other petroleum oils by clay-gel absorption chromatography according to ASTM D2007-11. The characteristic base in the derived oil is 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).

實施形態之含有石油系芳香族之油的使用HPLC所分離之二環芳香族份之比率相對於上述芳香族份100質量%為16質量%以上，較佳為17質量%以上，更佳為19質量%以上，進而較佳為20質量%以上。實施形態之含有石油系芳香族之油的使用HPLC所分離之二環芳香族份之比率相對於上述芳香族份100質量%為29質量%以下，較佳為未達23質量%，更佳為22質量%以下。作為上述數值之數值範圍之一例，實施形態之含有石油系芳香族之油的使用HPLC所分離之二環芳香族份之比率相對於上述芳香族份100質量%，可為16質量%以上29質量%以下，可為17質量%以上且未達23質量%，可為19質量%以上22質量%以下，可為20質量%以上22質量%以下。此處，藉由使上述二環芳香族份之比率滿足上述數值，而使含有上述油之橡膠組合物或輪胎之tanδ(50℃)及tanδ(0℃)之值變得良好，從而兼具濕地抓地性能及滾動阻力性能。 根據下述實施例所示之資料進行研究，芳香族份之中二環以上之芳香族份之比率大為有助於兼具濕地抓地性能及滾動阻力性能。其中，二環芳香族份除了提高濕地抓地性能及滾動阻力性能以外，進而就滿足REACH法規之觀點而言亦具有良好之性質。The ratio of the bicyclic aromatic content of the petroleum-based aromatic-containing oil of the embodiment separated by HPLC is 16 mass % or more, preferably 17 mass % or more, more preferably 19 mass % with respect to 100 mass % of the above-mentioned aromatic content mass % or more, more preferably 20 mass % or more. The ratio of the bicyclic aromatic content of the petroleum-based aromatic-containing oil of the embodiment separated by HPLC is 29 mass % or less, preferably less than 23 mass %, more preferably 100 mass % of the above-mentioned aromatic content. 22 mass % or less. As an example of the numerical range of the above-mentioned numerical value, the ratio of the bicyclic aromatic fraction separated by HPLC of the petroleum-based aromatic-containing oil of the embodiment may be 16 mass % or more and 29 mass % with respect to the above-mentioned aromatic fraction of 100 mass %. % or less, may be 17 mass % or more and less than 23 mass %, may be 19 mass % or more and 22 mass % or less, and may be 20 mass % or more and 22 mass % or less. Here, by making the ratio of the above-mentioned bicyclic aromatic part satisfy the above-mentioned numerical value, the values of tan δ (50° C.) and tan δ (0° C.) of the rubber composition or tire containing the above-mentioned oil become good, and both Wet grip performance and rolling resistance performance. According to the data shown in the following examples, the ratio of the aromatic part having two or more rings in the aromatic part is very helpful for both the wet grip performance and the rolling resistance performance. Among them, in addition to improving wet grip performance and rolling resistance performance, the bicyclic aromatic part also has favorable properties from the viewpoint of satisfying REACH regulations.

實施形態之含有石油系芳香族之油的使用HPLC所分離之一環芳香族份之比率相對於上述芳香族份100質量%，較佳為48質量%以上，更佳為超過60質量%，進而較佳為超過62質量%。實施形態之含有石油系芳香族之油的使用HPLC所分離之一環芳香族份之比率相對於上述芳香族份100質量%，較佳為80質量%以下，更佳為78質量%以下，進而較佳為76質量%以下。作為上述數值之數值範圍之一例，實施形態之含有石油系芳香族之油的使用HPLC所分離之一環芳香族份之比率相對於上述芳香族份100質量%，可為48質量%以上80質量%以下，可超過60質量%且為78質量%以下，可超過62質量%且為76質量%以下。 上述一環芳香族份之比率與上述二環以上之芳香族份之比率為相反關係，藉由使上述一環芳香族份之比率滿足上述數值，而使含有上述油之橡膠組合物或輪胎之tanδ(50℃)及tanδ(0℃)之值變得良好，從而兼具濕地抓地性能及滾動阻力性能。The ratio of the one-ring aromatic content of the petroleum-based aromatic-containing oil of the embodiment separated by HPLC is preferably 48 mass % or more, more preferably more than 60 mass %, and more preferably 100 mass % of the above-mentioned aromatic content. Preferably, it exceeds 62 mass %. The ratio of the one-ring aromatic content of the petroleum-based aromatic-containing oil of the embodiment separated by HPLC is preferably 80 mass % or less, more preferably 78 mass % or less, and more preferably 100 mass % of the above-mentioned aromatic content. Preferably it is 76 mass % or less. As an example of the numerical range of the above-mentioned numerical value, the ratio of the one-ring aromatic content of the petroleum-based aromatic-containing oil of the embodiment separated by HPLC may be 48 mass % or more and 80 mass % with respect to 100 mass % of the above-mentioned aromatic content. Below, it may exceed 60 mass % and may be 78 mass % or less, and may exceed 62 mass % and may be 76 mass % or less. The ratio of the above-mentioned one-ring aromatic part has an inverse relationship with the ratio of the above-mentioned bicyclic or more aromatic parts, and by making the ratio of the above-mentioned one-ring aromatic part satisfy the above-mentioned numerical value, the rubber composition or tire containing the above-mentioned oil has a tanδ ( 50°C) and tanδ (0°C) became good, so that both wet grip performance and rolling resistance performance were achieved.

實施形態之含有石油系芳香族之油的使用HPLC所分離之三環以上之芳香族份之比率相對於上述芳香族份100質量%，較佳為4質量%以上，更佳為5質量%以上，進而較佳為6質量%以上。實施形態之含有石油系芳香族之油的使用HPLC所分離之三環以上之芳香族份之比率相對於上述芳香族份100質量%，較佳為20質量%以下，更佳為18質量%以下，進而較佳為未達16質量%。作為上述數值之數值範圍之一例，實施形態之含有石油系芳香族之油的使用HPLC所分離之三環以上之芳香族份之比率相對於上述芳香族份100質量%，可為4質量%以上20質量%以下，可為5質量%以上18質量%以下，可為6質量%以上且未達16質量%。 藉由使上述三環以上之芳香族份之比率滿足上述數值，而使含有上述油之橡膠組合物或輪胎之tanδ(50℃)及tanδ(0℃)之值變得良好，從而兼具濕地抓地性能及滾動阻力性能，進而就滿足REACH法規之方面而言亦良好。The ratio of the tricyclic or more aromatic content of the petroleum-based aromatic-containing oil of the embodiment separated by HPLC is preferably 4 mass % or more, more preferably 5 mass % or more with respect to 100 mass % of the above-mentioned aromatic content , more preferably 6 mass % or more. The ratio of the tricyclic or more aromatic content of the petroleum-based aromatic-containing oil of the embodiment separated by HPLC is preferably 20 mass % or less, more preferably 18 mass % or less with respect to 100 mass % of the above-mentioned aromatic content , and more preferably less than 16% by mass. As an example of the numerical range of the above-mentioned numerical value, the ratio of the tricyclic or more aromatic content of the petroleum-based aromatic-containing oil of the embodiment separated by HPLC may be 4 mass % or more with respect to 100 mass % of the above-mentioned aromatic content It may be 20 mass % or less, 5 mass % or more and 18 mass % or less, and 6 mass % or more and less than 16 mass %. By making the ratio of the above-mentioned tricyclic or more aromatic parts satisfy the above-mentioned numerical value, the values of tanδ (50°C) and tanδ (0°C) of the rubber composition or tire containing the above-mentioned oil become good, so that both moisture The ground grip performance and rolling resistance performance are also favorable in terms of satisfying REACH regulations.

使用HPLC所進行之芳香族份之分離可藉由下述實施例所記載之測定條件而求出。The separation of the aromatic fraction by HPLC can be obtained under the measurement conditions described in the following examples.

關於實施形態之含有石油系芳香族之油， 苯并(a)芘之含量為1質量ppm以下， 下述1)～8)之特定芳香族化合物(PAHs)之含量之合計為10質量ppm以下。 1)苯并(a)芘(BaP) 2)苯并(e)芘(BeP) 3)苯并(a)蒽(BaA) 4)䓛(CHR) 5)苯并(b)螢蒽(BbFA) 6)苯并(j)螢蒽(BjFA) 7)苯并(k)螢蒽(BkFA) 8)二苯并(a,h)蒽(DBAhA)。Regarding the petroleum-based aromatic-containing oil of the embodiment, The content of benzo(a)pyrene is 1 mass ppm or less, The total content of the 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) Qi (CHR) 5) Benzo (b) Fluoranthene (BbFA) 6) Benzo (j) Fluoranthene (BjFA) 7) Benzo (k) Fluoranthene (BkFA) 8) Dibenzo(a,h)anthracene (DBAhA).

藉由使該等苯并(a)芘及上述特定芳香族化合物(PAHs)之含量為上述範圍內，可製成遵守REACH法規中之對增量油之含有限制的安全性更高之橡膠調配油。By making the content of these benzo(a)pyrenes and the above-mentioned specific aromatic compounds (PAHs) within the above-mentioned ranges, it is possible to make rubber formulations with higher safety that comply with the REACH regulation on the content of extender oils. Oil.

該等化合物之含量可藉由如下方式而獲取，即，將對象成分進行分離、濃縮後，製備添加有內部標準物質之試樣，並藉由GC-MS(Gas chromatography-mass spectrometry，氣相層析-質譜)分析進行定量分析。 苯并(a)芘及特定芳香族化合物(PAHs)之含量可根據歐洲標準EN 16143：2013石油製品-增量油中之苯并(a)芘(BaP)及選擇之多環芳香族烴(PAH)含量之測定-使用雙LC清洗及GC/MS分析之程序(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)之規定而求出。The content of these compounds can be obtained by separating and concentrating the target components, preparing a sample to which an internal standard substance is added, and performing GC-MS (Gas chromatography-mass spectrometry, gas chromatography) analysis-mass spectrometry) analysis for quantitative analysis. The content of benzo(a)pyrene and certain aromatic compounds (PAHs) can be determined according to European standard EN 16143:2013 Petroleum products - Benzo(a)pyrene (BaP) and selected polycyclic aromatic hydrocarbons ( Determination of PAH) content - Procedure using double LC cleaning and GC/MS analysis (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).

實施形態之含有石油系芳香族之油於100℃下之動黏度較佳為8 mm2 /s以上，更佳為10 mm2 /s以上，進而較佳為14 mm2 /s以上。實施形態之含有石油系芳香族之油於100℃下之動黏度較佳為未達25 mm2 /s，更佳為23 mm2 /s以下，進而較佳為22 mm2 /s以下。作為上述數值之數值範圍之一例，實施形態之含有石油系芳香族之油於100℃下之動黏度可為8 mm2 /s以上且未達25 mm2 /s之範圍，可為10 mm2 /s以上23 mm2 /s以下之範圍，可為14 mm2 /s以上22 mm2 /s以下之範圍。若上述動黏度之值滿足上述數值，則包含含有石油系芳香族之油的橡膠組合物或輪胎之黏度變得良好，因此tanδ(50℃)及tanδ(0℃)之值變得更良好，從而使濕地抓地性能及滾動阻力性能之兼具變得更良好。進而，若上述動黏度之值為上述上限值以下，則用於將含有石油系芳香族之油調配於橡膠之移行或作業性變得良好。The kinematic viscosity at 100°C of the petroleum-based aromatic-containing oil of the embodiment is preferably 8 mm 2 /s or more, more preferably 10 mm 2 /s or more, and still more preferably 14 mm 2 /s or more. The kinematic viscosity at 100°C of the petroleum-based aromatic-containing oil of the embodiment is preferably less than 25 mm 2 /s, more preferably 23 mm 2 /s or less, and still more preferably 22 mm 2 /s or less. As an example of the numerical range of the above-mentioned numerical values, the kinematic viscosity of the petroleum-based aromatic-containing oil of the embodiment at 100° C. may be in the range of 8 mm 2 /s or more and less than 25 mm 2 /s, and may be 10 mm 2 The range from 14 mm 2 /s to 22 mm 2 /s may be within the range of 14 mm 2 /s or more and 23 mm 2 /s or less. If the value of the above kinematic viscosity satisfies the above numerical value, the viscosity of the rubber composition or tire containing the petroleum-based aromatic oil becomes good, so the values of tanδ (50°C) and tanδ (0°C) become more favorable, Thus, the combination of wet grip performance and rolling resistance performance becomes better. Furthermore, when the value of the said kinematic viscosity is below the said upper limit, the migration and workability|operativity for preparing the oil containing a petroleum-based aromatic in rubber become favorable.

100℃下之動黏度可根據JIS K2283：2000之規定而求出。The kinematic viscosity at 100°C can be obtained according to the regulations of JIS K2283:2000.

實施形態之含有石油系芳香族之油之苯胺點較佳為52℃以上，更佳為56℃以上，進而較佳為60℃以上。實施形態之含有石油系芳香族之油之苯胺點較佳為95℃以下，更佳為92℃以下，進而較佳為88℃以下，特佳為84℃以下。作為上述數值之數值範圍之一例，實施形態之含有石油系芳香族之油之苯胺點可為52℃以上95℃以下之範圍，可為52℃以上92℃以下之範圍，可為56℃以上88℃以下之範圍，可為60℃以上84℃以下之範圍。苯胺點係等量之苯胺與油發生混合之溫度，成為橡膠相容性之指標。若苯胺點為上述上限值以下，則即便不進行過度之加溫，油亦與苯胺溶合，橡膠相容性較高而較佳。即，若苯胺點之值滿足上述數值，則含有石油系芳香族之油對於橡膠之親和性變得良好，使所製造之橡膠組合物或輪胎之物理特性變得更良好。The aniline point of the petroleum-based aromatic-containing oil of the embodiment is preferably 52°C or higher, more preferably 56°C or higher, and still more preferably 60°C or higher. The aniline point of the petroleum-based aromatic-containing oil of the embodiment is preferably 95°C or lower, more preferably 92°C or lower, still more preferably 88°C or lower, and particularly preferably 84°C or lower. As an example of the numerical range of the above-mentioned numerical values, the aniline point of the petroleum-based aromatic-containing oil in the embodiment may be in the range of 52°C or higher and 95°C or lower, 52°C or higher and 92°C or lower, or 56°C or higher. 88 The range of ℃ or less may be the range of 60°C or more and 84°C or less. The aniline point is the temperature at which equal amounts of aniline and oil are mixed, and is an indicator of rubber compatibility. If the aniline point is below the above-mentioned upper limit value, the oil and the aniline are fused even without excessive heating, and the rubber compatibility is high and preferable. That is, when the value of the aniline point satisfies the above-mentioned value, the affinity of the oil containing a petroleum-based aromatic to rubber becomes good, and the physical properties of the produced rubber composition and tire become more favorable.

苯胺點可根據ASTM D611-12石油製品與烴溶劑之苯胺點及混合苯胺點之標準測試方法(Standard Test Methods for Aniline Point and Mixed Aniline Point of Petroleum Products and Hydrocarbon Solvents)之規定而求出。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.

實施形態之含有石油系芳香族之油之玻璃轉移點(Tg)較佳為-60℃以上，更佳為-56℃以上，進而較佳為-54℃以上。實施形態之含有石油系芳香族之油之玻璃轉移點(Tg)較佳為-34℃以下，更佳為-36℃以下，進而較佳為-38℃以下。作為上述數值之數值範圍之一例，實施形態之含有石油系芳香族之油之玻璃轉移點(Tg)可為-60℃以上-34℃以下之範圍，可為-56℃以上-36℃以下之範圍，可為-54℃以上-38℃以下之範圍。若玻璃轉移點滿足上述數值，則所製造之橡膠組合物或輪胎之物理特性變得更良好，對提高濕地抓地性能及滾動阻力性能較為重要。The glass transition point (Tg) of the petroleum-based aromatic-containing oil of the embodiment is preferably -60°C or higher, more preferably -56°C or higher, and further preferably -54°C or higher. The glass transition point (Tg) of the petroleum-based aromatic-containing oil of the embodiment is preferably -34°C or lower, more preferably -36°C or lower, and still more preferably -38°C or lower. As an example of the numerical range of the above-mentioned numerical values, the glass transition point (Tg) of the petroleum-based aromatic-containing oil of the embodiment may be in the range of -60°C or higher and -34°C or lower, and may be in the range of -56°C or higher and -36°C or lower. The range can be in the range of -54°C or higher and -38°C or lower. When the glass transition point satisfies the above-mentioned values, the physical properties of the produced rubber composition or tire become more favorable, and it is important to improve wet grip performance and rolling resistance performance.

玻璃轉移點可藉由下述實施例所記載之測定條件而求出。The glass transition point can be determined by the measurement conditions described in the following examples.

實施形態之含有石油系芳香族之油之黏度比重常數(VGC)較佳為0.85以上，更佳為0.86以上，進而較佳為0.87以上。實施形態之含有石油系芳香族之油之黏度比重常數(VGC)較佳為0.92以下，更佳為0.91以下，進而較佳為0.90以下。作為上述數值之數值範圍之一例，實施形態之含有石油系芳香族之油之黏度比重常數(VGC)可為0.85以上0.92以下，可為0.86以上0.91以下，可為0.87以上0.90以下。黏度比重常數係表示油之組成之指數，一般而言，有若鏈烷性變高，則值變低，若芳香性較高，則值變高之傾向。若上述黏度比重常數之值滿足上述數值，則包含含有石油系芳香族之油之橡膠組合物或輪胎之物理特性變得良好，因此tanδ(50℃)及tanδ(0℃)之值變得更良好，從而使濕地抓地性能及滾動阻力性能之兼具變得更良好。The viscosity specific gravity constant (VGC) of the petroleum-based aromatic-containing oil of the embodiment is preferably 0.85 or more, more preferably 0.86 or more, and still more preferably 0.87 or more. The viscosity specific gravity constant (VGC) of the petroleum-based aromatic-containing oil of the embodiment is preferably 0.92 or less, more preferably 0.91 or less, and still more preferably 0.90 or less. As an example of the numerical range of the above-mentioned numerical values, the viscosity specific gravity constant (VGC) of the petroleum-based aromatic-containing oil of the embodiment can be 0.85 or more and 0.92 or less, 0.86 or more and 0.91 or less, and 0.87 or more and 0.90 or less. The viscosity specific gravity constant is an index indicating the composition of the oil. Generally speaking, the higher the paraffinicity, the lower the value, and the higher the aromaticity, the higher the value. If the value of the above-mentioned viscosity specific gravity constant satisfies the above-mentioned numerical value, the physical properties of the rubber composition or tire containing the oil containing petroleum-based aromatics become good, so the values of tanδ (50°C) and tanδ (0°C) become higher. Good, so that the combination of wet grip performance and rolling resistance performance becomes better.

黏度比重常數(VGC)可根據ASTM D2140-08計算石油來源之絕緣油之碳型成分之標準操作(Standard Practice for Calculating Carbon-Type Composition of Insulating Oils of Petroleum Origin)之規定而求出。The viscosity specific gravity constant (VGC) can be obtained according to ASTM D2140-08 Standard Practice for Calculating Carbon-Type Composition of Insulating Oils of Petroleum Origin.

實施形態之含有石油系芳香族之油的利用環分析所得之%CA較佳為8以上，更佳為9以上，進而較佳為10以上。實施形態之含有石油系芳香族之油的利用環分析所得之%CA較佳為28以下，更佳為26以下，進而較佳為24以下。作為上述數值之數值範圍之一例，實施形態之含有石油系芳香族之油的利用環分析所得之%CA可為8以上28以下，可為9以上26以下，可為10以上24以下。 若上述%CA滿足上述數值，則有抑制致癌性較高之多環芳香族量，同時帶有提高與橡膠之相容性之芳香性之傾向，使含有上述油之橡膠組合物或輪胎之tanδ(50℃)及tanδ(0℃)之值變得良好，從而使濕地抓地性能及滾動阻力性能之兼具變得更良好。The %CA obtained by the ring analysis of the petroleum-based aromatic-containing oil of the embodiment is preferably 8 or more, more preferably 9 or more, and still more preferably 10 or more. The %CA obtained by the ring analysis of the petroleum-based aromatic-containing oil of the embodiment is preferably 28 or less, more preferably 26 or less, and still more preferably 24 or less. As an example of the numerical range of the above-mentioned numerical value, the %CA obtained by the ring analysis of the petroleum-based aromatic-containing oil of the embodiment may be 8 or more and 28 or less, 9 or more and 26 or less, and 10 or more and 24 or less. If the above-mentioned %CA satisfies the above-mentioned value, the amount of polycyclic aromatics with high carcinogenicity is suppressed, and the aromaticity of the compatibility with rubber tends to be improved, so that the tanδ of the rubber composition or tire containing the above-mentioned oil tends to be reduced. The values of (50°C) and tanδ (0°C) became good, and the combination of wet grip performance and rolling resistance performance became more favorable.

%CA可根據ASTM D2140-08計算石油來源之絕緣油之碳型成分之標準操作之規定而求出。%CA can be determined according to ASTM D2140-08 Standard Practice for Calculating the Carbon-Type Composition of Petroleum-derived Insulating Oils.

實施形態之含有石油系芳香族之油適宜用作混合於橡膠中而使用之增量油或加工處理油。The petroleum-based aromatic-containing oil of the embodiment is suitably used as an extender oil or a processing oil to be mixed with rubber.

[含有石油系芳香族之油之製造方法] 以下，對於實施形態之含有石油系芳香族之油之製造方法進行說明。根據上述方法，可製造本發明之含有石油系芳香族之油。本發明之含有石油系芳香族之油不限定於藉由下述實施形態之含有石油系芳香族之油之製造方法所製造者。[Production method of petroleum-based aromatic oil] Hereinafter, the production method of the petroleum-based aromatic-containing oil according to the embodiment will be described. According to the above-mentioned 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 according to the following embodiments.

實施形態之含有石油系芳香族之油之製造方法包括： 獲得將經溶劑萃取所獲得之萃餘物進一步進行溶劑萃取所獲得之萃取物之步驟；或 獲得將經溶劑萃取所獲得之萃取物進一步進行溶劑萃取所獲得之萃餘物之步驟；或 使將經溶劑萃取所獲得之萃餘物進一步進行溶劑萃取所獲得之萃取物、與將經溶劑萃取所獲得之萃餘物進一步進行溶劑萃取所獲得之萃餘物或將該萃餘物進行精製所得之基油加以混合之步驟。 作為溶劑萃取之對象物，可列舉：對將原油進行常壓蒸餾所得之殘渣進行減壓蒸餾所得之減壓蒸餾餾分。於溶劑萃取中，萃取物可藉由如下方式獲得，即，藉由對於芳香族烴具有親和性之溶劑對溶劑萃取之對象物進行萃取處理，對溶劑與萃取物(extract)進行分離回收。起始原料之原油可單獨或混合使用鏈烷系原油、環烷系原油等各種原油，特佳為使用鏈烷系原油。The manufacturing method of the petroleum-based aromatic-containing oil of the embodiment includes: a step of obtaining an extract obtained by subjecting the raffinate obtained by solvent extraction to further solvent extraction; or a step of obtaining a raffinate obtained by subjecting the extract obtained by solvent extraction to further solvent extraction; or The raffinate obtained by subjecting the raffinate obtained by solvent extraction to further solvent extraction, and the raffinate obtained by subjecting the raffinate obtained by solvent extraction to further solvent extraction or refining the raffinate The step of mixing the resulting base oils. Examples of the object of solvent extraction include a vacuum distillation fraction obtained by vacuum distillation of a residue obtained by subjecting crude oil to atmospheric distillation. In the solvent extraction, the extract can be obtained by subjecting the solvent-extracted object to extraction treatment with a solvent having an affinity for aromatic hydrocarbons to separate and recover the solvent and the extract. Various kinds of crude oil such as paraffinic crude oil and naphthenic crude oil can be used alone or in combination as the crude oil of the starting material, and paraffinic crude oil is particularly preferably used.

以下，對於使將經溶劑萃取所獲得之萃餘物進一步進行溶劑萃取所獲得之萃取物、與將經溶劑萃取所獲得之萃餘物進一步進行溶劑萃取所獲得之萃餘物或將該萃餘物進行精製所得之基油加以混合之步驟進行說明。 圖1係對實施形態之含有石油系芳香族之油之製造方法之一例進行說明的步驟圖。原油首先藉由常壓蒸餾裝置(未圖示)進行處理，藉此獲得常壓蒸餾殘渣。常壓蒸餾殘渣被送至減壓蒸餾裝置10進行減壓蒸餾，從而獲得減壓蒸餾餾分11。減壓蒸餾餾分11被送至第1溶劑萃取裝置30a。於第1溶劑萃取裝置30a中，將減壓蒸餾餾分11分離成萃餘物31a及萃取物33a。所分離之萃餘物31a被送至第2溶劑萃取裝置30b。於第2溶劑萃取裝置30b中，將萃餘物31a分離成萃餘物31b及萃取物33b。萃餘物31b藉由氫化精製裝置40進行氫化精製而成為氫化精製油41，進而藉由脫蠟裝置50進行脫蠟，從而獲得脫蠟油51。可將所獲得之脫蠟油51與萃取物33b加以混合而獲得含有石油系芳香族之油62。Hereinafter, for the raffinate obtained by subjecting the raffinate obtained by solvent extraction to further solvent extraction, the raffinate obtained by subjecting the raffinate obtained by solvent extraction to further solvent extraction, or the raffinate obtained by subjecting the raffinate obtained by solvent extraction to further solvent extraction The procedure for mixing the base oil obtained by refining the product will be explained. FIG. 1 is a process diagram illustrating an example of a method for producing a petroleum-based aromatic-containing oil according to an embodiment. The crude oil is first processed by an atmospheric distillation apparatus (not shown), thereby obtaining an atmospheric distillation residue. The atmospheric distillation residue is sent to a vacuum distillation apparatus 10 for vacuum distillation, whereby a vacuum distillation fraction 11 is obtained. The vacuum distillation fraction 11 is sent to the first solvent extraction device 30a. In the first solvent extraction apparatus 30a, the vacuum distillation fraction 11 is separated into the raffinate 31a and the extract 33a. The separated raffinate 31a is sent to the second solvent extraction device 30b. In the second solvent extraction apparatus 30b, the raffinate 31a is separated into the raffinate 31b and the extract 33b. The raffinate 31b is hydro-refined by the hydro-refining apparatus 40 to become the hydro-refined oil 41 , which is further dewaxed by the dewaxing apparatus 50 to obtain the dewaxed oil 51 . The obtained dewaxed oil 51 and the extract 33b can be mixed to obtain the petroleum-based aromatic-containing oil 62 .

此處，對將脫蠟油51與萃取物33b加以混合而獲得含有石油系芳香族之油62之情形進行了說明，但亦可將萃餘物31b或氫化精製油41代替脫蠟油51與萃取物33b混合。Here, the case where the oil 62 containing petroleum-based aromatics is obtained by mixing the dewaxed oil 51 and the extract 33b has been described, but the raffinate 31b or the hydrorefined oil 41 may be replaced by the dewaxed oil 51 and Extracts 33b were mixed.

又，亦可將萃取物33b設為含有石油系芳香族之油62。Moreover, the extract 33b can also be made into the oil 62 containing a petroleum-based aromatic.

又，雖未圖示，但亦可將使萃取物33a進一步進行溶劑萃取所獲得之萃餘物設為含有石油系芳香族之油。In addition, although not shown in the figure, the raffinate obtained by subjecting the extract 33a to further solvent extraction may be an oil containing petroleum-based aromatics.

減壓蒸餾於餾出油之終沸點以常壓換算成為580℃以上之條件或殘渣之初餾點成為450℃以上之條件下進行由於可容易將所獲得之萃取物中之芳香族含量調整至特定範圍，故而較佳。 溶劑萃取為了獲得萃取物33a、33b，較佳為進行藉由對芳香族烴具有選擇性親和性之溶劑進行萃取之處理。作為對芳香族烴具有選擇性親和性之溶劑，可為極性溶劑，可使用選自由糠醛、苯酚及N-甲基-2-吡咯啶酮所組成之群中之1種或其以上。由於用於使萃取物產率變為上述範圍之具體之萃取條件亦取決於脫瀝青油組成，故而無法單一地決定，可藉由適當選定溶劑比、壓力、溫度等而進行。一般而言，於塔頂溫度：較佳為100～155℃、更佳為100～140℃、塔底溫度：較佳為40～120℃、更佳為50～110℃、相對於油1之溶劑比：較佳為1～5、更佳為1.5～4.5之條件下與溶劑接觸即可。 另一方面，溶劑萃取為了獲得萃餘物31a、31b，較佳為進行藉由對芳香族烴具有親和性之溶劑進行萃取之溶劑精製處理。作為對芳香族烴具有選擇性親和性之溶劑，可自糠醛、苯酚及N-甲基-2-吡咯啶酮中選擇1種或其以上使用。於該溶劑精製步驟中，於通常之精製潤滑油基油之條件下，例如於使用糠醛作為萃取溶劑之情形時，於塔頂溫度：較佳為60～150℃、更佳為70～140℃、塔底溫度：較佳為40～90℃、更佳為50～80℃、相對於油1之溶劑比：較佳為0.5～4、更佳為1～3之條件下與溶劑接觸即可。 根據其他所需，藉由氫化精製及/或溶劑脫蠟或氫化脫蠟處理對萃餘物進行脫蠟，藉此可獲得更佳之基油。上述氫化精製於將鎳、鈷、鉬等活性金屬1種以上擔載於氧化鋁或二氧化矽-氧化鋁等載體而成之觸媒之存在下，於氫壓5～15 MPa、溫度250～400℃、液體空間速度(LHSV)1～5 h-1 之條件下進行即可。又，上述溶劑脫蠟例如於甲基乙基酮/甲苯之混合溶劑下，於溶劑/油比(體積比)＝1/1～5/1、溫度-10～-40℃之條件下進行即可，又，氫化脫蠟於沸石觸媒之存在下，於氫壓5～15 MPa、溫度300～400℃、LHSV 1～5 Hr-1 之條件下進行即可。 氫化精製係於觸媒存在下使高溫高壓之氫與原料油接觸，藉此可將硫份、氮份等對加工處理油之使用、保存等帶來不良影響之雜質作為氫化輕質反應物而去除，結果可提高穩定性或色相等。溶劑脫蠟係使用選自由丙酮、甲基乙基酮、苯、甲苯所組成之群中之1種或其以上之溶劑混合於原料油，其後，經過冷卻步驟使以正構鏈烷為代表之蠟餾分析出，藉由過濾器將其過濾而分離去除，藉此可實現提高低溫流動性。 藉由將以上述方式獲得之萃餘物進一步進行溶劑萃取所得之萃取物，可製造實施形態之含有石油系芳香族之油。 或，藉由將以上述方式獲得之萃取物進一步進行溶劑萃取所得之萃餘物，可製造實施形態之含有石油系芳香族之油。 或，藉由以質量比計95/5～5/95、特佳為80/20～20/80之比率將以上述方式獲得之萃取物與基油加以混合，可製造實施形態之含有石油系芳香族之油。The distillation under reduced pressure is carried out under the condition that the final boiling point of the distillate is 580°C or higher in normal pressure conversion or the initial boiling point of the residue is 450°C or higher, because the aromatic content in the obtained extract can be easily adjusted to A specific range is therefore preferred. Solvent Extraction In order to obtain the extracts 33a and 33b, it is preferable to perform extraction with a solvent having a selective affinity for aromatic hydrocarbons. As the 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 can be used. Since the specific extraction conditions for making the extract yield into the above range also depend on the composition of the deasphalted oil, it cannot be determined solely, and can be performed by appropriately selecting the solvent ratio, pressure, temperature, and the like. In general, the temperature at the top of the tower: preferably 100-155°C, more preferably 100-140°C, and the temperature at the bottom of the tower: preferably 40-120°C, more preferably 50-110°C, relative to oil 1 Solvent ratio: preferably 1 to 5, more preferably 1.5 to 4.5, the solvent may be contacted with the solvent. On the other hand, in order to obtain the raffinates 31a and 31b in the solvent extraction, it is preferable to perform a solvent purification treatment by extraction with a solvent having an affinity for aromatic hydrocarbons. As the 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 conditions of the usual refining lubricating oil base oil, for example, when furfural is used as the extraction solvent, the temperature at the top of the tower: preferably 60-150°C, more preferably 70-140°C , The temperature at the bottom of the tower: preferably 40-90 ℃, more preferably 50-80 ℃, relative to the solvent ratio of oil 1: preferably 0.5-4, more preferably 1-3 under the conditions of contact with the solvent . According to other requirements, the raffinate can be dewaxed by hydrofinishing and/or solvent dewaxing or hydrodewaxing treatment, whereby better base oils can be obtained. The above-mentioned hydro-refining 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 °C and liquid space velocity (LHSV) of 1 to 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 temperature of -10 to -40°C. Alternatively, the hydrodewaxing may 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, whereby impurities such as sulfur and nitrogen that adversely affect the use and storage of the processed oil can be removed as hydrogenated light reactants. Removed, the result can be improved stability or color, etc. The solvent dewaxing system uses one or more solvents selected from the group consisting of acetone, methyl ethyl ketone, benzene, and toluene to mix with the feedstock oil, and then passes through a cooling step to make n-paraffin as a representative The wax distillate is analyzed, and it is separated and removed by filtration through a filter, thereby improving low temperature fluidity. By subjecting the raffinate obtained as described above to the extract obtained by further solvent extraction, the petroleum-based aromatic-containing oil of the embodiment can be produced. Alternatively, the raffinate obtained by subjecting the extract obtained in the above-described manner to further solvent extraction, the petroleum-based aromatic-containing oil of the embodiment can be produced. Alternatively, by mixing the extract obtained in the above-mentioned manner with the base oil in a mass ratio of 95/5 to 5/95, particularly preferably 80/20 to 20/80, the petroleum-based oil-containing system of the embodiment can be produced. Aromatic oil.

≪橡膠組合物≫ 以下，對於實施形態之橡膠組合物進行說明。本發明之橡膠組合物不限定於下述橡膠組合物。 圖2A及B係對由原料橡膠製備輪胎組合物之過程之一例進行說明之步驟圖。成為輪胎原料之輪胎組合物調配有原料橡膠、及各種調配劑。合成橡膠有時於其合成時調配增量油，可使用預先含有增量油之橡膠組合物(亦被稱為充油橡膠)作為原料橡膠(參照圖2A)。或亦可使用不含有增量油之原料橡膠(亦被稱為非充油橡膠)(參照圖2B)。於原料橡膠中添加加工處理油及各種調配劑(參照圖2A及B)。 作為充油橡膠之原料橡膠(橡膠組合物)可藉由將單體供於聚合反應而獲得，於該過程中可添加增量油而製造。例如，藉由將包含作為原料橡膠之橡膠原料之單體及增量油之反應液供於聚合反應之方法，或使包含作為原料橡膠之橡膠原料之單體之反應液發生聚合反應後，於聚合物溶液中添加增量油之方法，可製造充油橡膠(圖2A)。 輪胎組合物(橡膠組合物)可藉由例如公知之橡膠用混練機例如滾壓機、混合機、捏合機等對上述原料橡膠、本發明之含有石油系芳香族之油、及調配劑進行混練而製造。輪胎組合物可於任意之條件下進行硫化。 於本說明書中，將含有原料橡膠及實施形態之含有石油系芳香族之油(增量油或加工處理油)者稱為橡膠組合物。 實施形態之橡膠組合物適宜作為用於輪胎之製造之輪胎用橡膠組合物。作為一實施形態，本發明提供一種含有原料橡膠、本發明之含有石油系芳香族之油、及調配劑之輪胎組合物。輪胎組合物視作包含於實施形態之橡膠組合物之概念。輪胎組合物(橡膠組合物)可經硫化，亦可未硫化。 此處，將增量油與加工處理油區分表示，但有時其等被統稱為加工處理油。≪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 a process for preparing a tire composition from raw rubber. The tire composition used as a tire raw material is formulated with raw rubber and various compounding agents. Synthetic rubber may be prepared with an extender oil at the time of its synthesis, and a rubber composition (also called oil-extended rubber) containing an extender oil in advance can be used as the raw rubber (refer to FIG. 2A ). Alternatively, a raw rubber (also referred to as non-oil-extended rubber) that does not contain extender oil may be used (refer to FIG. 2B ). Processing oil and various formulations are added to the raw rubber (see FIGS. 2A and B ). The raw material rubber (rubber composition) of the oil-extended rubber can be obtained by subjecting a monomer to a polymerization reaction, and an extender oil can be added during the process to produce it. For example, by a method of subjecting a reaction liquid containing a monomer and an extender oil as a raw rubber raw material to a polymerization reaction, or by subjecting a reaction liquid containing a monomer of a rubber raw material as a raw rubber to a polymerization reaction, then The method of adding extender oil to the polymer solution can produce oil-extended rubber (Fig. 2A). The tire composition (rubber composition) can be kneaded with the above-mentioned raw rubber, the petroleum-based aromatic-containing oil of the present invention, and the compounding agent by, for example, a known rubber kneader such as a roller press, a mixer, a kneader, or the like. And manufacture. The tire composition can be vulcanized under any conditions. In this specification, what contains the raw material rubber and the petroleum-based aromatic-containing 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 a raw rubber, the petroleum-based aromatic-containing 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 processing oil are shown separately, but they may be collectively referred to as the processing oil in some cases.

以下，對於橡膠組合物及輪胎組合物之組成進行說明。Hereinafter, the composition of the rubber composition and the tire composition will be described.

作為原料橡膠，可使用彈性體性聚合物，例如可列舉：天然橡膠、異戊二烯橡膠、丁二烯橡膠、1,2-丁二烯橡膠、苯乙烯-丁二烯橡膠、異戊二烯-丁二烯橡膠、苯乙烯-異戊二烯-丁二烯橡膠、乙烯-丙烯-二烯橡膠、鹵化丁基橡膠、鹵化異戊二烯橡膠、鹵化異丁烯共聚物、氯丁二烯橡膠、丁基橡膠及鹵化異丁烯-對甲基苯乙烯橡膠、腈橡膠、氯丁二烯橡膠等二烯系橡膠、丁基橡膠、乙烯-丙烯系橡膠(EPDM、EPM)、乙烯-丁烯橡膠(BBM)、氯磺化聚乙烯、丙烯酸系橡膠、氟橡膠等烯烴系橡膠、表氯醇橡膠、聚硫橡膠、矽酮橡膠、胺基甲酸酯橡膠等，又，亦可為可經氫化之聚苯乙烯系彈性體性聚合物(SBS、SIS、SEBS)、聚烯烴系彈性體性聚合物、聚氯乙烯系彈性體性聚合物、聚胺基甲酸酯系彈性體性聚合物、聚酯系彈性體性聚合物或聚醯胺系彈性體性聚合物等熱塑性彈性體。該等可單獨使用，或作為任意摻合物而使用。 就與含有石油系芳香族之油之相容性之觀點而言，彈性體性聚合物較佳為選自由天然橡膠、異戊二烯橡膠、苯乙烯-丁二烯橡膠、丁二烯橡膠、丁基橡膠、氯丁二烯橡膠、及丙烯腈橡膠所組成之群中之至少一種。進而，就可適宜使用於發揮作為輪胎性能之滾動阻力性能及濕地抓地性能之胎面部之觀點而言，彈性體性聚合物較佳為選自由天然橡膠、異戊二烯橡膠、苯乙烯丁二烯橡膠、丁二烯橡膠所組成之群中之至少一種。As the raw material rubber, an elastomeric polymer can be used, for example, natural rubber, isoprene rubber, butadiene rubber, 1,2-butadiene rubber, styrene-butadiene rubber, isoprene Ethylene-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-butylene rubber ( BBM), chlorosulfonated polyethylene, acrylic rubber, fluororubber and other olefin-based rubbers, epichlorohydrin rubber, polysulfide rubber, silicone rubber, urethane rubber, etc., and can also be hydrogenated Polystyrene-based elastomeric polymers (SBS, SIS, SEBS), polyolefin-based elastomeric polymers, polyvinyl chloride-based elastomeric polymers, polyurethane-based elastomeric polymers, poly Thermoplastic elastomers such as ester-based elastomeric polymers and polyamide-based elastomeric polymers. These can be used alone, or as any admixture. From the viewpoint of compatibility with petroleum-based aromatic-containing 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, the elastomeric polymer is preferably selected from the group consisting of natural rubber, isoprene rubber, and styrene from the viewpoint of being suitably used for the tread portion that exhibits rolling resistance performance and wet grip performance as tire performance. At least one of the group consisting of butadiene rubber and butadiene rubber.

作為增量油、或加工處理油，可使用實施形態之含有石油系芳香族之油。As the extender oil or the processing oil, the petroleum-based aromatic-containing oil of the embodiment can be used.

作為調配劑，可列舉：填充劑、防老化劑、抗氧化劑、交聯劑(硫化劑)、交聯促進劑、樹脂、塑化材料、硫化促進劑、硫化促進助劑(硫化助劑)等。As the preparation agent, fillers, antiaging agents, antioxidants, crosslinking agents (vulcanizing agents), crosslinking accelerators, resins, plasticizing materials, vulcanization accelerators, vulcanization accelerator assistants (vulcanization assistants), etc. can be mentioned. .

作為填充劑，可列舉：碳黑、二氧化矽、矽烷化合物(矽烷偶合劑)等，較佳為二氧化矽及/或矽烷偶合劑。 碳黑基於粒徑被分類成硬碳及軟碳。軟碳對於橡膠之補強性較低，硬碳對於橡膠之補強性較強。於實施形態之橡膠組合物含有碳黑之情形時，特佳為使用補強性較強之硬碳。相對於彈性體性聚合物100質量份，碳黑較佳為調配有10～250質量份，更佳為調配有20～200質量份，進而較佳為調配有30～50質量份。 作為二氧化矽，無特別限定，例如可列舉：乾式法白碳、濕式法白碳、膠體二氧化矽、及沈澱二氧化矽等。該等之中，較佳為以含水矽酸作為主成分之濕式法白碳。該等二氧化矽可分別單獨使用或組合2種以上使用。該等二氧化矽之比表面積無特別限制，當以氮吸附比表面積(BET法)計通常為10～400 m2 /g、較佳為20～300 m2 /g、進而較佳為120～190 m2 /g之範圍時，對於改善補強性、耐磨耗性及發熱性等較為適宜。此處，氮吸附比表面積係依據ASTM D3037-81藉由BET法進行測定所得之值。 作為矽烷化合物，無特別限制，較佳為含有硫之矽烷偶合劑，更佳為雙(3-三乙氧基矽烷基丙基)二硫化物。As a filler, carbon black, silica, a silane compound (silane coupling agent) etc. are mentioned, Preferably it is a silica and/or a silane coupling agent. Carbon black is classified into hard carbon and soft carbon based on particle size. Soft carbon has low reinforcement for rubber, and hard carbon has strong reinforcement for rubber. In the case where the rubber composition of the embodiment contains carbon black, it is particularly preferable to use a hard carbon with strong reinforcing properties. It is preferable to mix|blend 10-250 mass parts of carbon black with respect to 100 mass parts of elastomeric polymers, It is more preferable to mix|blend 20-200 mass parts, and it is still more preferable to mix|blend 30-50 mass parts. Although it does not specifically limit as silica, For example, dry process white carbon, wet process white carbon, colloidal silica, and precipitated silica etc. are mentioned. Among these, wet-process white carbon containing hydrous silicic acid as a main component is preferable. These silicas may be used alone or in combination of two or more. The specific surface area of these silicas is not particularly limited, and is usually 10-400 m 2 /g, preferably 20-300 m 2 /g, and more preferably 120- The range of 190 m 2 /g is suitable for improving reinforcement, abrasion resistance and heat generation. 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 preferable, and bis(3-triethoxysilylpropyl)disulfide is more preferable.

作為交聯劑(硫化劑)，可列舉：粉末硫、沈澱性硫、高分散性硫、表面處理硫、不溶性硫等。As a crosslinking agent (vulcanizing agent), powder sulfur, precipitation sulfur, highly dispersible sulfur, surface-treated sulfur, insoluble sulfur, etc. are mentioned.

作為硫化促進劑，可列舉：二硫化四甲基秋蘭姆(TMTD)、二硫化四乙基秋蘭姆(TETD)等秋蘭姆系、六亞甲基四胺等醛-氨系、二苯胍等胍系、二硫化二苯并噻唑(DM)等噻唑系、N-環己基-2-苯并噻唑次磺醯胺等環己基苯并噻唑次磺醯胺系等。Examples of vulcanization accelerators include thiuram-based tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD) and the like, aldehyde-ammonia-based such as hexamethylenetetramine, Guanidine systems such as benzoguanidine, thiazole systems such as dibenzothiazole disulfide (DM), cyclohexylbenzothiazole sulfenamide systems such as N-cyclohexyl-2-benzothiazole sulfenamide, and the like.

作為硫化促進助劑，可列舉：乙酸、丙酸、丁酸、硬脂酸、丙烯酸、順丁烯二酸等脂肪酸、乙酸鋅、丙酸鋅、丁酸鋅、硬脂酸鋅、丙烯酸鋅、順丁烯二酸鋅等脂肪酸鋅、鋅白等。Examples of the vulcanization accelerator 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.

該等原料橡膠、本發明之含有石油系芳香族之油、及調配劑之調配量只要不違反本發明之目的，則可設為一般之調配量。The compounding amounts of these raw rubber, the petroleum-based aromatic-containing oil of the present invention, and the compounding agent can be set to general compounding amounts as long as the object of the present invention is not violated.

作為一例，可例示：相對於彈性體性聚合物100質量份，調配填充劑：30～100質量份、含有石油系芳香族之油：80質量份以下、防老化劑：0.5～5質量份、交聯劑：1～10質量份、樹脂：0～20質量份、硫化促進劑：0.5～5質量份、硫化促進助劑：1～10質量份。 於使用二氧化矽及/或矽烷偶合劑作為填充劑之情形時，相對於彈性體性聚合物100質量份，二氧化矽及/或矽烷偶合劑較佳為調配有10～300質量份，更佳為調配有50～150質量份，進而較佳為調配有70～100質量份。相對於彈性體性聚合物100質量份，矽烷化合物(矽烷偶合劑)之含量較佳為0.1～30質量份，更佳為1～20質量份。 相對於彈性體性聚合物100質量份，含有石油系芳香族之油較佳為調配有0.5～80質量份，更佳為調配有10～50質量份，進而較佳為調配有20～40質量份。As an example, with respect to 100 parts by mass of the elastomeric polymer, filler: 30 to 100 parts by mass, petroleum-based aromatic-containing oil: 80 parts by mass or less, antiaging agent: 0.5 to 5 parts by mass, Crosslinking agent: 1 to 10 parts by mass, resin: 0 to 20 parts by mass, vulcanization accelerator: 0.5 to 5 parts by mass, and vulcanization accelerator: 1 to 10 parts by mass. In the case of using silica and/or silane coupling agent as filler, the amount of silica and/or silane coupling agent is preferably 10-300 parts by mass relative to 100 parts by mass of the elastomeric polymer, more It is preferable to mix|blend 50-150 mass parts, and it is more preferable to mix|blend 70-100 mass parts. The content of the silane compound (silane coupling agent) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the elastomeric polymer. With respect to 100 parts by mass of the elastomeric polymer, the amount of the oil containing petroleum-based aromatics is preferably 0.5 to 80 parts by mass, more preferably 10 to 50 parts by mass, and more preferably 20 to 40 parts by mass share.

根據實施形態之橡膠組合物，可提供一種滾動阻力性能及濕地抓地性能優異之橡膠組合物。According to the rubber composition of the embodiment, a rubber composition excellent in rolling resistance performance and wet grip performance can be provided.

≪輪胎、輪胎之製造方法≫ 實施形態之輪胎含有上述實施形態之含有石油系芳香族之油。 實施形態之輪胎可藉由調配橡膠與實施形態之含有石油系芳香族之油進行硫化而製造。 換言之，實施形態之輪胎可包含上述輪胎組合物(橡膠組合物)，可藉由對輪胎組合物進行硫化而製造。具體而言，例如，可使上述輪胎組合物硫化成形而製造輪胎。更具體而言，例如，對上述輪胎組合物進行加熱熔融，擠出經加熱熔融之輪胎組合物，其次，使用輪胎成型機成形後，使用硫化機進行加熱、加壓，藉此可製造輪胎。≪Tire, tire manufacturing method≫ The tire of the embodiment contains the petroleum-based aromatic-containing oil of the above-described embodiment. The tire of the embodiment can be produced by vulcanizing the rubber and the petroleum-based aromatic-containing oil of the embodiment. In other words, the tire of the embodiment can contain the above-mentioned tire composition (rubber composition), and can be produced by vulcanizing the tire composition. Specifically, for example, the tire composition described above can be vulcanized and molded to manufacture a tire. More specifically, for example, a tire can be manufactured by heating and melting the above-mentioned tire composition, extruding the heat-melted tire composition, and then molding with a tire building machine, then heating and pressurizing with a vulcanizer.

作為一例，輪胎包含胎面、胎體(Carcass)、胎壁(side wall)、氣密層(inner liner)、胎面基部(under tread)、帶束部(belt)等輪胎各部。實施形態之輪胎較佳為於胎面部含有上述實施形態之含有石油系芳香族之油。實施形態之輪胎較佳為具有包含實施形態之輪胎組合物之輪胎面。藉由成為接地面之胎面部包含含有石油系芳香族之油，而良好地發揮滾動阻力性能及濕地抓地性能。As an example, the 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-containing oil of the above-described embodiment in the tread portion. The tire of the embodiment preferably has a tire tread containing the tire composition of the embodiment. Rolling resistance performance and wet grip performance are well exhibited by containing oil containing petroleum-based aromatics in the tread portion that becomes the ground contact surface.

根據實施形態之輪胎及輪胎之製造方法，可提供一種滾動阻力性能及濕地抓地性能優異之輪胎。According to the tire and the tire manufacturing method of the embodiment, a tire excellent in rolling resistance performance and wet grip performance can be provided.

關於為何實施形態之含有石油系芳香族之油對輪胎組合物(橡膠組合物)之濕地抓地性能及滾動阻力性能之兼具發揮效果，推定如下。 由於兩種性能自相矛盾，故而若不有損一者地提高另一者，則結果為可兼具。通常，藉由於被稱為省燃耗輪胎者調配二氧化矽而試圖兼具兩者，特別是省燃耗性能，但二氧化矽於表面親水基較多，難以與橡膠聚合物親和，因此有二氧化矽彼此凝集之傾向。於該情形時，當輪胎於行駛中變形時，二氧化矽彼此發生摩擦等而發熱，產生多餘之能量損失。因此，如何使二氧化矽分散於橡膠聚合物中成為要點。認為以特定量包含上述特定成分之含有石油系芳香族之油包含二氧化矽，對各種調配劑之分散或溶解發揮作用，該等於橡膠聚合物中之行為對各物理特性帶來較佳之影響，結果實現矛盾性能之兼具。 [實施例]The reason why the petroleum-based aromatic-containing oil of the embodiment exhibits both the wet grip performance and the rolling resistance performance of the tire composition (rubber composition) is estimated as follows. Since the two properties are contradictory, if one improves the other without compromising the other, the result is both. Usually, the so-called fuel-efficient tires are formulated with silicon dioxide to try to have both, especially the fuel-saving performance. However, silicon dioxide has many hydrophilic groups on the surface, which is difficult to have affinity with rubber polymers. The tendency of silica to agglomerate with each other. In this case, when the tire is deformed during running, the silica rubs against each other and generates heat, resulting in excess energy loss. Therefore, how to disperse the silica in the rubber polymer becomes the point. It is believed that the petroleum-based aromatic-containing oil containing the above-mentioned specific components in a specific amount contains silica, which has an effect on the dispersion or dissolution of various formulations, which is equivalent to the behavior in the rubber polymer has a better effect on various physical properties, As a result, a combination of contradictory performances is achieved. [Example]

其次，顯示實施例進一步詳細地說明本發明，但本發明不限定於以下之實施例。Next, the present invention will be described in more detail by showing examples, but the present invention is not limited to the following examples.

1.加工處理油之製造1. Manufacture of processing oil

＜實施例1-1＞ 將環烷原油供給至常壓蒸餾裝置，將所獲得之常壓蒸餾殘渣供給至減壓蒸餾裝置，將所獲得之相當於500 N之減壓蒸餾餾分供給至第一糠醛萃取裝置(於運轉條件：塔頂溫度70～100℃、塔底溫度40～70℃、溶劑比1.0～2.0之範圍內進行調整)，將所獲得之萃餘物餾分供給至第二糠醛萃取裝置(於運轉條件：塔頂溫度100～130℃、塔底溫度70～90℃、溶劑比2.0～3.0之範圍內，以萃取物餾分之100℃動黏度成為20 mm2 /s左右之方式進行調整)，將所獲得之萃取物餾分設為實施例1之加工處理油。<Example 1-1> The naphthenic crude oil was supplied to the atmospheric distillation apparatus, the obtained atmospheric distillation residue was supplied to the vacuum distillation apparatus, and the obtained vacuum distillation fraction corresponding to 500 N was supplied to the first distillation apparatus. Furfural extraction device (operating conditions: tower top temperature 70-100°C, tower bottom temperature 40-70°C, and solvent ratio 1.0-2.0), the obtained raffinate fraction is supplied to the second furfural extraction Apparatus (operating conditions: column top temperature 100-130°C, column bottom temperature 70-90°C, solvent ratio 2.0-3.0, and the kinematic viscosity of the extract fraction at 100°C is about 20 mm 2 /s. adjustment), the obtained extract fraction was set as the processed oil of Example 1.

＜實施例2-1＞ 將中東原油供給至常壓蒸餾裝置，將所獲得之常壓蒸餾殘渣供給至減壓蒸餾裝置，將所獲得之相當於500 N之減壓蒸餾餾分供給至第一糠醛萃取裝置(於運轉條件：塔頂溫度100～130℃、塔底溫度70～100℃、溶劑比1.6～3.0之範圍內進行調整)，將所獲得之萃取物餾分供給至第二糠醛萃取裝置(於運轉條件：塔頂溫度70～100℃、塔底溫度40～70℃、溶劑比1.0～2.0之範圍內，以萃餘物餾分之100℃動黏度成為20 mm2 /s左右之方式進行調整)，將所獲得之萃餘物餾分設為實施例2之加工處理油。<Example 2-1> The Middle East crude oil was supplied to the atmospheric distillation apparatus, the obtained atmospheric distillation residue was supplied to the vacuum distillation apparatus, and the obtained vacuum distillation fraction corresponding to 500 N was supplied to the first furfural Extraction device (operating conditions: tower top temperature 100-130°C, tower bottom temperature 70-100°C, and solvent ratio 1.6-3.0), and the obtained extract fraction is supplied to the second furfural extraction device ( In the operating conditions: the temperature at the top of the tower is 70 to 100°C, the temperature at the bottom of the tower is 40 to 70°C, and the solvent ratio is within the range of 1.0 to 2.0, and the kinematic viscosity of the raffinate fraction at 100°C is adjusted to be about 20 mm 2 /s. ), the obtained raffinate fraction was set as the processing oil of Example 2.

＜實施例3-1＞ 將中東原油供給至常壓蒸餾裝置，將所獲得之常壓蒸餾殘渣供給至減壓蒸餾裝置，將所獲得之相當於350 N之減壓蒸餾餾分供給至第一糠醛萃取裝置(於運轉條件：塔頂溫度80～100℃、塔底溫度50～70℃、溶劑比1.0～1.5之範圍內進行調整)，將所獲得之萃餘物餾分供給至第二糠醛萃取裝置(於運轉條件：塔頂溫度105～125℃、塔底溫度75～95℃、溶劑比2.0～3.0之範圍內進行調整)，將所獲得之萃取物餾分設為萃取物(M)。 將中東原油供給至常壓蒸餾裝置，將所獲得之常壓蒸餾殘渣供給至減壓蒸餾裝置，將所獲得之相當於900 N之減壓蒸餾餾分供給至第一糠醛萃取裝置(於運轉條件：塔頂溫度80～100℃、塔底溫度50～70℃、溶劑比0.8～1.4之範圍內進行調整)，將所獲得之萃餘物餾分供給至第二糠醛萃取裝置(於運轉條件：塔頂溫度110～130℃、塔底溫度80～100℃、溶劑比2.0～3.0之範圍內進行調整)，將所獲得之萃取物餾分設為萃取物(N)。 將中東原油供給至常壓蒸餾裝置，將所獲得之常壓蒸餾殘渣供給至減壓蒸餾裝置，將所獲得之相當於900 N之減壓蒸餾餾分供給至糠醛萃取裝置(於運轉條件：塔頂溫度105～125℃、塔底溫度65～85℃、溶劑比1.0～3.0之範圍內進行調整)，將所獲得之萃餘物餾分供給至氫化精製裝置(於運轉條件：使用貴金屬系觸媒、液體空間速度1.0～2.0 h-1 、反應溫度270～330℃、氫油比1400～2800 NL/L、氫分壓4.0～6.0 MPa之範圍內進行調整)，將所獲得之氫化精製油供給至溶劑脫蠟裝置(於運轉條件：甲基乙基酮與甲苯之混合溶劑、一次溶劑比0.7～2.0、二次溶劑比0.7～2.0、脫蠟溫度-15～-25℃之範圍內進行調整)，將所獲得之脫蠟油設為脫蠟油(O)。 將萃取物(M)/萃取物(N)/脫蠟油(O)以重量比計混合成25/50/25，從而獲得實施例3之加工處理油。<Example 3-1> The Middle East crude oil was supplied to an atmospheric distillation apparatus, the obtained atmospheric distillation residue was supplied to a vacuum distillation apparatus, and the obtained vacuum distillation fraction corresponding to 350 N was supplied to the first furfural Extraction device (adjusted under operating conditions: tower top temperature 80-100°C, tower bottom temperature 50-70°C, and solvent ratio 1.0-1.5), supplying the obtained raffinate fraction to the second furfural extraction device (Operating conditions: tower top temperature 105-125°C, tower bottom temperature 75-95°C, and solvent ratio 2.0-3.0 are adjusted), and the obtained extract fraction is referred to as extract (M). 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 900 N was supplied to the first furfural extraction device (under operating conditions: The temperature at the top of the tower is 80-100°C, the temperature at the bottom of the tower is 50-70°C, and the solvent ratio is adjusted within the range of 0.8-1.4), and the obtained raffinate fraction is supplied to the second furfural extraction device (operating conditions: tower top The temperature is 110-130°C, the column bottom temperature is 80-100°C, and the solvent ratio is adjusted in the range of 2.0-3.0), and the obtained extract fraction is referred to as the extract (N). 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 900 N was supplied to the furfural extraction device (in operation conditions: tower top) temperature 105-125°C, column bottom temperature 65-85°C, and solvent ratio are adjusted within the range of 1.0-3.0), and the obtained raffinate fraction is supplied to a hydrotreating device (operating conditions: using a precious metal-based catalyst, liquid space velocity 1.0～2.0 h -1 , reaction temperature 270～330°C, hydrogen oil ratio 1400～2800 NL/L, hydrogen partial pressure 4.0～6.0 MPa), and the obtained hydrorefined oil was supplied to Solvent dewaxing device (operating conditions: mixed solvent of methyl ethyl ketone and toluene, primary solvent ratio 0.7～2.0, secondary solvent ratio 0.7～2.0, dewaxing temperature -15～-25℃) , and the obtained dewaxed oil is referred to as dewaxed oil (O). The extract (M)/extract (N)/dewaxed oil (O) were mixed in a weight ratio of 25/50/25 to obtain the processed oil of Example 3.

＜實施例4-1＞ 將中東原油供給至常壓蒸餾裝置，將所獲得之常壓蒸餾殘渣供給至減壓蒸餾裝置，將所獲得之減壓蒸餾殘渣供給至利用經壓縮液化之丙烷之脫瀝青萃取裝置(於運轉條件：塔頂溫度55～85℃、塔底溫度45～75℃、溶劑比1.0～4.0之範圍內進行調整)，將所獲得之脫瀝青油供給至糠醛萃取裝置(於運轉條件：塔頂溫度110～130℃、塔底溫度60～80℃、溶劑比3.0～4.0之範圍內進行調整)，將所獲得之萃取物餾分設為萃取物(E)。 將上述萃取物(E)/下述脫蠟油(F)以重量比計混合成40/60，從而獲得實施例4之加工處理油。<Example 4-1> The Middle East crude oil was supplied to the atmospheric distillation unit, the obtained atmospheric distillation residue was supplied to the vacuum distillation unit, and the obtained vacuum distillation residue was supplied to the deasphalting extraction unit using the compressed liquefied propane (under operating conditions) : tower top temperature 55-85°C, tower bottom temperature 45-75°C, solvent ratio is adjusted within the range of 1.0-4.0), and the obtained deasphalted oil is supplied to the furfural extraction device (under operating conditions: tower top temperature 110°C) -130°C, column bottom temperature of 60 to 80°C, and solvent ratio adjusted within the range of 3.0 to 4.0), and the obtained extract fraction was referred to as extract (E). The above-mentioned extract (E)/the following dewaxed oil (F) was mixed in a weight ratio of 40/60 to obtain the processed oil of Example 4.

＜比較例1-1＞ 將中東原油供給至常壓蒸餾裝置，將所獲得之常壓蒸餾殘渣供給至減壓蒸餾裝置，將所獲得之相當於500 N之減壓蒸餾餾分供給至糠醛萃取裝置(於運轉條件：塔頂溫度100～130℃、塔底溫度50～80℃、溶劑比1.0～3.0之範圍內進行調整)，將所獲得之萃餘物餾分供給至氫化精製裝置(於運轉條件：使用貴金屬系觸媒、液體空間速度1.0～3.0 h-1 、反應溫度280～340℃、氫油比1500～2500 NL/L、氫分壓6.0～10.0 MPa之範圍內進行調整)，將所獲得之氫化精製油供給至溶劑脫蠟裝置(於運轉條件：甲基乙基酮與甲苯之混合溶劑、一次溶劑比1.0～2.0、二次溶劑比0.5～1.4、脫蠟溫度-15～-25℃之範圍內進行調整)，將所獲得之脫蠟油設為脫蠟油(G)。 將中東原油供給至常壓蒸餾裝置，將所獲得之常壓蒸餾殘渣供給至減壓蒸餾裝置，將所獲得之減壓蒸餾殘渣設為減壓蒸餾殘渣(H)。 將環烷原油供給至常壓蒸餾裝置，將所獲得之常壓蒸餾殘渣供給至減壓蒸餾裝置，將所獲得之相當於1000 N之減壓蒸餾餾分供給至氫化精製裝置(於運轉條件：使用貴金屬系觸媒、液體空間速度1.0～3.0 h-1 、反應溫度270℃～340℃、氫油比1400～2800 NL/L、氫分壓3.0～9.0 MPa之範圍內進行調整)，將所獲得之氫化精製油設為氫化精製油(I)。 將環烷原油供給至常壓蒸餾裝置，將所獲得之常壓蒸餾殘渣供給至減壓蒸餾裝置，將所獲得之減壓蒸餾殘渣設為減壓蒸餾殘渣(J)。 將脫蠟油(G)/減壓蒸餾殘渣(H)以重量比計混合成50/50，將氫化精製油(I)/減壓蒸餾殘渣(J)以重量比計混合成50/50，將兩者以100℃下之動黏度成為30 mm2 /s左右之方式進行混合，從而獲得比較例1之加工處理油。<Comparative Example 1-1> Middle East crude oil was supplied to an atmospheric distillation apparatus, the obtained atmospheric distillation residue was supplied to a vacuum distillation apparatus, and the obtained vacuum distillation fraction corresponding to 500 N was supplied to a furfural extraction apparatus (Operating conditions: tower top temperature 100-130°C, tower bottom temperature 50-80°C, and solvent ratio 1.0-3.0 are adjusted), the obtained raffinate fraction is supplied to the hydrotreating device (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 within the range of 6.0～10.0 MPa), The obtained hydrorefined 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 Adjusted within the range of °C), and the obtained dewaxed oil was referred to as dewaxed oil (G). The Middle East crude oil was supplied to an atmospheric distillation apparatus, the obtained atmospheric distillation residue was supplied to a vacuum distillation apparatus, and the obtained vacuum distillation residue was referred to as a vacuum distillation residue (H). The naphthenic crude oil was supplied to the atmospheric distillation apparatus, the obtained atmospheric distillation residue was supplied to the vacuum distillation apparatus, and the obtained vacuum distillation fraction equivalent to 1000 N was supplied to the hydrorefining apparatus (under operating conditions: using 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 3.0～9.0 MPa), the obtained The hydrorefined oil is referred to as hydrorefined oil (I). The naphthenic crude oil was supplied to an atmospheric distillation apparatus, the obtained atmospheric distillation residue was supplied to a vacuum distillation apparatus, and the obtained vacuum distillation residue was referred to as a vacuum distillation residue (J). Dewaxed oil (G)/vacuum distillation residue (H) was mixed in a weight ratio of 50/50, and hydrorefined oil (I)/vacuum distillation residue (J) was mixed in a weight ratio of 50/50, The two were mixed so that the kinematic viscosity at 100° C. would be about 30 mm 2 /s to obtain the processing oil of Comparative Example 1.

＜比較例2-1＞ 將環烷原油供給至常壓蒸餾裝置，將所獲得之常壓蒸餾殘渣供給至減壓蒸餾裝置，將所獲得之相當於2000 N之減壓蒸餾餾分供給至氫化精製裝置(於運轉條件：使用貴金屬系觸媒、液體空間速度1.0～3.0 h-1 、反應溫度270℃～340℃、氫油比1400～2800 NL/L、氫分壓3.0～9.0 MPa之範圍內進行調整)，將所獲得之氫化精製油設為比較例2之加工處理油。<Comparative Example 2-1> Naphthenic crude oil was supplied to an atmospheric distillation apparatus, the obtained atmospheric distillation residue was supplied to a vacuum distillation apparatus, and the obtained vacuum distillation fraction corresponding to 2000 N was supplied to hydrorefining Device (operating conditions: using 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.

＜比較例3-1＞ 將中東原油供給至常壓蒸餾裝置，將所獲得之常壓蒸餾殘渣供給至減壓蒸餾裝置，將所獲得之相當於500 N之減壓蒸餾餾分供給至糠醛萃取裝置(於運轉條件：塔頂溫度105～125℃、塔底溫度55～75℃、溶劑比1.2～2.8之範圍內進行調整)，將所獲得之萃餘物餾分供給至氫化精製裝置(於運轉條件：使用貴金屬系觸媒、液體空間速度2.0～3.0 h-1 、反應溫度310～360℃、氫油比1500～2500 NL/L、氫分壓8.5～12.0 MPa之範圍內進行調整)，將所獲得之氫化精製油供給至溶劑脫蠟裝置(於運轉條件：甲基乙基酮與甲苯之混合溶劑、一次溶劑比1.0～2.0、二次溶劑比0.5～1.4、脫蠟溫度-15～-25℃之範圍內進行調整)，將所獲得之脫蠟油設為脫蠟油(F)。將上述脫蠟油(F)設為比較例3之加工處理油。<Comparative Example 3-1> Middle East crude oil was supplied to an atmospheric distillation apparatus, the obtained atmospheric distillation residue was supplied to a vacuum distillation apparatus, and the obtained vacuum distillation fraction corresponding to 500 N was supplied to a furfural extraction apparatus (Operating conditions: tower top temperature 105-125°C, tower bottom temperature 55-75°C, and solvent ratio 1.2-2.8 are adjusted), and the obtained raffinate fraction is supplied to the hydrotreating device (operating conditions : Use precious 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 in the range), adjust all The obtained hydrorefined 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 Adjusted within the range of °C), and the obtained dewaxed oil was referred to as dewaxed oil (F). The above-mentioned dewaxed oil (F) was used as the processed oil of Comparative Example 3.

＜比較例4-1＞ 將上述萃取物(E)/脫蠟油(F)以重量比計混合成80/20，從而獲得比較例4之加工處理油。<Comparative Example 4-1> The above-mentioned extract (E)/dewaxed oil (F) were mixed in a weight ratio of 80/20 to obtain the processed oil of Comparative Example 4.

2.加工處理油之性狀測定 將由上述實施例及比較例所獲得之加工處理油設為試樣，進行下述項目之測定。2. Determination of properties of processed oil The processing oil obtained by the said Example and the comparative example was used as a sample, and the measurement of the following items was performed.

[黏土凝膠法] 根據黏土凝膠法(黏土凝膠管柱層析法)：ASTM D2007-11用黏土-凝膠吸收層析法對橡膠增量劑及加工處理油以及其他石油衍生油中之特徵性基進行標準測試之方法，求出芳香族份、飽和份、極性成分(質量%)。[clay gel method] Standardization of characteristic bases in rubber extenders and processing oils and other petroleum-derived oils according to the clay-gel method (clay-gel column chromatography): ASTM D2007-11 by clay-gel absorption chromatography As a test method, the aromatic content, the saturated content, and the polar component (mass %) were determined.

[使用HPLC進行之芳香族份之分離] 使用HPLC(高壓液相層析法)進行之芳香族份之分離係以(先前報道：Analytical Chemistry, 1983, 55, p.1375-1379)所刊登之「Separation of aromatic and polar compounds in fossil fuel liquids by liquid chromatography」作為參考，藉由以下之程序而實施。 藉由利用己烷將試樣稀釋成5倍而進行預處理。管柱使用Waters公司製造之Spherisorb A5Y 250×4.6 mm，流量設為2.5 mL/分鐘，檢測器使用UV(ultraviolet，紫外線)檢測器，於波長270 nm下進行測定。關於溶離液，導入試樣起之時間自0至10.0分鐘使用己烷，自10.0至30.0分鐘由己烷100質量%直線性增加二氯甲烷含量而成為二氯甲烷40質量%與己烷60質量%之混合溶液。導入試樣起之時間於30.0～30.1分鐘期間，將二氯甲烷40質量%與己烷60質量%之混合溶液變更成二氯甲烷100質量%，於30.1分鐘以後使用二氯甲烷100質量%。 根據以下之式由所獲得之峰面積求出不同環之芳香族烴之含量(質量%)。此處，一環面積係自苯之峰至萘之正前方之峰為止的峰面積之合計，二環面積係自萘之峰至蒽之正前方之峰為止的峰面積之合計，又，三環以上面積係蒽之峰以後之峰面積之合計。 一環芳香族份(質量%)＝(一環面積/(一環面積＋0.1×二環面積＋0.025×三環以上面積))×100； 二環芳香族份(質量%)＝(0.1×二環面積/(一環面積＋0.1×二環面積＋0.025×三環以上面積))×100； 三環以上之芳香族份(質量%)＝(0.025×三環面積/(一環面積＋0.1×二環面積＋0.025×三環以上面積))×100[Separation of Aromatics by HPLC] The separation of aromatic components using HPLC (High Pressure Liquid Chromatography) is described in "Separation of aromatic and polar compounds in fossil fuel liquids" (previously reported: Analytical Chemistry, 1983, 55, p. 1375-1379). by liquid chromatography" as a reference, was carried out by the following procedure. Pretreatment was performed by diluting the sample 5-fold with hexane. As the column, Spherisorb A5Y 250×4.6 mm manufactured by Waters Corporation was used, the flow rate was set to 2.5 mL/min, and the detector was a UV (ultraviolet, ultraviolet) detector, and the measurement was performed at a wavelength of 270 nm. As for the eluent, hexane was used from 0 to 10.0 minutes from the introduction of the sample, and the dichloromethane content was linearly increased from 100 mass % of hexane to 40 mass % of dichloromethane and 60 mass % of hexane from 10.0 to 30.0 minutes. the mixed solution. The time from the introduction of the sample was 30.0 to 30.1 minutes, the mixed solution of 40 mass % of methylene chloride and 60 mass % of hexane was changed to 100 mass % of methylene chloride, and 100 mass % of methylene chloride was used after 30.1 minutes. The content (mass %) of aromatic hydrocarbons in different rings was determined from the obtained peak areas according to the following formula. Here, the area of one ring is the sum of the peak areas from the peak of benzene to the peak immediately in front of naphthalene, the area of the bicyclic ring is the sum of the areas of the peaks from the peak of naphthalene to the peak immediately in front of anthracene, and the tricyclic area is The above area is the total of the peak areas after the peak of anthracene. Aromatic fraction of one ring (mass %)=(area of one ring/(area of one ring+0.1×area of two rings+0.025×area of more than three rings))×100; Bicyclic aromatic fraction (mass %)=(0.1×area of bicyclic rings/(area of one ring+0.1×area of bicyclic rings+0.025×area of more than three rings))×100; Aromatic content of more than 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

[動黏度(100℃)] 根據JIS K2283：2000之規定進行測定。[Kinematic viscosity (100℃)] Measured according to the regulations of JIS K2283:2000.

[苯胺點] 根據ASTM D611-12石油製品與烴溶劑之苯胺點及混合苯胺點之標準測試方法之規定進行測定。[Aniline point] Determined in accordance with ASTM D611-12 Standard Test Methods for Aniline Point and Mixed Aniline Point of Petroleum Products and Hydrocarbon Solvents.

[玻璃轉移點(Tg)] 設為根據以一定之升溫速度進行升溫時藉由DSC(示差掃描熱量計)所測定的玻璃轉移區域中之熱量變化峰所獲得之玻璃轉移點。初始溫度通常設為較預期玻璃轉移點低30℃～50℃左右或低於其之溫度，以上述初始溫度保持一定時間後，開始升溫。具體而言，藉由以下之條件進行測定。 裝置：Hitachi High-Tech Science製造之DSC7020 初始溫度：-90℃、保持10分鐘 升溫速度：10℃/分鐘 結束溫度：30℃、保持5分鐘[Glass transition point (Tg)] The glass transition point was obtained from the heat change peak in the glass transition region measured by DSC (differential scanning calorimeter) when the temperature was increased at a constant temperature increase 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, and the temperature is raised after the initial temperature is maintained for a certain period of time. Specifically, the measurement was performed under the following conditions. Device: DSC7020 manufactured by Hitachi High-Tech Science Initial temperature: -90°C, hold for 10 minutes Heating rate: 10°C/min End temperature: 30°C, hold for 5 minutes

[黏度比重常數(VGC)] 根據ASTM D2140-08計算石油來源之絕緣油之碳型成分之標準操作之規定進行測定。[Viscosity Specific Gravity Constant (VGC)] Determined in accordance with ASTM D2140-08 Standard Practice for Calculating the Carbon-Type Content of Petroleum-Derived Insulating Oils.

[%CA] 根據ASTM D2140-08計算石油來源之絕緣油之碳型成分之標準操作之規定進行測定。[%CA] Determined in accordance with ASTM D2140-08 Standard Practice for Calculating the Carbon-Type Content of Petroleum-Derived Insulating Oils.

[苯并(a)芘及特定芳香族化合物(PAHs)之含量] 根據歐洲標準EN 16143：2013石油製品-增量油中之苯并(a)芘(BaP)及選擇之多環芳香族烴(PAH)含量之測定-使用雙LC清洗及GC/MS分析之程序之規定進行測定。 PAHs意指以下內容。 1)苯并(a)芘(BaP) 2)苯并(e)芘(BeP) 3)苯并(a)蒽(BaA) 4)䓛(CHR) 5)苯并(b)螢蒽(BbFA) 6)苯并(j)螢蒽(BjFA) 7)苯并(k)螢蒽(BkFA) 8)二苯并(a,h)蒽(DBAhA)[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 oils - Procedure using dual LC cleaning and GC/MS analysis measure according to the regulations. PAHs means the following. 1) Benzo(a)pyrene (BaP) 2) Benzo(e)pyrene (BeP) 3) Benzo (a) Anthracene (BaA) 4) Qi (CHR) 5) Benzo (b) Fluoranthene (BbFA) 6) Benzo (j) Fluoranthene (BjFA) 7) Benzo (k) Fluoranthene (BkFA) 8) Dibenzo (a, h) anthracene (DBAhA)

3.橡膠組合物之製造 ＜實施例1-2～實施例4-2＞ 按下述組成調製橡膠聚合物、上述實施例1-1～4-1所製造之加工處理油、及其他各調配劑(二氧化矽、矽烷偶合劑、防老化劑、硫化助劑、氧化鋅、硫、硫化促進劑)後，進行混練，獲得未硫化之橡膠組合物後，於160℃下進行加壓硫化成形。3. Manufacture of rubber composition <Example 1-2 to Example 4-2> The rubber polymer, the processing oil produced in the above Examples 1-1 to 4-1, and other formulations (silicon dioxide, silane coupling agent, anti-aging agent, vulcanization aid, zinc oxide) were prepared according to the following compositions , sulfur, vulcanization accelerator), and kneading to obtain an unvulcanized rubber composition, which is then subjected to pressure vulcanization molding at 160°C.

＜比較例1-2～比較例4-2＞ 按下述組成調製橡膠聚合物、上述比較例1-1～4-1所製造之加工處理油、及其他各調配劑(同上)後，進行混練，獲得未硫化之橡膠組合物後，於160℃下進行加壓硫化成形。<Comparative Example 1-2 to Comparative Example 4-2> The rubber polymer, the processing oil produced in Comparative Examples 1-1 to 4-1, and other formulations (same as above) were prepared according to the following compositions, and kneaded to obtain an unvulcanized rubber composition. Press vulcanization molding at ℃.

將輪胎組合物之組成示於下述表1。表中之phr表示相對於橡膠聚合物100質量份之各種調配劑之質量份。The composition of the tire composition is shown in Table 1 below. The phr in the table represents the parts by mass of each formulation with respect to 100 parts by mass of the rubber polymer.

[表1]    調配量(phr) 橡膠聚合物(SBR) 100 二氧化矽 80 矽烷偶合劑 6.4 防老化劑 2 硫化助劑 1 氧化鋅 3 加工處理油 37.5 硫 2.2 硫化促進劑A 1.7 硫化促進劑B 2.0 [Table 1] Volume (phr) Rubber polymer (SBR) 100 silica 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

・橡膠聚合物(SBR)：  Lanxess製造 BunaVSL4526 ・二氧化矽：         Evonik製造 ULTRASIL7000GR ・矽烷偶合劑：      Evonik製造 Si75 ・防老化劑：         大內新興化學工業製造 Nocrack 6C ・硫化助劑：         日油製造 硬脂酸 ・氧化鋅：            東邦亞鉛製造 氧化鋅3號 ・加工處理油：      實施例及比較例所製造之各加工處理油 ・硫：                   市售硫化用硫 ・硫化促進劑A：    大內新興化學工業製造 Nocceler cz ・硫化促進劑B：    大內新興化學工業製造 Nocceler d・Rubber polymer (SBR): BunaVSL4526 made by Lanxess ・Silicon dioxide: ULTRASIL7000GR made by Evonik ・Silane coupling agent: Si75 made by Evonik ・Anti-aging agent: Nocrack 6C manufactured by Ouchi Sunshine Chemical Industry ・Vulcanization aid: stearic acid manufactured by NOF ・Zinc oxide: Zinc oxide No. 3 made by Toho Asia Lead ・Processing oil: Each processing oil produced in Examples and Comparative Examples ・Sulfur: Commercially available sulfur for vulcanization ・Vulcanization accelerator A: Nocceler cz, manufactured by Ouchi Sunshine Chemical Industry Co., Ltd. ・Vulcanization accelerator B: Nocceler d, manufactured by Ouchi Sunshine Chemical Industry Co., Ltd.

橡膠之混練方法：設為下述所示之二階段混練。 (第一階段) ・試驗機：       東洋精機製作所製造之Laboplastomill B-600 ・試驗機容積： 600 cc ・填充率：       70%(質量比) ・轉速：           100 rpm ・溫度：           以100℃開始上限設為155℃ ・混練時間：    約9分鐘 (第二階段) ・試驗機：       池田機械工業製造之電加熱式高溫滾壓機 ・尺寸：           6英吋

Figure 02_image001
×16英吋 ・轉速：          前輥25 rpm ・速度比：       前後比1：1.22 ・溫度：          23±10℃Kneading method of rubber: The following two-stage kneading is used. (First stage) ・Testing machine: Laboplastomill B-600 manufactured by Toyo Seiki Co., Ltd. ・Testing machine volume: 600 cc ・Filling rate: 70% (mass ratio) ・Rotation speed: 100 rpm ・Temperature: The upper limit is set at 100°C 155℃ ・Kneading time: about 9 minutes (second stage) ・Testing machine: Electric heating type high temperature rolling machine manufactured by Ikeda Machinery Industry ・Size: 6 inches
Figure 02_image001
×16 inches ・Rotation speed: Front roller 25 rpm ・Speed ratio: Front to back ratio 1:1.22 ・Temperature: 23±10℃

4.橡膠組合物之物性測定 由上述實施例及比較例之加壓硫化成形後之橡膠混練片製作8 mm

Figure 02_image001
×10 mm之試片，對上述試片進行下述項目之測定。4. Determination of the physical properties of the rubber composition 8 mm of rubber kneaded sheets after pressure vulcanization molding in the above examples and comparative examples were made
Figure 02_image001
For the test piece of ×10 mm, the following items were measured on the above-mentioned test piece.

[tanδ(0℃)] 使用TAINSTRUMENTS製造之黏彈性測定裝置ARES，於扭轉模式下，於頻率10 Hz、測定溫度範圍-50℃～100℃、升溫速度2℃/min、動態應變0.1%之條件下進行測定。自所獲得之溫度可變tanδ選出0℃之值。 tanδ(0℃)係濕地抓地性能之指標，該值越大，意味著濕地抓地性能越優異。[tanδ(0℃)] Using the viscoelasticity measuring device ARES manufactured by TAINSTRUMENTS, in the torsion mode, the measurement was performed under the conditions of a frequency of 10 Hz, a measurement temperature range of -50°C to 100°C, a heating rate of 2°C/min, and a dynamic strain of 0.1%. The value of 0°C was selected from the obtained temperature variable tanδ. tanδ (0°C) is an index of wet grip performance, and the larger the value, the better the wet grip performance.

[tanδ(50℃)] 使用TAINSTRUMENTS製造之黏彈性測定裝置ARES，於扭轉模式下，於頻率10 Hz、測定溫度範圍-50℃～100℃、升溫速度2℃/min、動態應變0.1%之條件下進行測定。自所獲得之溫度可變tanδ選出50℃之值。 tanδ(50℃)係滾動阻力性能之指標，該值越小，意味著滾動阻力性能越優異。[tanδ(50℃)] Using the viscoelasticity measuring device ARES manufactured by TAINSTRUMENTS, in the torsion mode, the measurement was performed under the conditions of a frequency of 10 Hz, a measurement temperature range of -50°C to 100°C, a heating rate of 2°C/min, and a dynamic strain of 0.1%. The value of 50°C was selected from the obtained temperature variable tanδ. tanδ (50°C) is an index of rolling resistance performance, and the smaller the value, the better the rolling resistance performance.

5.結果 將上述測定結果示於以下。上述實施例1-1及實施例1-2簡稱為實施例1。對於其他實施例及比較例，亦以相同之方式簡稱。5. Results The above measurement results are shown below. The above-mentioned Example 1-1 and Example 1-2 are simply referred to as Example 1. The other examples and comparative examples are also abbreviated in the same manner.

將各項目之測定結果示於下述表2。tanδ(0℃)及tanδ(50℃)之值係以將實施例4之實數值(分別為0.594、0.105)設為1之相對值記載。The measurement results of each item are shown in Table 2 below. The values of tan δ (0° C.) and tan δ (50° C.) are described as relative values obtained by setting the real values (0.594 and 0.105, respectively) of Example 4 as 1.

Figure 109106270-A0305-02-0038-1
Figure 109106270-A0305-02-0038-1

實施例1～4之加工處理油滿足實施形態所規定之「利用黏土凝膠法所得之飽和份之比率」、及「使用HPLC所分離之二環芳香族份之比率」之範圍，調配上述加工處理油所獲得之實施例1～4之橡膠組合物兼具濕地抓地性能及滾動阻力性能，非常優異。 可知，特別是調配「利用黏土凝膠法所得之芳香族份之比率」滿足實施形態所規定之範圍之加工處理油所獲得的實施例1～3之橡膠組合物能夠以良好之數值兼具濕地抓地性能及滾動阻力性能。 又，可確認，實施例及比較例中之所有加工處理油之苯并(a)芘及特定芳香族化合物(PAHs)之含量皆滿足REACH法規。The processed oils of Examples 1 to 4 satisfy the ranges of "the ratio of saturated content obtained by the clay gel method" and "the ratio of bicyclic aromatic content separated by HPLC" specified in the embodiment, and the above-mentioned processed oils were formulated. The rubber compositions of Examples 1 to 4 obtained by treating the oil had both wet grip performance and rolling resistance performance, and were very excellent. In particular, it was found that the rubber compositions of Examples 1 to 3 obtained by preparing a processing oil whose "ratio of aromatic content obtained by the clay gelation method" satisfies the range specified in the embodiment can have favorable numerical values and have both wet and dry properties. Grip performance and rolling resistance performance. In addition, it was confirmed that the contents of benzo(a)pyrene and specific aromatic compounds (PAHs) in all the processed oils in the Examples and Comparative Examples complied with REACH regulations.

以上，各實施形態中之各構成及其等之組合等為一例，可於不脫離本發明之主旨之範圍，進行構成之添加、省略、取代、及其他變更。又，本發明不受各實施形態限定，僅受請求項(claim)之範圍限定。 [產業上之可利用性]The above-mentioned respective configurations and combinations thereof in each embodiment are examples, and additions, omissions, substitutions, and other modifications of configurations can be made without departing from the gist of the present invention. In addition, this invention is not limited to each embodiment, and is limited only by the scope of a claim. [Industrial Availability]

本發明可提供一種含有石油系芳香族之油，其可製造滾動阻力性能及濕地抓地性能優異之橡膠組合物，且滿足REACH法規。The present invention can provide a petroleum-based aromatic oil, which can produce a rubber composition excellent in rolling resistance performance and wet grip performance, and satisfies REACH regulations.

10:減壓蒸餾裝置 11:減壓蒸餾餾分 30a:溶劑萃取裝置 30b:溶劑萃取裝置 31a:萃餘物 31b:萃餘物 33a:萃取物 33b:萃取物 40:氫化精製裝置 41:氫化精製油 50:脫蠟裝置 51:脫蠟油 62:含有石油系芳香族之油10: Vacuum distillation unit 11: vacuum distillation fraction 30a: Solvent extraction device 30b: Solvent extraction device 31a: Raffinate 31b: Raffinate 33a: Extract 33b: Extract 40: Hydrorefining unit 41: Hydrogenated Refined Oil 50: Dewaxing device 51: Dewaxed oil 62: Contains petroleum-based aromatic oils

圖1係對本發明之一實施形態之含有石油系芳香族之油之製造方法之一例進行說明的步驟圖。 FIG. 1 is a process diagram illustrating an example of a method for producing a petroleum-based aromatic-containing oil according to an embodiment of the present invention.

圖2A係對製備本發明之一實施形態之輪胎組合物之過程之一例進行說明的步驟圖。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.

圖2B係對製備本發明之一實施形態之輪胎組合物之過程之一例進行說明的步驟圖。FIG. 2B is a step diagram illustrating an example of a process for preparing a tire composition according to an embodiment of the present invention.

Claims (9)

一種含有石油系芳香族之油，其利用黏土凝膠法所得之飽和份之比率為45質量%以下，利用黏土凝膠法所得之芳香族份之比率為50質量%以上74質量%以下，使用HPLC所分離之二環芳香族份之比率相對於利用黏土凝膠法所得之芳香族份100質量%為16質量%以上29質量%以下，苯并(a)芘之含量為1質量ppm以下，且下述1)~8)之特定芳香族化合物之含量之合計為10質量ppm以下；1)苯并(a)芘2)苯并(e)芘3)苯并(a)蒽4)
Figure 109106270-A0305-02-0041-3
5)苯并(b)螢蒽6)苯并(j)螢蒽7)苯并(k)螢蒽8)二苯并(a,h)蒽。 An oil containing petroleum-based aromatics, the ratio of the saturated content obtained by the clay gel method is 45 mass % or less, and the ratio of the aromatic content obtained by the clay gel method is 50 mass % to 74 mass %, using The ratio of the bicyclic aromatic content separated by HPLC is 16 mass % or more and 29 mass % or less with respect to 100 mass % of the aromatic content obtained by the clay gel method, and 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 2) Benzo(e) Pyrene 3) Benzo(a) Anthracene 4)
Figure 109106270-A0305-02-0041-3
5) benzo(b) fluoranthene 6) benzo(j) fluoranthene 7) benzo(k) fluoranthene 8) dibenzo(a, h) anthracene. 如請求項1之含有石油系芳香族之油，其中上述利用黏土凝膠法所得之飽和份之比率為22質量%以上。 The petroleum-based aromatic-containing oil according to claim 1, wherein the ratio of the saturated fraction obtained by the clay gel method is 22% by mass or more. 如請求項1或2之含有石油系芳香族之油，其中上述使用HPLC所分離 之二環芳香族份之比率相對於上述利用黏土凝膠法所得之芳香族份100質量%未達23質量%。 The petroleum-based aromatic-containing oil according to claim 1 or 2, wherein the above is separated by HPLC The ratio of the bicyclic aromatic part is less than 23 mass % with respect to 100 mass % of the aromatic part obtained by the above-mentioned clay gel method. 如請求項1或2之含有石油系芳香族之油，其中上述利用黏土凝膠法所得之飽和份之比率為36質量%以下。 The petroleum-based aromatic-containing oil according to claim 1 or 2, wherein the ratio of the saturated fraction obtained by the clay gel method is 36% by mass or less. 如請求項1或2之含有石油系芳香族之油，其中上述使用HPLC所分離之二環芳香族份之比率相對於上述利用黏土凝膠法所得之芳香族份100質量%為22質量%以下。 The petroleum-based aromatic-containing oil according to claim 1 or 2, wherein the ratio of the bicyclic aromatic content separated by HPLC is 22 mass % or less relative to 100 mass % of the aromatic content obtained by the clay gel method . 如請求項1或2之含有石油系芳香族之油，其係混合於橡膠中而使用之增量油或加工處理油。 The oil containing petroleum-based aromatics as claimed in claim 1 or 2 is an extender oil or a processing oil that is mixed with rubber and used. 一種橡膠組合物，其含有如請求項1或2之含有石油系芳香族之油、及橡膠。 A rubber composition comprising the petroleum-based aromatic-containing oil as claimed in claim 1 or 2, and rubber. 一種輪胎，其含有如請求項1或2之含有石油系芳香族之油。 A tire containing the petroleum-based aromatic-containing oil as claimed in claim 1 or 2. 一種如請求項8之輪胎之製造方法，其包括調配橡膠、及如請求項1或2之含有石油系芳香族之油進行硫化。A method for producing a tire according to claim 8, comprising compounding rubber and vulcanizing the oil containing petroleum-based aromatics according to claim 1 or 2.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201038725A (en) * 2009-03-27 2010-11-01 Nippon Oil Corp Rubber compounding oil and method for producing same
TW201100483A (en) * 2009-03-27 2011-01-01 Nippon Oil Corp Rubber compounding oil, aromatic compound-containing base oil, and methods for producing same
TW201544543A (en) * 2014-05-22 2015-12-01 Otsuka Chemical Co Ltd Rubber composition, tire, bisphenyl diamine compound and anti-aging agent

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3624646B2 (en) * 1997-09-12 2005-03-02 新日本石油株式会社 Rubber compounding oil
KR100687395B1 (en) * 1999-08-31 2007-02-27 신닛테츠가가쿠 가부시키가이샤 Aromatic Oligomer and Use Thereof
JP2004107560A (en) * 2002-09-20 2004-04-08 Fuji Kosan Kk Improved aromatic rubber-containing oil
JP4914069B2 (en) * 2006-01-16 2012-04-11 Ｊｘ日鉱日石エネルギー株式会社 Method for producing lubricating base oil
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JP2012153787A (en) 2011-01-25 2012-08-16 Sumitomo Rubber Ind Ltd Rubber composition for tire, and pneumatic tire
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Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW201038725A (en) * 2009-03-27 2010-11-01 Nippon Oil Corp Rubber compounding oil and method for producing same
TW201100483A (en) * 2009-03-27 2011-01-01 Nippon Oil Corp Rubber compounding oil, aromatic compound-containing base oil, and methods for producing same
TW201544543A (en) * 2014-05-22 2015-12-01 Otsuka Chemical Co Ltd Rubber composition, tire, bisphenyl diamine compound and anti-aging agent

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