593252 A7 B7 五、發明説明（]) 〔技術領域〕 (請先閱讀背面之注意事項再填寫本頁) 本發明係有關製造雙酚類用酸性陽離子交換樹脂固定 床之製造方法，更詳細而言，有關鹼性陽離子交換樹脂以 含有氮硫黃化合物於均勻部分經予以中和的製造雙酚類用 酸性陽離子父換樹脂固定床之製備方法。 〔背景技術〕 經濟部智慧財產局員工消費合作社印製 雙酚類，例如2 ，2 -雙（4 一羥基苯基）丙烷（以 下，略稱雙酚A )、聚碳酸酯樹脂或聚芳基化合物樹脂等 之工程塑膠或以環氧樹脂等之原料作爲重要化合物係爲人 所知，近年其需求係爲日漸增大的傾向。此雙酚A爲首的 雙酚類，使用酸性陽離子交換樹脂（以下，也可簡稱作離 子交換樹脂。）固定床使苯酚類與羰基化合物反應可予以 製造一事係爲公知。又，此情形，若將取雙酚爲例爲抑制 異構體2 — ( 2、一經基苯基）一 2 — ( 4 -經基苯基）丙 烷之副產品，將離子交換樹脂之一部分以含有氮硫黃化合 物使均勻予以中和作爲觸媒使用一事亦令人所知，至於其 中和法係用各種方法予以嘗試著。 例如’日本特公昭6 2 - 7 4 8號公報內，揭示有於 離子交換樹脂固定床中使已添加鹽酸之液體循環的方法。 不過，由於使用鹽酸會有裝置之腐蝕問題。又日本特開平 8 - 4 0 9 6 1號公報內，雖然揭示有於中和劑之含氮硫 黃化合物內添加芳香族磺酸之方法，對芳香族磺酸雖未有 腐触之問題，但離子交換樹脂以水洗淨或以苯酚取代之情 本紙張尺度適用中國國家標準（CNS ) A4規格（hOXW?公釐） ' ~ — 593252 A7 _ B7 五、發明説明（2) 形，酸之去除變壞，結果反應開始時的產品之品質係有所 謂壞影響之問題。 (請先閱讀背面之注意事項再填寫本頁) 〔發明之揭示〕 本發明係由上述觀點所形成者，其目的係提供製造雙 酚類用陽離子交換樹脂固定床之製備方法，該法於將酸性 陽離子交換樹脂予以均勻的部分中和後，即無裝置腐蝕之 問題，且以水洗淨及以苯酚取代之際，酸之去除良好。 本發明人經重複精心硏究結果，藉以使用烷基磺酸作 爲酸，發現經予達成上述發明之目的結果，以至完成本發 明。 亦即，本發明之要點如下述： 1 . 一種製造雙酚類用酸性陽離子交換樹脂固定床之 製備方法，其特徵在於： 經濟部智慧財產局員工消費合作社印製 於酸性陽離子交換樹脂以含有氮硫黃化合物經予均勻 部分中和的製造雙酚類用酸性陽離子交換樹脂固定床之製 備方法，於反應器塡充酸性陽離子交換樹脂使形成固定床 後，在反應開始前，使烷基磺酸類之水溶液及含有氮硫黃 化合物之水溶液裝入該反應器予以循環。 2 .如前述第1項之製造雙酚類用酸/注陽離子交換樹 脂固定床之製備方法，其中烷基磺酸類之水溶液之濃度係 爲0 . 1毫摩爾/升以上。 3 .如前述第1項或第2項之製造雙酚.類用酸性陽離 子交換樹脂固定床之製備方法，其中酸性陽離子交換樹脂 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -5- 593252 A7 B7 五、發明説明（3) 係爲磺酸型陽離子交換樹脂。 ’ (請先閲讀背面之注意事項再填寫本頁) 4 ·如則述第1至3項之任一項中之製造雙·類用酸 丨生(W離子父換樹脂固定床之製備方法，其中含有氮硫薈化 合物係指氫硫基烷基胺類或噻唑烷類。 5 ·如前述第1至4項之任一項中之製造雙酚類用酸 性陽離子交換樹脂固定床之製備方法，其中雙g分類係指2 ’2 —雙（4 一烴基苯基）丙烷。 〔實施發明之最佳形態〕 以下，詳細說明本發明。 對於本發明，雙酚類係使酚類與羰基化合物反應予以 製造。 經濟部智慧財產局員工消費合作社印製 酚類係有必要對氫氧基上於對位上不具取代基。具體 的可舉出酣、鄰甲酚、間甲酚、鄰第三丁基苯酚、2 ，6 一二甲苯酚、2，6 -二一第三丁基苯酚等之烷基苯酚式 鄰氣酚、間一氯酚、2 ’ 6 —二氯酚等之鹵化酚。當爲鑛 基化合物，具體的可舉出丙酮、甲基乙基甲酮、甲基異丁 基甲酮、甲基一 η —丙基甲酮、苯乙酮、環乙酮等之酮類 或甲醛溶液（福爾馬林）、乙醛、苯甲醛等之醛基類。 較適合的，將丙酮與酚作爲原料，可適用於製造雙酚 Α。 乂 . 作爲使用觸媒之酸性陽離子交換樹脂，宜爲磺酸系者 ’當爲成具體之樹脂，雖然係有苯乙烯-二乙烯基苯共聚 合物系全氟乙烯（Perfluoroethylene )其聚合物系，酚一甲593252 A7 B7 V. Description of the invention ()) [Technical Field] (Please read the notes on the back before filling out this page) This invention relates to a method for manufacturing a fixed bed of acidic cation exchange resins for bisphenols, in more detail The preparation method of acidic cation parent exchange resin fixed bed for producing bisphenols with basic cation exchange resin containing nitrogen and sulfur compounds in a uniform part is neutralized. [Background Technology] Bisphenols printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, such as 2,2-bis (4-hydroxyphenyl) propane (hereinafter, referred to as bisphenol A), polycarbonate resin or polyaryl Engineering resins such as compound resins, or raw materials such as epoxy resins are known as important compounds, and their demand has been increasing in recent years. It is known that bisphenols such as bisphenol A can be produced by using an acidic cation exchange resin (hereinafter, also referred to as ion exchange resin) in a fixed bed to react phenols with carbonyl compounds. Also, in this case, if bisphenol is taken as an example to suppress the isomer 2 — (2, tris-phenylphenyl) to 2 — (4-striphenyl) propane as a by-product, a part of the ion exchange resin contains Nitrogen and sulfur compounds are known to be used as a catalyst to neutralize them uniformly. As for the neutralization method, various methods have been tried. For example, Japanese Patent Publication No. 6 2-7 48 discloses a method of circulating a liquid to which hydrochloric acid has been added in an ion exchange resin fixed bed. However, due to the use of hydrochloric acid, there is a problem of corrosion of the device. In Japanese Patent Application Laid-Open No. 8-4 0 9 61, although a method of adding an aromatic sulfonic acid to a nitrogen-containing sulfur compound of a neutralizing agent is disclosed, although there is no problem with the aromatic sulfonic acid, However, if the ion exchange resin is washed with water or replaced with phenol, the paper size is subject to the Chinese National Standard (CNS) A4 (hOXW? Mm) '~ — 593252 A7 _ B7 V. Description of the invention (2) Deterioration is eliminated, and as a result, the quality of the product at the beginning of the reaction has a problem of so-called bad influence. (Please read the notes on the back before filling this page) [Disclosure of the invention] The present invention was formed by the above point of view, and its purpose is to provide a method for preparing a fixed bed of cation exchange resin for bisphenols. After the acidic cation exchange resin is uniformly partially neutralized, there is no problem of corrosion of the device, and when it is washed with water and replaced with phenol, the acid is removed well. The inventors have repeatedly and meticulously investigated the results, by using an alkylsulfonic acid as an acid, and found that the object of the above invention has been achieved, and the present invention has been completed. That is, the main points of the present invention are as follows: 1. A method for preparing a fixed bed of acidic cation exchange resin for bisphenols, characterized in that: the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed on the acidic cation exchange resin to contain nitrogen A method for preparing a fixed bed of acidic cation exchange resin for producing bisphenols by uniformly and partially neutralizing sulfur compounds. After the reactor is filled with acidic cation exchange resin to form a fixed bed, the alkylsulfonic acid is made before the reaction starts. The aqueous solution and the aqueous solution containing nitrogen and sulfur compounds were charged into the reactor and circulated. 2. The method for preparing an acid / cation exchange resin fixed bed for producing bisphenols as described in item 1 above, wherein the concentration of the aqueous solution of the alkylsulfonic acid is 0.1 mmol / liter or more. 3. The method for preparing bisphenol. Acidic cation exchange resin fixed bed as described in item 1 or 2 above, wherein the paper size of the acid cation exchange resin is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -5- 593252 A7 B7 5. Description of the invention (3) It is a sulfonic acid type cation exchange resin. '(Please read the precautions on the back before filling out this page) 4 · If so, describe the manufacturing method of double-type acids in any one of items 1 to 3 (W ion parent-resin fixed bed preparation method, The compounds containing nitrogen and thionine refer to hydrogenthioalkylamines or thiazolidines. 5 · A method for preparing an acidic cation exchange resin fixed bed for bisphenols as described in any one of the foregoing items 1 to 4, The double g classification refers to 2'2-bis (4-hydrocarbylphenyl) propane. [Best Mode for Carrying Out the Invention] Hereinafter, the present invention will be described in detail. For the present invention, bisphenols react phenols with carbonyl compounds. It is necessary for the phenols printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs to have no substituents on the para position of the hydroxyl group. Specific examples include fluorene, o-cresol, m-cresol, and o-third butyl. Alkyl phenols, 2,6-xylenol, 2,6-di-tert-butylphenol, etc. are alkylphenol-type orthophenols, m-chlorophenol, 2'6-dichlorophenol, etc. halogenated phenols. When Is a mineral-based compound, and specific examples include acetone, methyl ethyl ketone, and methyl isobutyl Ketones, methyl-n-propyl ketones, acetophenone, cycloethyl ketones and other ketones or formaldehyde solutions (formalin), aldehydes, aldehydes and other aldehyde groups. More suitable, acetone With phenol as raw material, it can be used in the production of bisphenol A. 乂. As an acidic cation exchange resin using a catalyst, it is preferable to use a sulfonic acid as a specific resin, although a styrene-divinylbenzene Polymer is Perfluoroethylene, its polymer is phenol-methyl
本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 593252 A7 B7 五、發明説明（4) 醛聚合物系等，但宜爲苯乙烯-二乙烯基苯。雖然此等樹 脂無論任一個凝膠（G e 1 )型，多孔（p0rous )型均可 使用，但交聯度6 6較低者宜爲2 - 8 %。將此酸性陽離 子交換樹脂塡充反應器使形成固定.床。 本發明係關於反應器塡充酸性陽離子交換樹脂使％ $ 固定床後，在反應開始前，使熔基磺酸類之水溶液及含有 氮硫黃化合物之水溶液裝入該反應器予以循環，以該含氮 硫黃化合物經均勻的部分中和酸性陽離子交換樹脂。 可適合的舉出上述之作爲院基磺酸類以下式一般式（ 1 )表示者。 R-S〇3H .........(1) (式中，R係表示碳數1〜4之烷基。） 可舉出作爲R之具體例，甲基、乙基、正一丙基、異 丙基、正一丁基、第二丁基、異丁基、第三丁基。 此烷基磺酸類之水溶液之濃度係宜爲〇·1毫摩爾/ 升以上。如未滿0 · 1毫摩爾/升’則係有離子交換樹脂 之中和的均勻性有不足情形。 上述之作爲含氮硫黃化合物，雖然可舉出例如2 -氫 硫基乙胺（硫酚）、3 -氫硫基丁基胺等之氫硫基烷基胺 類、2 ，2 —二甲基噻唑烷、2 —甲基一 2 —乙基噻唑烷 、環基烷基噻唑烷、2 一甲基一 2 —苯基噻唑烷、3 -甲 基噻唑烷等之噻唑烷類、1 ’ 4 -氨基苯硫酚等之氨基苯 硫酚類、3 -氫硫基甲基吼d定、3 —氫硫基.乙基吼d定、4 -氫硫基乙基吡啶等之氫硫基烷基_ D定類等’但其中宜爲 本紙張尺度適用中國國家標準（CNS〉A4規格（210x297公* ) " (請先閱讀背面之注意事項再填寫本頁) ^衣· 、1Τ 經濟部智慧財產局員工消費合作社印繁 經濟部智慧財產局員工消費合作社印製 593252 A7 ______ B7 五、發明説明（5) 氫硫基烷基吡啶類及噻唑烷類。該含氮硫黃化合物之水溶 液之濃度宜爲1〜1 0質量％者，如經使用較好，全使用 量對於酸性陽離子交換樹脂之磺酸基係宜爲2〜5 0 mo 1%，較宜爲5〜3〇mo 1.%。 將院基磺酸之水溶液與含有氮硫黃化合物之水溶液裝 入反應器’兩者預先進行混合亦好，含有氮硫黃化合物水 溶液開始裝入後、或裝入結束後，始將裝入含有氮硫黃水 溶液亦可。又將烷基磺酸類水溶液開始裝入後、或裝入結 束後，始將裝入含有氦硫黃化合物水溶液亦可。 尙且’烷基磺酸類水溶液與含有氦硫黃化合物水溶液 之循環，當然成爲兩者混合物之循環，如進行至離子交換 樹脂所求的中和率亦可。 此所求的中和率2〜5 0 %，係宜爲5〜3 0 %。此 中和率即使過低或過局，即不能充分發揮觸媒之活性。 關於進行中和溫度，室溫亦可，或加溫至3 0〜 1〇0 °C亦可。如超過1 〇 〇 °C，離子交換樹脂之磺酸的 脫離而成激烈即不宜。 於本發明，如使用烷基磺酸作爲酸，與芳香族磺酸比 較分子較小，又與芳香族比較由於與細孔內的樹脂本體間 之親和性惡劣等的理由，推定離子交換樹脂之水洗淨與以 酚取代後酸之去除成爲較好。 其次，雖然依實施例具體的說明本發明，但並非受限 於此等之實施例。 於內徑2 5 m m，長度2 0 c m之玻璃柱塡充經水膨 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） (請先閲讀背面之注意事項再填寫本頁) -口The size of this paper is applicable to Chinese National Standard (CNS) A4 (210X297 mm) 593252 A7 B7 5. Description of the invention (4) Aldehyde polymer, etc., but styrene-divinylbenzene is preferred. Although these resins can be used with any of the gel (G e 1) type and the porous (p0rous) type, the lower the cross-linking degree of 66, the better is 2-8%. This acidic cation exchange resin was charged into the reactor to form a fixed bed. The present invention relates to a reactor filled with an acidic cation exchange resin so that a fixed bed, before the reaction starts, an aqueous solution of molten sulfonic acids and an aqueous solution containing nitrogen and sulfur compounds are charged into the reactor and circulated. The nitrogen-sulfur compound neutralizes the acidic cation exchange resin uniformly and partially. As the above-mentioned, as the novolac sulfonic acid, the following general formula (1) can be suitably cited. RS〇3H ... (1) (where R represents an alkyl group having 1 to 4 carbon atoms.) Specific examples of R include methyl, ethyl, and n-propyl Methyl, isopropyl, n-butyl, second butyl, isobutyl, third butyl. The concentration of the aqueous solution of the alkyl sulfonic acid is preferably 0.1 mmol / L or more. If it is less than 0.1 mmol / L ', the uniformity of neutralization of the ion exchange resin may be insufficient. Examples of the nitrogen-containing sulfur compounds mentioned above include, for example, hydrothioalkylamines such as 2-hydrothioethylamine (thiophenol), 3-hydrothiobutylamine, and 2,2-dimethylamine. Thiazolidine, 2-methyl-2-ethylthiazolidine, cycloalkylthiazolidine, 2-methyl-2-phenylthiazolidine, 3-thiazolidine and other thiazolidines, 1 '4 -Aminothiophenols such as aminothiophenols, 3-thiothiomethylamines, 3-hydrothio groups, ethylthiothiones, 4-hydrothioethylpyridines, and other hydrothioalkanes Basic _ D classification, etc., but it is appropriate to apply the Chinese national standard (CNS> A4 size (210x297) *) " (Please read the precautions on the back before filling this page) ^ Clothing, 1T Ministry of Economic Affairs Printed by the Intellectual Property Bureau's Consumer Cooperative Cooperative, printed by the Ministry of Economic Affairs's Employees' Cooperative Cooperative, printed by 5929252 A7 ______ B7 V. Description of the Invention (5) Hydrosulfanylpyridines and thiazolidines. The concentration should be 1 to 10% by mass. If it is used well, the total amount is suitable for the sulfonic acid group of the acidic cation exchange resin. 2 ~ 50 mol 1%, more preferably 5 ~ 30 mol 1.%. Fill the reactor with an aqueous solution of sulfonic acid and an aqueous solution containing nitrogen sulfur compounds into the reactor. It is also good to mix the two in advance, containing nitrogen. After the sulfur compound aqueous solution is started to be filled, or after the filling is completed, the nitrogen sulfur sulfur-containing aqueous solution may be filled. After the alkylsulfonic acid aqueous solution is started to be filled, or after the filling is completed, the An helium sulfur compound aqueous solution is also possible. 尙 And the cycle of the alkyl sulfonic acid aqueous solution and the helium sulfur compound-containing aqueous solution is, of course, a cycle of the mixture of the two. If the neutralization rate required for the ion exchange resin is reached. The required neutralization rate is 2 to 50%, preferably 5 to 30%. Even if the neutralization rate is too low or too low, the catalyst activity cannot be fully exerted. Regarding the neutralization temperature, the room temperature is also Yes, or it can be heated to 30 to 100 ° C. If it exceeds 1000 ° C, the sulfonic acid of the ion exchange resin becomes violently separated, which is not suitable. In the present invention, if alkyl sulfonic acid is used as Acid, smaller molecule compared to aromatic sulfonic acid, and For reasons such as poor affinity between the resin bodies in the pores, it is presumed that the water washing of the ion exchange resin and the removal of the acid after substitution with phenol are better. Second, although the present invention will be specifically described according to the examples, it is not affected. It is limited to these examples. Glass columns filled with 25 mm inner diameter and 20 cm long are filled with water-swellable paper. The size of the paper is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read first Note on the back then fill out this page)-口
593252 A7 B7 五、發明説明（6) 潤的狀態之磺酸型陽離子交換樹脂（三菱化學公司製、φ 醛系樹脂（dicl1〇n) SK— 104) 5 0 cc ，其中裝入二甲 基噻唑烷之1 ·· 3 8質量％水溶液1 〇 〇 c c ，結束後， 將甲磺酸之1 0 4毫摩爾/升水溶液1 〇 〇 c c裝入離子 交換樹脂床放上1小時，流出水溶液使循環。使經過7 2 小時循ί哀’將離子父換樹脂以5分比率提出並測定中和率 。結果示於第1表。尙且，中和率以下述之式求出。 由和士 m ηη、/ π中和處理樹脂之酸當量（遞 中和率（％)=100 X 运棚旨之酸當量（聊./i〇 ] (以上式，酸當量係使用氫氧化鈉水溶液之滴定法測 定。） 〔比較例1〕. 對於實施例1 ，除未使用甲磺酸外，餘以同法求出實 施交換樹脂之中和率。結果示於第1表。 (請先閱讀背面之注意事項再填寫本頁} 經濟部智慧財產局員工消黄合作社印製 離子交換樹脂之取出位置 實施例1 比較例1 1 (上流側） 23 99 2 18 0 3 19 0 4 18 0 .5 (下流側）· 22 0 〔產業上之可能利用性〕 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -9- 593252 A7 B7 五、發明説明（7) 如根據本發明，將酸性陽離子交換樹脂均勻的部分中 和後，未有裝置腐蝕之問題，且水洗淨及以酚取代之際之 酸的去除性良好可提供製造雙酚類用酸性陽離子交換樹脂 之製備方法。 (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 公會件搴 I國93年4月19日修正 η 申請曰崩 W-- ' --一.. 90年 3月23日 案 號 90106895 類 別 (以上各欄由本局填註） Α4 C4 593252 f|專利説明書 中 文 製ifi雙酚類用酸性陽離子交換樹脂固定床之製造方法 發明 新型 名稱 英 文593252 A7 B7 V. Description of the invention (6) Sulfuric acid type cation exchange resin (made by Mitsubishi Chemical Corporation, φ aldehyde resin (dicl10n) SK-104) 50 0 cc, which is filled with dimethylthiazole 1 · 38 of a 38% by mass aqueous solution of alkane. After the end, 100 cc of methanesulfonic acid solution of 100 mmol / l aqueous solution was charged into an ion exchange resin bed and left for 1 hour. . After 72 hours, the ion-exchange resin was raised at a ratio of 5 points and the neutralization rate was measured. The results are shown in Table 1. The neutralization rate is determined by the following formula. Neutralize the acid equivalent of the resin by the yeh m ηη, / π (the neutralization rate (%) = 100 X acid equivalent of the transport purpose (Liao. / I〇) (the above formula, the acid equivalent is using sodium hydroxide Measurement by aqueous solution titration method.] [Comparative Example 1] For Example 1, except that methanesulfonic acid was not used, the neutralization rate of the exchange resin was calculated by the same method. The results are shown in Table 1. (Please first Read the notes on the back and fill in this page again} Take-out position of the ion exchange resin printed by the staff of the Intellectual Property Bureau of the Ministry of Economic Affairs, Yellow Cooperative Example 1 Comparative Example 1 1 (upstream side) 23 99 2 18 0 3 19 0 4 18 0. 5 (downstream side) · 22 0 [Industrial potential availability] This paper size applies Chinese National Standard (CNS) A4 (210X297 mm) -9-593252 A7 B7 V. Description of the invention (7) According to the invention After neutralizing the uniform part of the acidic cation exchange resin, there is no problem of corrosion of the device, and the removal of the acid when washed with water and replaced with phenol is good, and a method for preparing an acidic cation exchange resin for bisphenols can be provided . (Please read the notes on the back before filling (Written on this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Employees' Cooperatives, this paper is printed in accordance with the Chinese National Standard (CNS) A4 (210X297 mm). Guild documents. I am amended on April 19, 1993. Application for the collapse of W-- '-I .: Case number 90106895 of March 23, 1990 (the above columns are filled by this bureau) Α4 C4 593252 f | Patent Specification Chinese made ifi bisphenol acidic cation exchange resin fixed bed for bed invention invention New name in English
PROCESS FOR PREPARING A FIXED BED OF AN ACIDIC CATION EXCHANGE RESIN FOR PRODUCING BISPHENOLS 姓 名 (1) 猿渡鐵也 Saruwatari, Tetsuya (2) 岩原昌宏 Iwahara, Masahiro 國 籍 ^發明 、創作 人 住、居所 (1) 日本國山口縣德山市新宮町--- 1-1, Shingu-cho, Tokuyama-shi, Yamaguchi, Japan (2) 日本國山口縣德山市新宮町--- 1-1, Shingu-cho, Tokuyama-shi, Yamaguchi, Japan 裝 訂 姓 名 (名稱） (1)出光石油化學股份有限公司 Idemitsu Petrochemical Co” Ltd· !· 經濟部智惡財屹^㈣工⑺骨合作社印货 線 國’籍 申請人 住、居所 (事務所） 代表人 姓 名 (1)日本 (1)日本國東京都墨田區橫網一丁目六一一 6-1, Yokoarai 1-chome, Sumida-ku, Tokyo, Japan (1)富永一途 Tominaga, Kazuto 本紙張尺度適用中國國家標準（CNS) A4規格（210X 297公釐）PROCESS FOR PREPARING A FIXED BED OF AN ACIDIC CATION EXCHANGE RESIN FOR PRODUCING BISPHENOLS Shingu-cho, Yamaguchi --- 1-1, Shingu-cho, Tokuyama-shi, Yamaguchi, Japan (2) Shingu-cho, Tokuyama-shi, Yamaguchi, Tokuyama, Japan , Japan Binding Name (Name) (1) Idemitsu Petrochemical Co., Ltd. Idemitsu Petrochemical Co "Ltd.! · Ministry of Economic Affairs, Intellectual Property, Evil ^ ㈣㈣⑺ 骨 合作 印 印行 国 国 'Residence, Residence (Office ） Name of Representative (1) Japan (1) Yokohama Ichome 6-1, Sumida, Sumida-ku, Tokyo, Japan 6-1, Yokoarai 1-chome, Sumida-ku, Tokyo, Japan (1) Toyaga Tominaga, Kazuto This paper Standards apply to China National Standard (CNS) A4 (210X 297 mm)