JP7104507B2 - セルロースの分離方法 - Google Patents
セルロースの分離方法 Download PDFInfo
- Publication number
- JP7104507B2 JP7104507B2 JP2017215194A JP2017215194A JP7104507B2 JP 7104507 B2 JP7104507 B2 JP 7104507B2 JP 2017215194 A JP2017215194 A JP 2017215194A JP 2017215194 A JP2017215194 A JP 2017215194A JP 7104507 B2 JP7104507 B2 JP 7104507B2
- Authority
- JP
- Japan
- Prior art keywords
- cellulose
- separating agent
- separating
- wood
- tank
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0003—General processes for their isolation or fractionation, e.g. purification or extraction from biomass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C11/00—Regeneration of pulp liquors or effluent waste waters
- D21C11/0007—Recovery of by-products, i.e. compounds other than those necessary for pulping, for multiple uses or not otherwise provided for
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C3/00—Pulping cellulose-containing materials
- D21C3/003—Pulping cellulose-containing materials with organic compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C3/00—Pulping cellulose-containing materials
- D21C3/20—Pulping cellulose-containing materials with organic solvents or in solvent environment
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/02—Washing ; Displacing cooking or pulp-treating liquors contained in the pulp by fluids, e.g. wash water or other pulp-treating agents
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/02—Washing ; Displacing cooking or pulp-treating liquors contained in the pulp by fluids, e.g. wash water or other pulp-treating agents
- D21C9/04—Washing ; Displacing cooking or pulp-treating liquors contained in the pulp by fluids, e.g. wash water or other pulp-treating agents in diffusers ; Washing of pulp of fluid consistency without substantially thickening
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/12—Bleaching ; Apparatus therefor with halogens or halogen-containing compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/18—De-watering; Elimination of cooking or pulp-treating liquors from the pulp
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/02—Chemical or chemomechanical or chemothermomechanical pulp
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/12—Pulp from non-woody plants or crops, e.g. cotton, flax, straw, bagasse
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
- D21H11/14—Secondary fibres
Description
また、特許文献7、6記載の方法では加圧熱水処理や機械的な微細化処理の場合ではエネルギー消費量が大きい。
しかも、この残渣成分は腐敗しやすいので、有効利用するためには糖液からの残渣の分離や乾燥などを必要とするが、それには相当のエネルギーとコストがかかる。
Claims (8)
- ヘミセルロース、セルロース及びリグニンを主成分とする木質系原料からセルロースを 分離する方法であって、
エチレングリコール類が分離剤として収蔵された溶解槽(1、100、300)に、木 質系原料を投入し、溶解槽(1、100、300)内の分離剤を常圧下で260°C~280°Cの範囲内の温度まで加熱し、
木質系原料を分離剤と反応させ、分離剤から蒸発するヘミセルロース成分を凝縮させ、 分離剤の温度上昇に伴って凝縮液のpH値が酸性から中性に向けて変化する凝縮液のpH を監視し、凝縮液の温度を凝縮液のpH値の変化が小さくなったときの温度に保持し、リグニンを分離剤に溶解させる一方、分離剤中に浮遊する粗セルロースを分離・回収するようにしたことを特徴とするセルロースの分離方法。 - 上記分離剤から分離回収した粗セルロールを水中で回転する翼によって攪拌洗浄するとともに、切断を行って微小セルロースを得るようにした請求項1記載のセルロースの分離方法。
- 上記微小セルロースを次亜塩素酸とカセイソーダの水溶液に浸漬して漂白するとともに 微小化するようにした請求項2記載のセルロースの分離方法。
- 上記微小セルロースに対して更に機械的な加圧力を与えて微細化するようにした請求項3記載のセルロースの分離方法。
- 上記木質系原料が、竹、木及び木綿の群から選ばれる1又は複数からなる木質繊維、野 菜、果物及び穀物の群から選ばれる1又は複数からなる食物繊維、あるいは綿又はパルプ からなる再生繊維である請求項1記載のセルロースの分離方法。
- ヘミセルロースを含有しない原料を上記木質系原料とともに溶解槽(1、100、30 0)内の分離剤に投入するようにした請求項1記載のセルロースの分離方法。
- ヘミセルロース、セルロース及びリグニンを主成分とする木質系原料からセルロースを分離する方法を実施する設備であって、
エチレングリコール類又はそれを主成分とする分離剤と、
該分離剤と木質系原料とを収蔵し、加熱手段により分離剤を200°C~280°Cの範囲内の温度まで加熱して両者を反応させ、木質系原料から分離剤に溶出したヘミセルロースを分離剤から蒸発させる一方、リグニンを分離剤に溶解させて、これらと分離剤に溶解しないセルロースを分離する溶解槽(1、100、300)と、
上記分離剤から蒸発するヘミセルロースの凝縮液のpH値を測定し、pH値の変化を検出するpH検出手段と、を備え
上記pH検出手段の検出する上記凝集液のpH値の変化に基づいて分離剤の加熱温度を保持調整し、上記溶解槽中の分離剤に浮遊する粗セルロースを分離・回収することを特徴とするセルロースの分離設備。 - 更に、上記溶解槽から回収した粗セルロースを洗浄切断して微小セルロースとする回転切断水槽9、109,309と、該槽で得られる微小セルロースを次亜塩素酸と苛性ソーダの水溶液で漂白化する漂白槽10、112,307と、を有する請求項7記載のセルロース分離設備。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2017215194A JP7104507B2 (ja) | 2017-11-08 | 2017-11-08 | セルロースの分離方法 |
TW107129799A TWI768109B (zh) | 2017-11-08 | 2018-08-27 | 纖維素的分離方法 |
CN201811229167.XA CN109957983B (zh) | 2017-11-08 | 2018-10-22 | 纤维素分离方法 |
US16/183,138 US10920372B2 (en) | 2017-11-08 | 2018-11-07 | Method for separating cellulose |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2017215194A JP7104507B2 (ja) | 2017-11-08 | 2017-11-08 | セルロースの分離方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2019085500A JP2019085500A (ja) | 2019-06-06 |
JP7104507B2 true JP7104507B2 (ja) | 2022-07-21 |
Family
ID=66328367
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2017215194A Active JP7104507B2 (ja) | 2017-11-08 | 2017-11-08 | セルロースの分離方法 |
Country Status (4)
Country | Link |
---|---|
US (1) | US10920372B2 (ja) |
JP (1) | JP7104507B2 (ja) |
CN (1) | CN109957983B (ja) |
TW (1) | TWI768109B (ja) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20210230375A1 (en) * | 2018-11-07 | 2021-07-29 | Earthrecycle Co., Ltd. | Method for separating cellulose |
JP6570101B1 (ja) * | 2019-04-10 | 2019-09-04 | 株式会社Rinnovation | 紙糸、紙布及び布製品 |
CN112064393A (zh) * | 2020-09-07 | 2020-12-11 | 顾理富 | 植物纤维素制备设备及工艺 |
CN115976866A (zh) * | 2022-11-22 | 2023-04-18 | 中国科学院广州能源研究所 | 一种有机溶剂预处理木质纤维素类生物质组分分离的方法 |
CN115850724B (zh) * | 2022-11-22 | 2024-02-06 | 中国科学院广州能源研究所 | 一种保留木质纤维素类生物质中碳水化合物同步分离木质素的预处理方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010084104A (ja) | 2008-10-02 | 2010-04-15 | Kri Inc | イオン液体によるリグノセルロース系バイオマスのセルロースとリグニンの分離化方法 |
JP2011168651A (ja) | 2010-02-16 | 2011-09-01 | Fujii Kiso Sekkei Jimusho:Kk | 層分離方法 |
JP2015080759A (ja) | 2013-10-23 | 2015-04-27 | 株式会社Kri | リグニン成分とセルロース成分の分離方法並びに熱可塑性リグニン複合物及び糖化原料の製造方法 |
US20150275432A1 (en) | 2014-03-31 | 2015-10-01 | Api Intellectual Property Holdings, Llc | Integration of non-woody biorefining at pulp and paper plants |
Family Cites Families (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB421379A (en) * | 1933-06-12 | 1934-12-12 | Henry Dreyfus | Improvements in or relating to the production of cellulose from lignocellulosic materials |
US2772968A (en) * | 1951-06-06 | 1956-12-04 | Research Corp | Process of pulping cellulosic materials with triethylene glycol |
BE756225A (fr) * | 1969-09-26 | 1971-03-01 | Brev Ind Et Chimiques Soc Gen | Procede de fabrication de pate cellulosique |
US4017642A (en) * | 1975-07-28 | 1977-04-12 | George O. Orth | Process of making food for ruminant animals from wood and/or woody products |
DE3161585D1 (en) * | 1980-06-20 | 1984-01-12 | Battelle Memorial Institute | A method for the delignification of wood and other ligno-cellulosic products |
CA1229334A (en) * | 1983-09-29 | 1987-11-17 | Ronnie S. Roberts | Biomass fractionation process |
JP3012296B2 (ja) * | 1990-08-24 | 2000-02-21 | 信夫 白石 | リグノセルロース物質の液化溶液の製造法 |
JP4522797B2 (ja) * | 2004-09-07 | 2010-08-11 | 月島機械株式会社 | リグノセルロースの前処理方法及びエタノール製造方法 |
JP5126728B2 (ja) | 2004-11-12 | 2013-01-23 | 独立行政法人産業技術総合研究所 | リグノセルロース系バイオマス処理方法 |
JP2006149343A (ja) | 2004-11-26 | 2006-06-15 | Daitoo Fujitekku:Kk | 木質系バイオマスからのグルコース生成物とグルコース生成物製造方法 |
CN1936174A (zh) * | 2005-09-19 | 2007-03-28 | 秦卫华 | 从木质纤维类材料分离纤维素与木质素的方法 |
JP2007202518A (ja) | 2006-02-03 | 2007-08-16 | Mitsui Eng & Shipbuild Co Ltd | 木質系バイオマスチップの前処理方法及び前処理装置 |
JP2008043328A (ja) | 2006-07-19 | 2008-02-28 | Taisei Corp | 木質系バイオマスの糖化方法 |
CN101143881B (zh) * | 2007-10-11 | 2011-03-16 | 孔延华 | 一种同时提取半纤维素、纤维素以及木质素并回收酚酸类物质的方法 |
JP2010094095A (ja) | 2008-10-17 | 2010-04-30 | Nagoya Univ | 木材の糖化方法 |
JP5353554B2 (ja) | 2009-08-20 | 2013-11-27 | 王子ホールディングス株式会社 | 木質系バイオマスからのエタノール製造方法 |
JP2011101608A (ja) | 2009-11-10 | 2011-05-26 | Ihi Corp | バイオマス処理システム及び方法 |
CN102080341B (zh) * | 2010-11-25 | 2013-04-24 | 山东轻工业学院 | 一种阳离子有机微粒及其制备与应用 |
CN102276760A (zh) * | 2011-08-10 | 2011-12-14 | 华南理工大学 | 梯度乙醇沉淀从农林生物质中分离纯化半纤维素的方法 |
FI20116156L (fi) * | 2011-11-21 | 2013-05-22 | Kemira Oyj | Biomassan käsittelymenetelmä |
CN102561082B (zh) * | 2012-03-01 | 2013-12-11 | 北京林业大学 | 从木质纤维原料提取半纤维素、纤维素和木质素的方法 |
CN203904778U (zh) * | 2014-03-31 | 2014-10-29 | 宋旭 | 一种高填充防电磁辐射聚合物改性纸 |
CN105745377B (zh) * | 2014-06-27 | 2019-07-30 | 因温特国际有限公司 | 生产高α-纤维素纸浆的方法 |
WO2016016234A1 (en) * | 2014-07-28 | 2016-02-04 | Purac Biochem Bv | Method of pre-treatment of lignocellulosic materials |
CN105672016B (zh) * | 2016-03-14 | 2018-03-30 | 齐鲁工业大学 | 一种有机溶剂法纸浆的洗涤和溶剂回收方法 |
CN109180838B (zh) * | 2018-07-25 | 2021-01-05 | 中国科学院广州能源研究所 | 一种两相熔盐体系分级分离木质纤维素类生物质组分的方法 |
-
2017
- 2017-11-08 JP JP2017215194A patent/JP7104507B2/ja active Active
-
2018
- 2018-08-27 TW TW107129799A patent/TWI768109B/zh active
- 2018-10-22 CN CN201811229167.XA patent/CN109957983B/zh active Active
- 2018-11-07 US US16/183,138 patent/US10920372B2/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010084104A (ja) | 2008-10-02 | 2010-04-15 | Kri Inc | イオン液体によるリグノセルロース系バイオマスのセルロースとリグニンの分離化方法 |
JP2011168651A (ja) | 2010-02-16 | 2011-09-01 | Fujii Kiso Sekkei Jimusho:Kk | 層分離方法 |
JP2015080759A (ja) | 2013-10-23 | 2015-04-27 | 株式会社Kri | リグニン成分とセルロース成分の分離方法並びに熱可塑性リグニン複合物及び糖化原料の製造方法 |
US20150275432A1 (en) | 2014-03-31 | 2015-10-01 | Api Intellectual Property Holdings, Llc | Integration of non-woody biorefining at pulp and paper plants |
Also Published As
Publication number | Publication date |
---|---|
TWI768109B (zh) | 2022-06-21 |
US10920372B2 (en) | 2021-02-16 |
CN109957983B (zh) | 2023-08-08 |
CN109957983A (zh) | 2019-07-02 |
TW201922801A (zh) | 2019-06-16 |
JP2019085500A (ja) | 2019-06-06 |
US20190136448A1 (en) | 2019-05-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP7104507B2 (ja) | セルロースの分離方法 | |
US8268125B2 (en) | Method for vapor phase pulping with alcohol and sulfur dioxide | |
JP5894594B2 (ja) | 黒液からの沈殿リグニンの製造方法 | |
CA2641686C (en) | Method for recovering hydrolysis products | |
US20060169430A1 (en) | Method for producing pulp and lignin | |
KR20130038861A (ko) | 높은 알파 용해 펄프 제조를 위한 방법 및 시스템 | |
WO2009086265A2 (en) | Pre-extraction and solvent pulping of lignocellulosic material | |
Holmqvist et al. | Ultrafiltration of kraft black liquor from two Swedish pulp mills | |
JP5924188B2 (ja) | リグノセルロース含有バイオマスからのフルフラール類の製造方法 | |
JP6581137B2 (ja) | 溶解クラフトパルプの製造方法 | |
CN105672016A (zh) | 一种有机溶剂法纸浆的洗涤和溶剂回收方法 | |
US20210230375A1 (en) | Method for separating cellulose | |
CN109811572A (zh) | 一种在化学纸浆厂处理液流的方法和系统 | |
US10935314B2 (en) | Heating values of cellulosic waste | |
US6752903B2 (en) | Method for mitigating the interference caused by high-molecular weight by-products in pulping processes | |
JP6358771B2 (ja) | 溶解クラフトパルプの製造方法 | |
JP2022124426A (ja) | セルロース繊維束の分離方法 | |
US322882A (en) | Thomas geaham young | |
CN106755616B (zh) | 一种磷酸水解甘蔗渣制备木糖的复式渗浸水解方法 | |
CN105350367B (zh) | 棉花预处理的新方法 | |
NO134717B (ja) | ||
WO2023047423A1 (en) | Process for treatment of biomass for pulping and biorefinery applications | |
Fišerová et al. | BLEACHED KRAFT PULP FROM PRE-EXTRACTED BEECH WOOD | |
US20070227944A1 (en) | System and a method for extracting wax from pulp fibers and paper products | |
CN104179057A (zh) | 造纸废液草酸法新工艺 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20201019 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20211027 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20211220 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20220228 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20220616 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20220708 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 7104507 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |