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VKB Wealth Management Group
Kurt Veldhuizen, CFA, CFP®
Senior Vice President - Branch Director, Senior Portfolio Manager - Portfolio Focus
Kurt is a senior vice president – branch director and senior portfolio manager. As a senior portfolio manager, he helps clients pursue their objectives by managing, on a discretionary basis, his own personalized or defined strategies, which may incorporate individual stocks and bonds, RBC Wealth Management model portfolios, and third-party investment strategies.
He has been a financial advisor since 1989. Born in Watertown, Wisconsin, Kurt grew up in Minocqua and was educated at Carroll University in Waukesha, Wisconsin. Kurt earned two Bachelor of Arts degrees: one in economics, and the other in business administration with a finance emphasis, as well as a minor in German. Subsequent to his graduation from Carroll College, Kurt earned his CERTIFIED FINANCIAL PLANNER™ certification in 1992, which is awarded by the Certified Financial Planner Board of Standards, Inc. The Institute of Chartered Financial Analysts™ conferred the designation of Chartered Financial Analyst® (CFA®) to him in 1993. Kurt completed the Senior Financial Advisor's Program at The Wharton School of Business at the University of Pennsylvania. In addition, he completed the "Bond Analysis and Portfolio Management" course from the Executive Development Center of the University of Illinois, the "Institutional Options Program" from The Options Institute of the Chicago Board Options Exchange, as well te Merger & Acquisitions Program, "Creating Value Through Strategic Acquisitions and Alliances" from the J.L. Kellogg Graduate School of Management at Northwestern University.
Kurt believes strongly that everyone has a responsibility to give back to the community where they can. He has served on the board of directors of Ascension Wisconsin Health Care, as chairman of the board of Howard Young Health Care, on the board of directors of Ministry Health Care, on the board of directors of Wiscraft Inc., and was a founder and president of the Lakeland Little League. He also served on the board of directors of the North Central Wisconsin Conservatory of the Arts, a forerunner to the present-day Campanile Center for the Arts in Minocqua. Kurt also served as the Cubmaster for Pack 530 of the Boy Scouts of America.
Kurt believes in listening to his clients to fully understand them: their hopes, dreams, and goals. Once known, Kurt and his team utilize the vast resources of RBC Wealth Management and focus on helping these select clients, their families and their businesses manage all aspects of their financial lives. Kurt and the VKB Wealth Management Group work with their clients to develop a plan to grow and preserve their wealth.
Kurt and his wife, Michelle, were married in 1990, and have three sons: Abbott, Carter, and Davis. When not working, Kurt enjoys spending time with his family, golfing, downhill skiing, and many other outdoor activities. He is also known as a die-hard fan of the Chicago Cubs.
Matthew A. Kock, CFP®
Senior Vice President - Financial Advisor, Senior Portfolio Manager - Portfolio Focus
Matt is a senior vice president – financial advisor, having earned the CERTIFIED FINANCIAL PLANNER™ certification, awarded by the Certified Financial Planner Board of Standards, Inc. and the Chartered Retirement Planning CounselorSM certification awarded by the College for Financial Planning. Matt earned his Bachelor of Arts degree in business administration with an emphasis in finance from the University of Wisconsin at Oshkosh. He joined the financial services industry in 2003.
His approach to wealth management is long term, not simply market transactions. He is able to draw on the extensive wealth management resources available within RBC Wealth Management and deliver them as part of your plan.
Matt provides this personal, tailored service to a limited number of clients using a program of periodically scheduled contacts and portfolio reviews. This allows him to focus on issues important to you and your family, periodically updating your current situation to address risk tolerance, time horizon, liquidity needs, and overall investment goals.
Matt has also worked with clients that have sold their business, and has helped companies structure their business retirement plan. Using the entirety of the RBC Wealth Management organization, he has many resources available to help you make sound decisions. In addition, he often collaborates with your tax and legal advisors to develop tax-efficient strategies that optimize your overall financial situation.
When not busy with his family and work, Matt finds time to give back to his community. He is active in the community basketball program as one of the traveling team coaches. He serves on the board of elders at Trinity Lutheran Church and School, where he has also served on church council and school board. He is a past president of the local Rotary Club, and former board member of the Campanile Center for the Arts, local Junior Achievement chapter, and Lakeland Area Scholarship Fund.
Matt lives in Minocqua, Wisconsin, where he was born and raised, with his wife, Tamra, and their two children. In addition to work and family, Matt loves to play golf.
John M. Bennett, CFP®, CIMA®
John is a first vice president – financial advisor and portfolio manager in VKB Wealth Management Group. As portfolio manager, he helps clients pursue their objectives by managing, on a discretionary basis, the VKB team's own customized tactical strategies, which may incorporate individual stocks and bonds, RBC Wealth Management model portfolios and third-party investment strategies.
John earned his Bachelor of Business Administration degree in finance from the University of Wisconsin – Oshkosh, where he graduated cum laude. John also earned the CERTIFIED FINANCIAL PLANNER™ certification which is awarded by the Financial Planner Board of Standards, Inc. Additionally, John is a Certified Investment Management Analyst, conferred by the Investments & Wealth Institute™. He has been a financial services professional since 1999, advising clients on wealth accumulation, preservation and transfer. John delivers tailored wealth management strategies to high-net-worth families to address their current and evolving liquidity needs, risk tolerances, time horizon and overall wealth goals.
At the heart of John's philosophy is a desire to build enduring client relationships. He believes strong relationships are essential to better understand and anticipate financial needs in order to proactively plan for clients.
John grew up in Eagle River, Wisconsin, and feels blessed to be able to continue to live, work and play in the beautiful Northwoods. John is an active member of his church, currently serving on the church council and school board for Trinity Lutheran Church & School.
When not in the office, John enjoys spending family time with his wife, Wendi, and their two daughters. He is also an avid fisherman and loves the outdoors.
John Hilbert
Vice President - Financial Advisor
John is a partner in the VKB Wealth Management Group. He has been in the financial services industry since 1998 and joined RBC Wealth Management in 2019. John focuses on clients' goals, and concerns, offering the goals-based wealth management process.
John works to simplify high-net-worth clients' financial lives. He assists clients in identifying and prioritizing their various goals—including investments, tax minimization strategies, and wealth transfer, and retirement income. He then develops strategies that address their risk tolerance, time horizon, liquidity needs, and overall investment goals, and that may be customized to suit their personal circumstances and their own unique feelings and attitudes.
John lives in Manitowish Waters, where he is very active in the community. He is a founding board member of the Headwaters Basin Chapter of Walleyes for Tomorrow. He is also a member of the Manitowish Waters Lions Club, the Manitowish Waters Lakes Association, the Manitowish Waters Chamber of Commerce, and the Northwood's Wildlife & Wetlands Club. John enjoys hunting, fishing, and spending time outdoors with his wife, Dana, and their two children. Born and raised in Green Bay, John is an avid Packers fan.
Fritz G. Wotruba, CFP®
Fritz is a partner in the VKB Wealth Management Group. He has been in the financial services industry since 2006 and emphasizes goals-based planning and investing with clients. Fritz's approach to long-term planning focuses on developing and organizing a thoughtful individual wealth management plan with the desire of reaching lifestyle and family-focused goals. He enjoys developing deep relationships with clients and helping them gain a better understanding of how proper investing, diversification, and risk control can lead to a successful financial future.
Fritz was born and raised in Stevens Point, Wisconsin. He graduated from University of Wisconsin–Madison where he met his wife, Karla. They lived in Madison for many years, within sight of Camp Randall Stadium, which allowed them to enjoy many Badger football Saturdays. After living in Appleton for a while, they moved to the Northwoods with their two children and feel blessed to call Minocqua their home.
When Fritz is not at work, he is most likely found outdoors. In the summer, he enjoys fishing, hiking, and campfires. In the winter, he and the family are avid downhill skiers, having grown up skiing at Indianhead Mountain in the U.P. Fritz's second love is sports cars, especially Porsche. Many weekends have been enjoyed watching races all across the country.
Fritz is very active in the Minocqua community, serving as board member and past president of the Lakeland Rotary club, and committee chair for Ascension Lutheran Church.
Rick Brostowitz
Rick joined VKB Wealth Management Group in 2020. He strives to build life-long relationships through a trusted friend approach that gives clients the peace of mind that they are on track to achieve their financial needs, wants and wishes.
He began his career in the financial services industry in the retail banking division at U.S. Bank, where he served as a branch manager in Madison, Wisconsin. Prior to that, Rick was the director of season ticket sales for Madison Mallards Baseball Club. Rick graduated from the University of Wisconsin – Madison with a Bachelor of Business Administration degree, majoring in marketing. While a student, Rick performed in the UW marching band, playing trumpet for five seasons including three Rose Bowls. He has passed the Series 7 and 66 exams and holds a life and health insurance license.
A native of Wisconsin, Rick moved to Madison for college and has worked in the area since. In his free time, Rick enjoys cheering on the Wisconsin Badgers at Camp Randall Stadium and the Kohl Center. He also likes playing cards, kayaking and competing in tennis and softball. Rick volunteers his time at Ridgeway Church, where he serves as a youth leader for middle school and high school students.
Christine Ullius
Branch Service Mgr/Sr Registered Client Assoc
Christine is a registered senior client associate with the VKB Wealth Management Group. She has passed the Series 7 and Series 63 exams. Christine, a Minocqua resident since 1996, graduated from Luther College in Decorah, Iowa, with a bachelor's degree in accounting and a minor in economics. She has worked in the securities industry for more than 22 years and spends most of her free time with her husband, Rob, and three children.
Susan Knapstein
Sue is a registered senior client associate. She has passed her Series 7 and Series 66 exams. Sue earned her Associate of Accounting degree from Nicolet Area Technical College in Rhinelander. She was born in Illinois, raised in Howards Grove, Wisconsin, and feels blessed to live in Arbor Vitae, surrounded by the beautiful Northwoods.
Sue has served as treasurer for the Brandy Park Commission and is a past administrator and teacher for the North Central WI Conservatory of the Arts. When not in the office, she enjoys spending time with her husband, Dave, doing DIY renovations, and playing musical instruments. Their first priority is to make sure to spend time with their two adult children's families, especially their two granddaughters.
Kurt Veldhuizen, NMLS # 557314, Matthew A. Kock, NMLS # 557277, John M. Bennett, NMLS # 557230, John Hilbert, NMLS # 557268, Fritz G. Wotruba, NMLS # 1374983, and Rick Brostowitz, NMLS # 1519225 through City National Bank, may receive compensation from RBC Wealth Management for referring customers to City National Bank. Banking products and services are offered or issued by City National Bank, an affiliate of RBC Wealth Management, a division of RBC Capital Markets, LLC, Member NYSE/FINRA/SIPC and are subject to City National Banks terms and conditions. Products and services offered through City National Bank are not insured by SIPC. City National Bank Member FDIC.
, Kurt Veldhuizen, NMLS # 557314, Matthew A. Kock, NMLS # 557277, John M. Bennett, NMLS # 557230, John Hilbert, NMLS # 557268, Fritz G. Wotruba, NMLS # 1374983, and Rick Brostowitz, NMLS # 1519225 through City National Bank, may receive compensation from RBC Wealth Management for referring customers to City National Bank. Banking products and services are offered or issued by City National Bank, an affiliate of RBC Wealth Management, a division of RBC Capital Markets, LLC, Member NYSE/FINRA/SIPC and are subject to City National Banks terms and conditions. Products and services offered through City National Bank are not insured by SIPC. City National Bank Member FDIC.
Senior Vice President - Branch Director,
8613 US Hwy 51 N


Carolyn, So very sorry to hear of your Mom's passing. She was a lovely lady. Thinking of you and the entire family at this difficult time.
Condolence: To Debbie, Carolyn and Crystal, My deepest condolences on the loss of your mother.
Condolence: My heart goes out to you sisters. I have such special memories of your Mom as a child growing up; the friendship between families. I can still hear Anne's laugh and her voice as she spoke.
Condolence: Our condolences to her family.Our friendship began in highschool.RIP Anne.
Condolence: Crystal, Carolyn, Debbie, and family my heartfelt sympathies. May Anne rest in peace. Take care of each other, Aunt Maxine.


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Contact Avril
" We have parties at my house. My girlfriends and I play our iPods, with all of our favorite songs. We pick our songs and jump up on the counter and dance, and do runway stuff, and we take video with my camera. When I'm with my girlfriends, I act like I'm 19."
Avril Lavigne is a Canadian singer-songwriter and actress who titled "skater punk" persona and "pop punk princess" for her success in the music industry since her entry at the age of 17, selling more than 30 million albums and over 50 million singles worldwide since.
She was born on Thursday September 27th 1984, in Napanee, Belleville, Ontario, Canada.
2021 is a year of dynamic change for Avril Lavigne. Many surprises will come her way, and Avril better be open and ready to embrace new opportunities.
Lavigne must not be overly careful this year. 2021 is a year in which a major step forward can take place if she is willing to take some calculated risks and do a little gambling. Wisdom and prudence is the key, but Avril Lavigne will definitely be faced with choices that require fast action and a willingness to act before all the facts are in. This is an exciting year in which she will be required to promote herself in order to take full advantage of the opportunities that await her. There will be increased opportunity to travel and possibly a change of residence.
Avril may be tempted by the desires of the flesh: too much food, alcohol, sex, and drugs. She must be careful and discriminate. Lavigne could make mistakes in these areas.
She will have some unexpected adventures and lucky breaks during 2021. This can be an unsettling year if Avril Lavigne tries to cling to outmoded methods or characteristics. This a year to throw off the old and adopt the new. It is a rebirth and a release after last year's struggle.
2021 is a year in which change takes place consistently, and particularly so in April and May. July 2021 is a breakthrough, a time to enjoy life. September 2021 can be intense, while October 2021 requires tact and balance in relationships.
Let's take a look now at Avril's monthly forecast for January 2021.
You and Avril
About Avril's Personal Year Cycle
In numerology, each year of Avril's life is part of an evolving pattern that can be described as a nine-year cycle or epicycle. These cycles begin at Avril Lavigne's birth and progress, one by one, through nine steps that complete an epicycle, and then begin again.
Read more about our numerological yearly forecast for Avril Lavigne . . .
Other celebrities with yearly cycle number 5 as Avril Lavigne
Mark Zuckerberg (1984)
An American programmer, entrepreneur, philanthropist, and the chairman, chief executive officer, and co-founder of the social network Facebook, considered the 6th richest person in the world, with 2016 estimated net worth of US$51.2 billion
Avril Lavigne Numerology -- Yearly Forecast for 2021 | © Copyright 2009-2021 Celebrities Galore and Master Numerologist Hans Decoz

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Conductive Thermoplastic-Resin Film And Conductive Thermoplastic-Resin Laminate Film
The present invention provides a thermoplastic-resin film and a thermoplastic-resin laminate film which have excellent conductivity and are further excellent in water vapor barrier properties and/or tackiness. As an example, a conductive thermoplastic-resin film is provided which comprises a mixture of a thermoplastic resin and a conductive material and having a volume resistivity, as measured by the four-probe method in accordance with JIS K-7194, of 10 Ω·cm or lower and a moisture permeability, as measured at a film thickness of 100 μm by JIS K-7129 method B in an atmosphere of 40° C. and a relative humidity (RH) of 90%, of 10 g/(m2·24 hr) or lower.
Miyagawa, Michinari (Shiga, JP)
Imai, Takashi (Kanagawa, JP)
Sugie, Saori (Shiga, JP)
MITSUBISHI PLASTICS, INC. (CHIYODA-KU TOKYO JAPAN, JP)
252/500, 252/502
H01M4/64; B32B27/18; B32B27/20; C08J5/18; C08K3/00; C08K3/04; C08K7/06; C08L101/00; H01B1/00; H01B1/04; H01B1/24; H01B5/16; H01G11/68; H01M4/66
20070020495 Power generating apparatus using solid oxide fuel cell January, 2007 Tokutake et al.
20070166611 High power lithium unit cell and high power lithium battery pack having the same July, 2007 Oh et al.
20050244689 Separator and fuel cell system using that separator November, 2005 Horiguchi et al.
20070154766 Collapsible metal air battery July, 2007 Baik et al.
20060166099 Closed nickel-hydrogen storage battery and its production method July, 2006 Okabe et al.
20070224465 WATER CONTROLLER SYSTEM HAVING STABLE STRUCTURE FOR DIRECT METHANOL FUEL CELL September, 2007 Noh et al.
20030108788 Sodium-sulfur battery June, 2003 Miyoshi et al.
20060251964 Battery pack having non-orthogonal coupling slots November, 2006 Zedell et al.
20070020498 Densification of ceria based electrolytes January, 2007 Steele et al.
20050238952 High tin containing alloy for battery components October, 2005 Prengaman
20100047674 Safety Switch Using Heat Shrinkage Tube and Secondary Battery Including The Same February, 2010 Ryu et al.
ROBINSON, ELIZABETH A
OBLON, MCCLELLAND, MAIER & NEUSTADT, L.L.P. (ALEXANDRIA, VA, US)
1. A conductive thermoplastic-resin film which comprises a mixture of a thermoplastic resin and a conductive material and has a volume resistivity, as measured by the four-probe method in accordance with JIS K-7194, of 10 Ω·cm or lower and a moisture permeability, as measured at a film thickness of 100 μm by JIS K-7129 method B in an atmosphere of 40° C. and a relative humidity (RH) of 90%, of 10 g/(m2·24 hr) or lower.
2. The conductive thermoplastic-resin film according to claim 1, wherein the conductive material contained in the conductive thermoplastic-resin film A comprises: a graphite powder which has an average particle diameter of from 1 μm to 20 μm and in which particles having a particle diameter of 40 μm or smaller account for 80% by mass or more of the whole powder; and a carbon black powder.
3. The conductive thermoplastic-resin film according to claim 1, wherein the volume filling factor A of the carbon black powder and the volume filling factor B of the graphite powder in the conductive material contained in the conductive thermoplastic-resin film A are in the ranges represented by the following expressions:
0<A≦0.4×(1−B)
0<B≦0.5
A+B=1
4. A conductive thermoplastic-resin film which comprises a mixture of a thermoplastic resin and a conductive material and has a volume resistivity, as measured by the four-probe method in accordance with JIS K-7194, of 10 Ω·cm or lower and a peel strength in the range of 1-150 N as measured at 25° C. after disposing two sheets of the film (150 mm×25 mm) so as to face each other and laminating the sheets to each other by pressing these in an atmosphere of 25° C. at a pressure of 3.9×105 Pa for 1 minute.
5. The conductive thermoplastic-resin film according to claim 4, wherein that the conductive thermoplastic-resin film B comprises an amorphous propylene/butene copolymer or an amorphous propylene/ethylene/butene copolymer in an amount in the range of 30-65% by mass.
6. A conductive thermoplastic-resin laminate film which comprises: a conductive thermoplastic-resin film A, as a base, which comprises a mixture of a thermoplastic resin and a conductive material and having a volume resistivity, as measured by the four-probe method in accordance with JIS K-7194, of 10 Ω·cm or lower and a moisture permeability, as measured at a film thickness of 100 μm by JIS K-7129 method B in an atmosphere of 40° C. and a relative humidity (RH) of 90%, of 10 g/(m2·24 hr) or lower; and a conductive thermoplastic-resin film B having the following tackiness characteristics which has been laminated to at least one side of the film base: Tackiness Characteristics: the peel strength as measured at 25° C. after disposing two sheets of the film (150 mm×25 mm) so as to face each other and laminating the sheets to each other by pressing these in an atmosphere of 25° C. at a pressure of 3.9×105 Pa for 1 minute is in the range of 1 -150 N.
7. (canceled)
9. A current collector for an electric double-layer capacitor comprising the conductive thermoplastic-resin film according to claim 1.
10. A current collector for a proton-ion polymer battery comprising the conductive thermoplastic-resin film according to claim 1.
11. A current collector for an electric double-layer capacitor comprising the conductive thermoplastic-resin film according to claim 2.
19. A current collector for an electric double-layer capacitor comprising the conductive thermoplastic-resin laminate film according to claim 6.
20. A current collector for a proton-ion polymer battery comprising the conductive thermoplastic-resin laminate film according to claim 6.
CROSS REFERENCE TO PRIOR APPLICATION
This is a U.S. national phase application under 35 U.S.C. §371 of International Application No. PCT/JP2005/005429 filed Mar. 24, 2005 and claims the benefit of Japanese Applications No. 2004-086809, filed Mar. 24, 2004 and 2004-095040, filed Mar. 29, 2004. The International Application was published in Japanese on Sep. 29, 2005 as International Publication No. WO 2005/090452 under PCT Article 21(2).
TECHNICAL FIELD
The present invention relates to a thermoplastic-resin film and a thermoplastic-resin laminate film each having excellent electrical conductivity. More particularly, the invention relates to the thermoplastic-resin film and thermoplastic-resin laminate film further excellent in water vapor barrier properties and/or tackiness.
BACKGROUND ART
Electric double-layer capacitors are often used in the form of a combination of two or more electric double-layer capacitor cells connected in series or in parallel for the purpose of obtaining a higher output current. However, as a result of such combination of capacitor cells, the combined cells as a whole have an increased internal resistance and there are often cases where a low output current only can be obtained. Because of this, the internal resistance of the individual capacitor cells is desired to be reduced as much as possible. In particular, the resistance generating at the interface between the electrolytic liquid and activated-carbon electrode as components of each capacitor cell, the resistance generating at the interface between the activated-carbon electrode and the current collector, and the resistance possessed by the current collector itself are required to be reduced. Especially in electric double-layer capacitors employing an aqueous electrolytic liquid, the capacitor cells have a multilayer structure and to reduce the thickness-direction resistance of the current collector is necessary for reducing the resistance possessed by the current collector itself.
In electric double-layer capacitors employing an aqueous electrolytic liquid, an aqueous sulfuric acid solution of about 25-40% is in general use as the electrolytic liquid. Usually, these capacitors are used at a temperature of about 80° C. or lower. In case where such an electric double-layer capacitor is used in an environment having a temperature exceeding, e.g., 80° C., the water in the electrolytic liquid is apt to permeate through the current collector and this is causative of a decrease in the electrical conductivity of the electrolytic liquid, an increase in the overall resistance of the capacitor cells, etc. There is hence a problem that the life of this electric double-layer capacitor is shortened.
In proton-ion polymer batteries also, the battery cells are required to be reduced in internal resistance as in the capacitor cells whose internal resistance is required to be reduced. In the batteries in which the battery cells have a multilayer structure, it is desired to reduce the thickness-direction resistance of the current collector as in the electric double-layer capacitors.
Furthermore, proton-ion polymer batteries also generally employ an aqueous sulfuric acid solution of about 25-40% as the electrolytic liquid like the electric double-layer capacitors. In an environment having a temperature as high as, e.g., above 80° C., the water in the electrolytic liquid is apt to permeate through the current collector and this is causative of a decrease in the electrical conductivity of the electrolytic liquid, an increase in the overall resistance of the battery cells, etc. There is hence a problem that the life of this proton-ion polymer battery is shortened.
With respect to the reduction of the thickness-direction resistance of a current collector, for example, a technique is being employed in which a conductive film having a reduced thickness is used as a current collector to thereby attain a reduction in electrical resistance. For example, patent document 1 describes a technique which comprises dispersing 100 parts by weight of a rubber ingredient and 5-100 parts by weight of conductive carbon in an organic solvent, casting the dispersion on a releasable film with a bar coater, and then drying the dispersion to thereby produce a thin conductive film. There is a statement therein to the effect that this film has a volume resistance as low as 0.1-5.0 Ωcm.
However, the current collector produced by the method described above has the following and other problems because it is a product shaped by casting:
(1) the film is apt to deform,
(2) the film is apt to develop holes (pin-holes),
(3) the solvent is apt to remain, and
(4) productivity is poor, although the thickness-direction electrical resistance of the film is low. Especially because of the problem that the film is apt to develop pin-holes, the film does not have sufficient water vapor barrier properties.
For improving water vapor barrier properties, a technique has hitherto been employed in which a rubber having a low moisture permeability, such as butyl rubber, is kneaded together with conductive carbon and the resultant mixture is formed into a sheet to thereby produce a current collector having a low moisture permeability. However, when it is attempted to incorporate the conductive material in a large amount into the rubber for the purpose of further reducing the thickness-direction resistance of the conductive sheet, then there is a drawback that molding is difficult because the resultant mixture generally has a higher melt viscosity than in the case of kneading a resin together with the conductive material. There also is a problem that the difficulty in molding tends to give sheets having an increased thickness and this increases rather than reduces the resistance.
Furthermore, there are cases where capacitor cells or battery cells suffer positional shifting at the current collector contact surfaces between the cells. A technique for preventing this shifting is known which comprises dispersing and mixing a styrene/ethylene/butylene/styrene copolymer resin (SEBS), a conductive material, and either a pressure-sensitive adhesive or a process oil with an organic solvent to produce a solution, applying this solution to a releasable base, drying the solution, and then peeling the resultant coating from the base to thereby produce a current collector film. It has been reported that the current collector film produced by such method can reduce the resistance of contact with the polarizable electrode or electrode plate of an electric double-layer capacitor (see, for example, patent document 2 or 3). However, even in such a conductive film also, water vapor is apt to permeate therethrough because of the addition of a pressure-sensitive adhesive or process oil and there has been a problem that the film is apt to develop pin-holes.
In patent document 4 is proposed a conductive composite sheet which is based on a combination of a conductive thermoplastic elastomer and a conductive rubber and which is thin and has self-tackiness. However, the tackiness of the conductive rubber are insufficient in tack strength and there has been a problem that when the conductive composite sheet is used as a current collector for an electric double-layer capacitor or proton polymer ion battery, positional shifting between cells is apt to occur, resulting in an increase in the internal resistance of the electric double-layer capacitor or proton polymer ion battery. In addition, use of carbon black alone as the conductive material poses a problem that the water vapor barrier effect is low because the primary-particle diameters of the carbon black are small.
Patent Document 1: WO 97/25738
Patent Document 2: JP-A-10-4033
Patent Document 4: JP-A-64-54607
DISCLOSURE OF THE INVENTION
Problems that the Invention is to Solve
An object of the invention is to provide a thermoplastic-resin film and a thermoplastic-resin laminate film which have excellent conductivity and are further excellent in water vapor barrier properties and/or tackiness.
Means for Solving the Problems
The invention is based on the finding of a conductive thermoplastic-resin film and a thermoplastic-resin laminate film which are capable of eliminating the problems described above. Essential points of the invention are shown below.
(1) A conductive thermoplastic-resin film which comprises a mixture of a thermoplastic resin and a conductive material and has a volume resistivity, as measured by the four-probe method in accordance with JIS K-7194, of 10 Ω·cm or lower and a moisture permeability, as measured at a film thickness of 100 μm by JIS K-7129 method B in an atmosphere of 40° C. and a relative humidity (RH) of 90%, of 10 g/(m2·24 hr) or lower.
(2) The conductive thermoplastic-resin film according to the above (1), wherein the conductive material contained in the conductive thermoplastic-resin film A comprises: a graphite powder which has an average particle diameter of from 1 μm to 20 μm and in which particles having a particle diameter of 40 μm or smaller account for 80% by mass or more of the whole powder; and a carbon black powder.
(3) The conductive thermoplastic-resin film according to the above (1) or (2), wherein the volume filling factor A of the carbon black powder and the volume filling factor B of the graphite powder in the conductive material contained in the conductive thermoplastic-resin film A are in the ranges represented by the following expressions:
(4) A conductive thermoplastic-resin film which comprises a mixture of a thermoplastic resin and a conductive material and has a volume resistivity, as measured by the four-probe method in accordance with JIS K-7194, of 10 Ω·cm or lower and a peel strength in the range of 1-150N as measured at 25° C. after disposing two sheets of the film (150 mm×25 mm) so as to face each other and laminating the sheets to each other by pressing these in an atmosphere of 25° C. at a pressure of 3.9×105 Pa for 1 minute.
(5) The conductive thermoplastic-resin film according to the above (4), wherein the conductive thermoplastic-resin film B contains an amorphous propylene/butene copolymer or an amorphous propylene/ethylene/butene copolymer in an amount in the range of 30-65% by mass.
(6) A conductive thermoplastic-resin laminate film which comprises: a conductive thermoplastic-resin film A, as a base, which comprises a mixture of a thermoplastic resin and a conductive material and having a volume resistivity, as measured by the four-probe method in accordance with JIS K-7194, of 10 Ω·cm or lower and a moisture permeability, as measured at a film thickness of 100 μm by JIS K-7129 method B in an atmosphere of 40° C. and a relative humidity (RH) of 90%, of 10 g/(m2·24 hr) or lower; and a conductive thermoplastic-resin film B having the following tackiness characteristics which has been laminated to at least one side of the film base:
Tackiness Characteristics:
the peel strength as measured at 25° C. after disposing two sheets of the film (150 mm×25 mm) so as to face each other and laminating the sheets to each other by pressing these in an atmosphere of 25° C. at a pressure of 3.9×105 Pa for 1 minute is in the range of 1-150 N.
(7) The conductive thermoplastic-resin film or conductive thermoplastic-resin laminate film according to any one of the above (1) to (6), characterized by being used as a current collector for an electric double-layer capacitor and as a current collector for a proton-ion polymer battery.
Advantages of the Invention
The conductive thermoplastic-resin film and conductive thermoplastic-resin laminate film of the invention have not only excellent electrical conductivity but excellent water vapor barrier properties and/or excellent tackiness. They are highly applicable especially to current collectors for electric double-layer capacitors and current collectors for proton-ion polymer batteries.
[FIG. 1A ]diagrammatic view of an apparatus for measuring thickness-direction resistance.
[FIG. 2A ]view showing the arrangement of conductive thermoplastic-resin films and wound-free paper in producing a peel strength measurement sample through pressing.
[FIG. 3A ]view illustrating the sample fixed to tensile test jigs in peel strength evaluation.
DESCRIPTION OF THE REFERENCE NUMERALS
1: electrode made of brass (with gold-plated surface)
2: sample (conductive sheet)
3: conductive thermoplastic-resin film
4: wood-free paper
5: jig (chuck) of tensile tester
BEST MODE FOR CARRYING OUT THE INVENTION
The invention will be explained below in detail.
The thermoplastic resin to be used in the conductive thermoplastic-resin film and conductive thermoplastic-resin laminate film of the invention is not particularly limited.
Examples thereof include polyolefin (PO) resins or polyolefin elastomers such as homopolymers or copolymers of monomers including ethylene, amorphous polyolefin resins (APO) such as cyclic polyolefins, polystyrene resins such as polystyrene (PS), ABS, SBS, and SIS or hydrogenated styrene-based elastomers such as SEBS, SEPS, and SEEPS, poly(vinyl chloride) (PVC) resins, poly(vinylidene chloride) (PVDC) resins, acrylic resins such as poly(methyl methacrylate) (PMMA) and acrylic copolymers, polyester resins such as poly(ethylene terephthalate) (PET), polyamide (PA) resins such as nylon-6, nylon-12, and copolymer nylons, poly(vinyl alcohol) resins such as poly(vinyl alcohol) (PVA) resins and ethylene/vinyl alcohol copolymers (EVOH), polyimide (PI) resins, polyetherimide (PEI) resins, polysulfone (PS) resins, polyethersulfone (PES) resins, poly(amide-imide) (PAI) resins, polyetheretherketone (PEEK) resins, polycarbonate (PC) resins, poly(vinyl butyral) (PVB) resins, polyarylate (PAR) resins, fluororesins or fluoroelastomers such as vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene copolymers (THV), tetrafluoroethylene/hexafluoropropylene copolymers (FEP), vinylidene fluoride (PVDF), and vinyl fluoride (PVF), and (meth)acrylate resins.
Especially preferred of the resins enumerated above as examples are polyolefin (PO) resins, amorphous polyolefin resins (APO) such as cyclic polyolefins, hydrogenated styrene-based elastomers such as SEBS, SEPS, and SEEPS, polyolefin elastomers, fluororesins, or fluoroelastomers. These resins have relatively excellent water vapor barrier properties and excellent acid resistance. More preferred are PO resins, amorphous polyolefin resins (APO) such as cyclic polyolefins, polypropylene elastomers, and fluoroelastomers, because these resins are especially excellent in water vapor barrier properties and acid resistance.
It is also preferred to use a blend of those resins for the purpose of, e.g., imparting not only water vapor barrier properties and acid resistance but also mechanical properties and other performances required of the conductive thermoplastic-resin film.
Examples of the conductive material contained in the conductive thermoplastic-resin film of the invention include natural graphites, artificial graphite powders such as pyrolytic graphite and kish graphite, expanded graphites obtained by immersing those graphites in an acidic solution and then heating the graphites to expand these, carbon blacks such as Ketjen Black, acetylene black, and the carbon black produced by the furnace process, carbon fibers such as PAN-derived ones and pitch-derived ones, carbon nanofibers produced by the arc discharge method, laser deposition, vapor deposition, or the like, metal carbides such as tungsten carbide, silicon carbide, zirconium carbide, tantalum carbide, titanium carbide, niobium carbide, molybdenum carbide, and vanadium carbide, metal oxides such as titanium oxide, ruthenium oxide, and indium oxide, metal nitrides such as chromium nitride, aluminum nitride, molybdenum nitride, zirconium nitride, tantalum nitride, titanium nitride, gallium nitride, niobium nitride, vanadium nitride, and boron nitride, metal fibers such as iron fibers, copper fibers, and stainless-steel fibers, and metal powders such as a titanium powder, nickel powder, tin powder, tantalum powder, and niobium powder.
The conductive thermoplastic-resin film of the invention includes a conductive thermoplastic-resin film A which has excellent water vapor barrier properties besides conductivity (hereinafter referred to as "film A"). With respect to moisture permeability as a property among the water vapor barrier properties of this film, the moisture permeability of the film as measured at a film thickness of 100 μm by JIS K-7129 method B at 40° C. and a relative humidity (RH) of 90% should be 10 g/(m2·24 hr) or lower. The moisture permeability thereof is preferably 5 g/(m2·24 hr) or lower, more preferably 3 g/(m2·24 hr) or lower. The reasons for this are as follows.
In case where the moisture permeability of the film as measured at 40° C. and 90% RH at a film thickness of 100 μm exceeds 10 g/(m2·24 hr), use of this film as a current collector for an electric double-layer capacitor or as a current collector for a proton-ion polymer battery in a high-temperature atmosphere of at least about 80° C. arouses the following troubles. The water in the electrolytic liquid is apt to permeate through the current collector and this is causative of a decrease in the electrical conductivity of the electrolytic liquid, an increase in the overall resistance of the battery cell, etc. As a result, the life of this proton-ion polymer battery is shortened.
With respect to volume resistivity as a property among the conductivity of film A, the volume resistivity thereof as determined in accordance with JIS K 7194 should be 10 Ωcm or lower. The volume resistivity thereof is preferably 1 Ωcm or lower, more preferably 0.8 Ωcm or lower. The reason for this is as follows. In case where the volume resistivity of the film exceeds 10 Ωcm, use of this film as a current collector for an electric double-layer capacitor or as a current collector for a proton-ion polymer battery is apt to result in an increase in the internal resistance of the electric double-layer capacitor or proton-ion polymer battery.
The conductive material to be contained in film A preferably comprises a graphite powder having the effect of imparting low water vapor permeability to the film. The conductive material preferably further includes a carbon black powder, such as, e.g., Ketjen Black, which can impart high conductivity even when added in a small amount to the resin.
It is also preferred that the graphite powder to be contained in film A should be one which has an average particle diameter of from 1 μm to 20 μm and in which the weight of particles having a particle diameter of 40 μm or smaller accounts for 80% or more of the weight of the whole powder.
For example, in the case where a carbon black and a graphite are mixed with a thermoplastic resin, the resultant film preferably is one in which the volume filling factor A of the carbon black powder and the volume filling factor B of the graphite powder are in the ranges represented by the following expressions. Thus, film A having a low moisture permeability and a low volume resistivity can be obtained.
Incidentally, a graphite powder is one in which a hexagonal network structure has sufficiently grown in layer arrangement, such as, e.g., an artificial graphite, natural graphite, or expanded graphite. In examination by wide-angle X-ray diffractometry, a diffraction peak attributable to the (002) plane is observed as a sharp peak at an interplanar spacing d002 of 0.335 nm. The graphite powder to be contained in film A of the invention preferably is one in which the peak is observed in a range where d002 is 0.345 nm or shorter (lower limit is 0.335 nm), and especially preferably is one in which the peak is observed in a range where d002 is 0.341 nm or shorter.
For producing film A, ordinary film production processes can be used. However, the process in which a solution prepared by dispersing and mixing a thermoplastic resin and a conductive material with an organic solvent is applied to a releasable base and dried and the resultant coating film is peeled from the base to produce the target film is undesirable because it has a problem that pin-holes are apt to be formed. It is preferred to use a method in which a thermoplastic resin is thermally melted to produce a film by extrusion molding, roll forming, or the like.
The conductive thermoplastic-resin film of the invention may comprise the film A as the only constituent element thereof. However, a low-electrical-resistance layer having lower electrical resistance than film A may be formed on at least one side of film A to constitute a laminate film. This laminate film is effective in considerably reducing contact resistance when in contact with other members.
Especially in the case where the conductive thermoplastic-resin film of the invention is used as a current collector for an electric double-layer capacitor or proton-ion polymer battery, the members to be in contact with the film are an electrode and the outer case (stainless steel, etc.). In this case, by regulating the low-electrical-resistance layer of the laminate film so as to have lower electrical resistance than film A, the resistance of contact with those members can be reduced. Thus, the internal resistance of the electric double-layer capacitor or proton-ion polymer battery can be reduced.
The volume resistivity of the low-electrical-resistance layer, as measured by the four-probe method in accordance with JIS K-7194, is desirably regulated to up to one-half, preferably up to one-fifth, the thickness-direction volume resistivity of film A. In case where the volume resistivity of the low-electrical-resistance layer exceeds one-half the volume resistivity of film A, the resistance of contact with the members in contact with this film A is apt to be high.
The conductive material to be contained in the low-electrical-resistance layer desirably is fine carbon fibers excellent in corrosion resistance and conductivity. The fiber diameters of the fine carbon fibers are desirably in the range of 0.0035-0.5 μm, preferably 0.08-0.2 μm. The fiber lengths thereof are desirably in the range of 0.1-100 μm, preferably 1-50 μm. Such carbon fibers have excellent conductivity.
Examples of the fine carbon fibers herein include the so-called carbon nanotubes and carbon nanofibers. Examples of the carbon nanotubes include the single type in which the carbon tube has a single-layer structure, the double type in which the tube has a double-layer structure, and the multi-type structure in which the tube has a structure composed of three or more layers. Examples thereof further include other forms such as the nanohorn type in which one end of the tube is closed and the other end is open and the cup type in which many carbon network layers of a bottomless cup shape have been superposed, with the ring edges of the carbon network layers exposed.
The proportions of a thermoplastic resin and fine carbon fibers in the low-electrical-resistance layer may be suitably determined so that the volume resistivity of the low-electrical-resistance layer is up to one-half the volume resistivity of film A. It is, however, preferred that the proportion of the thermoplastic resin to the fine carbon fibers be in the range of from 15/85 to 85/15 by volume.
The thickness of the low-electrical-resistance layer is desirably in the range of 1-50 μm, preferably 3-20 μm. In case where the thickness of the low-electrical-resistance layer is smaller than 1 μm, the low-electrical-resistance layer is apt to develop pin-holes because of the small thickness and is apt to have areas having a higher volume resistivity. On the other hand, in case where the thickness of the low-electrical-resistance layer exceeds 50 μm, this is apt to pose a problem that the conductive resin film is brittle.
Methods for producing the low-electrical-resistance layer are not particularly limited. The layer may be produced, for example, by a process in which a solution prepared by dispersing and mixing a thermoplastic resin and a conductive material with an organic solvent is applied to a releasable base and dried and the resultant coating film is peeled from the base, or by a method in which a thermoplastic resin is thermally melted to form the target layer by extrusion molding, roll forming, or the like.
The conductive thermoplastic-resin film of the invention includes a conductive thermoplastic-resin film B which has excellent tackiness besides conductivity (hereinafter referred to as "film B"). The tackiness characteristics thereof should be in the range of 1-150 N in terms of peel strength as measured at 25° C. after disposing two sheets of film B (150 mm×25 mm) so as to face each other and laminating the sheets to each other by pressing these in an atmosphere of 25° C. at a pressure of 3.9×105 Pa for 1 minute. Preferably, the peel strength is in the range of 10-120 N. The reasons for that peel strength range are as follows. Peel strengths lower than 1 N are apt to pose a problem that when this film is used as a current collector for an electric double-layer capacitor or proton polymer ion battery, positional shifting between cells is apt to occur, resulting in an increase in the internal resistance of the electric double-layer capacitor or proton polymer ion capacitor. Peel strengths exceeding 150N pose a problem that the film is difficult to handle because of the too high tackiness.
Film B can be regulated so as to have tackiness within that range by using an amorphous propylene/butene copolymer or an amorphous propylene/ethylene/butene copolymer in an amount in a specific range. The copolymer is added in an amount of 30-65% by weight, preferably 40-60% by weight, based on the conductive thermoplastic-resin film. In case where the content of the amorphous propylene/butene copolymer or amorphous propylene/ethylene/butene copolymer in the conductive thermoplastic-resin film is lower than 30% by weight, the conductive thermoplastic-resin film is less apt to have tackiness. In this case, an electric double-layer capacitor or proton-ion polymer battery is apt to suffer positional shifting at the current collector contact surfaces between the cells, and this is apt to pose problems, for example, that the resistance value is unstable. In case where the content of the amorphous propylene/butene copolymer or amorphous propylene/ethylene/butene copolymer in film B exceeds 65% by weight, this is apt to pose a problem that the film is difficult to handle because of the too high tackiness.
For the purpose of imparting tackiness to the conductive thermoplastic-resin film, an amorphous polyolefin resin (APO) such as a cyclic polyolefin or a tackifier of the rosin, hydrogenated rosin, hydrogenated rosin ester, terpene, hydrogenated terpene, terpene-phenol, petroleum resin, hydrogenated petroleum resin, styrene, or isoprene type or the like may, for example, be added to the thermoplastic resin together with the propylene/butene copolymer or propylene/ethylene/butene copolymer. However, in case where an amorphous polyolefin resin (APO) such as a cyclic polyolefin or any of those tackifiers is added as the only ingredient for imparting tackiness to the conductive thermoplastic-resin film, this is apt to pose a problem that the film is considerably reduced in tackiness and elongation although high in strength or that the film is considerably reduced in mechanical strength although sufficient in tackiness and elongation. Use of an APO or tackifier as the only ingredient for imparting tackiness is hence undesirable.
Examples of the conductive material to be contained in film B include graphite powders such as natural graphites, pyrolytic graphite, and kish graphite, expanded graphites obtained by immersing those graphites in an acidic solution and then heating the graphites to expand these, carbon blacks such as Ketjen Black, acetylene black, and the carbon black produced by the furnace process, carbon fibers such as PAN-derived ones and pitch-derived ones, fine carbon fibers produced by the arc discharge method, laser deposition, vapor deposition, or the like, metal carbides such as tungsten carbide, silicon carbide, zirconium carbide, tantalum carbide, titanium carbide, niobium carbide, molybdenum carbide, and vanadium carbide, metal oxides such as titanium oxide, ruthenium oxide, and indium oxide, metal nitrides such as chromium nitride, aluminum nitride, molybdenum nitride, zirconium nitride, tantalum nitride, titanium nitride, gallium nitride, niobium nitride, vanadium nitride, and boron nitride, metal fibers such as iron fibers, copper fibers, and stainless-steel fibers, and metal powders such as a titanium powder, nickel powder, tin powder, tantalum powder, and niobium powder.
It is preferred to use carbon blacks such as Ketjen Black and fine carbon fibers among the conductive materials shown above because these carbon materials have especially excellent acid resistance and can impart conductivity even when added in a small amount.
The fiber diameters of the fine carbon fibers are desirably in the range of 0.0035-0.5 μm, preferably 0.08-0.2 μm. The fiber lengths thereof are desirably in the range of 0.1-100 μm, preferably 1-50 μm. Such carbon fibers have excellent conductivity. Examples of the fine carbon fibers are the same as those shown above in the explanation of the low-electrical-resistance layer.
With respect to the volume resistivity of film B of the invention, the volume resistivity thereof as determined in accordance with JIS K 7194is desirably 10Ωcm or lower, preferably 5 Ωcm or lower. The reason for this is as follows. In case where the volume resistivity of the film exceeds 10 Ωcm, use of this film as a current collector for an electric double-layer capacitor or as a current collector for a proton-ion polymer battery is apt to result in an increase in the internal resistance of the electric double-layer capacitor or proton-ion polymer battery.
A preferred process for producing film B is a method in which a thermoplastic resin is thermally melted to produce a film by extrusion molding, roll forming, or the like. The process in which a solution prepared by dispersing and mixing a thermoplastic resin and a conductive material with an organic solvent is applied to a releasable base and dried and the resultant coating film is peeled from the base to produce the target film is undesirable because pin-holes are apt to be formed.
An embodiment of the invention is a conductive thermoplastic-resin laminate film which comprises the film A described above, which has excellent water vapor barrier properties, as a base and film B, which has tackiness, laminated to at least one side of the film base.
A preferred process for producing the laminate film is as follows.
First, film B is formed in the following manner. A liquid composition prepared by dissolving or dispersing a thermoplastic resin, a tackifier, and a conductive material in a solvent is applied to a smooth surface of a substrate and dried to form film B on the substrate. Subsequently, film A which has been formed beforehand is laminated with this film B preferably by the following method. The film B is disposed on at least one side of the film A so that the film A and film B face each other. The film A and film B are laminated by hot pressing or the like. Thereafter, the substrate is stripped off.
As the substrate can be used any of various known films. Examples thereof include films of polyesters, polycarbonates, triacetyl cellulose, cellophane, polyamides, aromatic polyamides, polyimides, polyetherimides, poly(phenylene sulfide)s, polysulfones, polyethersulfones, and polypropylene. Surfaces of these films may be treated with a silicone or the like for imparting releasability according to need. Of such films, polypropylene films and polyester films which have undergone a releasability-imparting treatment with a silicone are preferred from the standpoints of ease of stripping, etc. The thickness of the substrate is in the range of 5-500 μm, preferably 10-300 μm. In case where the thickness thereof is smaller than 5 μm, this substrate cannot have sufficient strength required of base films and is apt to rumple. Thicknesses thereof exceeding 500 μm pose a problem that this film is so stiff that it is difficult to handle and has poor workability.
The conductive thermoplastic-resin film and conductive thermoplastic-resin laminate film of the invention are usable in the following applications. When the films are used as members of electricity storage devices, power generators, or the like, the films can reduce the internal resistance of these because of the excellent conductivity of the films. Furthermore, since the films are excellent also in water vapor barrier properties, they can be used as the current collector of an electric double-layer capacitor or proton-ion polymer battery which employs an aqueous electrolytic liquid.
The invention will be explained below by reference to Examples, but the invention should not be construed as being limited to the following Examples.
Examples 1 to 4
<Production of Films A>
Conductive thermoplastic-resin films (films A) were produced by mixing a thermoplastic resin with a conductive material in each of the proportions shown in Table 1 by means of a twin-screw extruder (extruder temperature, 230° C.) and then extruding the resultant mixture through the die orifice of a single-screw extruder (extruder temperature, 230° C.).
The films A obtained each had a thickness of 100 μm. The volume resistivity, thickness-direction resistance, and moisture permeability of each film are shown in Table 1. The thermoplastic resin and conductive material shown in Table 1 are as follows.
1. Polyolefin elastomer "M142E" manufactured by Idemitsu Kosan Co., Ltd.; specific gravity, 0.88
2. Carbon black "Ketjen Black EC600JD" manufactured by Lion Corp.; specific gravity, 1.5
3. Graphite (artificial graphite powder) "UFG-30" manufactured by Showa Denko K.K.; specific gravity, 2.2
<Production of Low-Electrical-Resistance Layer>
A styrene-based elastomer SEBS ("Tuftec H1041" manufactured by Asahi Chemical Industry Co., Ltd.; specific gravity, 0.91) and fine carbon fibers ("Vapor-Phase-Process Carbon Fiber VGCF" manufactured by Showa Denko K.K.; specific gravity, 2) were dispersed in a volume ratio of 80/20 in THF (tetrahydrofuran) so as to result in a solid concentration of 8% by weight. Thus, a dispersion was prepared.
The fine carbon fibers used had a fiber diameter of 150 nm, fiber length of 10-20 μm, bulk specific gravity of 0.035 g/cm3, and true specific gravity of 2.0 g/cm3.
This dispersion was applied to a base film (polypropylene film; thickness, 50 μm) with a bar coater ("#28" manufactured by Matsuo Sangyo Co., Ltd.) and dried at 80° C. to obtain a base film/low-electrical-resistance layer composite material.
The low-electrical-resistance layer was peeled from the base film/low-electrical-resistance layer composite material obtained. This low-electrical-resistance layer was examined for thickness and volume resistivity. As a result, the thickness of the low-electrical-resistance layer was found to be 3 μm. Performances of the film are shown in Table 2.
Examples 6 to 9 and ComparAtive Examples 3 and 4
<Production of Conductive Thermoplastic-Resin Laminate Films>
The films A obtained in Examples 1 to 4 and Comparative Examples 1 and 2 and the low-electrical-resistance layer film obtained in Example 5 were used in the following combinations. With respect to each combination, the films were disposed in the order of low-electrical-resistance layer/film A/low-electrical-resistance layer and united by means of a hot press to produce a conductive thermoplastic-resin laminate film.
The conditions for the hot pressing included a heating temperature of 140° C., pressure of 4.9×106 Pa (50 kgf/cm2), and pressing time of 5 minutes.
Film A obtained in Example 1/low-electrical-resistnace layer film obtained in Example 5.
Comparative Example 3
Conductive water vapor barrier layer film obtained in Comparative Example 1/low-electrical resistance layer film obtained in Example 5.
Film A obtained in Comparative Example 2/low-electrical-resistnace layer film obtained in Example 5.
The conductive thermoplastic-resin laminate films obtained each had a thickness of 105 μm. Performances of the films are shown in Table 3.
Method of Measuring Moisture Permeability (Water Vapor Permeability)
Moisture permeability in the invention was measured by JIS K-7129 method B at 40° C. and 90% RH using PERMATRAN W 3/31 (manufactured by MOCON Inc., USA). The unit is g/(m2·24)hr.
(Measurement of Volume Resistivity)
Volume resistivity in the invention was measured in accordance with JIS K 7194 under the following conditions. The unit is Ωcm.
1. Measuring Apparatus
Loresta HP (manufactured by Mitsubishi Chemical Corp.)
2. Measuring Method
Four-terminal four-probe method (ASP type probes)
3. Current Applied for Measurement
(Measurement of Film-Thickness-Direction Resistance)
The thickness-direction resistance of the low-electrical-resistance layer and that of each film A were evaluated by the following method.
Resistance meter: Type YMR-3 (manufactured by Yamasaki-Seiki Co., Ltd.)
Loading device: Type YSR-8 (manufactured by Yamasaki-Seiki Co., Ltd.)
Electrodes: two flat plates made of brass (area, 6.45 cm2; mirror finish; gold-plated surface)
2. Measurement Conditions
Method: four-terminal method
Applied current: 10 mA (alternating current; 287 Hz)
Open-terminal voltage: 20 mV peak or lower
Load: 1.8 MPa (18.6 kgf/cm2)
Measurement was made with the measuring apparatus shown in FIG. 1.
resistivity Thickness-
Polyolefin Carbon (four-probe direction Moisture
elastomer Graphite black method) resistance permeability
vol % vol % vol % Ωcm mΩ g/(m2 · 24 hr)
Ex. 1 80 10 10 0.32 4.4 2.31
Ex. 2 72 20 8 0.35 4.7 1.46
Ex. 3 64 30 6 0.36 7 1.24
Comp. 88 0 12 0.85 10 4.8
Ex. 1
Comp. 60 40 0 160 250 1
Table 1 shows Examples and Comparative Examples. As shown under Examples 1 to 4, the films made of the polyolefin elastomer containing graphite and carbon black have a moisture permeability of 1.06-2.31 g/m2/24 hr and a volume resistivity of 0.28-0.36 Ωcm. These films each are the conductive thermoplastic-resin film of the invention which has a moisture permeability of 3 g/m2/24 hr or lower and a volume resistivity of 0.5 Ωcm or lower. The values of thickness-direction resistance of these films are as low as 4.4-7.2 Ωcm, showing that these films have excellent electrical properties.
In contrast, the film made of the polyolefin elastomer containing carbon black only, as shown under Comparative Example 1, has a moisture permeability as high as 4.80 g/m2/24 hr and a volume resistivity as high as 0.85 Ωcm and, hence, has a thickness-direction resistance as high as 10.0 mΩ. This film is inferior to the films of the Examples.
Furthermore, the film made of the polyolefin elastomer containing graphite only, as shown under Comparative Example 2, has a volume resistivity as exceedingly high as 160 Ωcm, although the moisture permeability thereof is as low as 1.00 g/m2/24 hr. Consequently, this film has a thickness-direction resistance as high as 250 mΩ and lacks suitability for practical use.
Styrene- Fine resistivity Thickness-
based carbon (four-probe direction Moisture
elastomer fibers method) resistance permeability
vol % vol % Ωcm mΩ g/(m2 · 24 hr)
Ex. 5 80 20 0.1 0.2 ≧100
Moreover, the low-electrical-resistance layer having a volume resistivity of 0.10 Ωcm, which is shown in Table 2 under Example 5, has a moisture permeability of 100 g/m2/24 hr or higher. However, by laminating this layer to both sides of each of the films of Examples 1 to 4, conductive thermoplastic-resin films having the same moisture permeabilities as in Examples 1 to 4 in Table 1 and having thickness-direction resistances as exceedingly low as 1.1-2.0 mΩ can be obtained as shown in Table 3 under Examples 6 to 9.
Thickness-direction
resistance Moisture permeability
mΩ g/(m2 · 24 hr)
Example 6 1.1 2.31
Comparative 2.0 4.8
Comparative 150 1.0
In contrast, in Comparative Example 3 in Table 3, the moisture permeability is high although the thickness-direction resistance is low. In Comparative Example 4, the thickness-direction resistance is high although the moisture permeability is low. These laminate films lack suitability for practical use.
Examples 10 to 15 and Comparative Example 5 and 7)
<Production of Films B>
Conductive thermoplastic-resin films (films B) were produced by mixing a thermoplastic resin with a carbon black in each of the proportions shown in Table 4 by means of a twin-screw extruder (extruder temperature, 230° C.) and then extruding the resultant mixture through the die orifice of a single-screw extruder (extrude temperature, 230° C.).
The films B obtained each had a thickness of 50 μm. The volume resistivity, moisture permeability, and peel strength of each film are shown in Table 4. The thermoplastic resin and conductive material shown in Table 4 are as follows.
1. Blend of polypropylene and propylene-ethylene-butene copolymer
"T3714" manufactured by Sumitomo Chemical Co., Ltd.; specific gravity, 0.86
(Polypropylene/propylene-ethylene-butene copolymer=15/85 wt %)
2. Polyolefin elastomer
"M142E" manufactured by Idemitsu Kosan Co., Ltd.; specific gravity, 0.88
3. Carbon black
"Ketjen Black EC600JD" manufactured by Lion Corp.; specific gravity, 1.5
A styrene-based elastomer SEBS ("Tuftec H1221" manufactured by Asahi Chemical Industry Co., Ltd.; specific gravity, 0.91) and a carbon black ("Ketjen Black EC600JD" manufactured by Lion Corp.; specific gravity, 1.5) were dissolved or dispersed in the proportion shown in Table 4 in cyclohexane so as to result in a solid concentration of 20% by weight. Thus, a dispersion was produced.
This dispersion was applied to a base film (polypropylene film which had undergone releasability-imparting treatment; thickness, 50 μm) with a bar coater (#80, manufactured by Matsuo Sangyo Co., Ltd.) and dried at 80° C. to produce a composite film composed of the base film and a conductive film.
The conductive film was peeled from the composite film obtained. The conductive film thus obtained had a thickness of 50 μm. The volume resistivity, moisture permeability, and peel strength of this conductive film are shown in Table 4.
The method used for measuring volume resistivity and the method used for measuring moisture permeability are the same as those described hereinabove.
(Preparation of Peel Strength Measurement Sample)
A sample for peel strength evaluation in the invention was produced by the following method. Two sheets of a conductive thermoplastic-resin film which had been formed by extrusion and had dimensions of 150 mm×25 mm and a thickness of 50 μm were disposed so as to face each other and laminated to each other by applying a pressure of 3.9×105 Pa thereto for 1 minute in an atmosphere of 25° C. For the purpose of securing the holding allowance necessary for holding with the chucks of a tensile tester in the peel strength measurement to be conducted later, the laminating was conducted after wood-free paper having dimensions of 10 mm×25 mm and a thickness of 80 μm was inserted and disposed between the two sheets of the conductive thermoplastic-resin film so as to true up edges of the paper and conductive thermoplastic-resin film sheets at one end, as shown in FIG. 2.
(Method of Measuring Peel Strength)
IM-20ST (manufactured by Intesco Co., Ltd.) was used to conduct a peel test at 25° C. and a pulling rate of 20 mm/min in the manner shown in FIG. 3. Peel strength was evaluated according to the calculation method as provided for in JIS K 6854. The unit is N.
(Peeling Mode)
The case in which the conductive thermoplastic-resin films themselves suffered no breakage and could be separated at the interface between these in the peel test is referred to as "interfacial separation". The case in which either of the films themselves broke in the peel test before peeling completion because of considerably low film strength, too high film tackiness, etc. is referred to as "base breakage".
Table 4 shows Examples and Comparative Examples. Examples 10 to 15 are conductive films (thickness, 50 μm) produced by adding carbon black in a proportion of 12 vol % to a blend of PP, a propylene-ethylene-butene copolymer, and a polyolefin elastomer and forming the resultant composition into film by the same extrusion molding method as described above. These conductive films have a volume resistivity of 10 Ωcm or lower, moisture permeability of 20 g/m2/24 hr or lower, and peel strength in the range of 1-150 N. These films each are the conductive thermoplastic-resin film (film B) of the invention which combines a low resistance, low moisture permeability, and moderate peel strength.
In contrast, in Comparative Example 5, the peel strength is higher than 150 N and the peeling mode is base separation because the content of the amorphous propylene-ethylene-butene copolymer is higher than 65% by weight, although the volume resistivity and the moisture permeability are 10 Ωcm or lower and 20 g/m2/24 hr or lower, respectively. It can hence be seen that the tackiness is too high.
Content of
amorphous
PP/propylene- propylene- Volume
ethylene- Styrene- ethylene- resistivity
butene Polyolefin based Carbon butene (four-probe Moisture Peel
copolymer elastomer elastomer black copolymer method) permeability strength Peeling
vol % vol % vol % vol % wt % Ωcm g/(m2 · 24 hr) N mode
Ex. 10 83 5 0 12 64.7 1.6 11.4 120 interfacial
Ex. 11 79 9 0 12 61.5 1.4 11.1 70 interfacial
Ex. 12 75 13 0 12 58.4 1.2 10.5 60 interfacial
Ex. 13 70 18 0 12 54.4 1 10 39 interfacial
Ex. 14 62 26 0 12 48.1 1 9.5 27 interfacial
Ex. 15 53 35 0 12 41.1 0.9 9 20 interfacial
Comp. 88 0 0 12 68.7 1.7 12 160 base
Ex. 5 breakage
Comp. 0 0 88 12 0 0.9 32 0.8 base
Comp. 0 88 0 12 0 0.9 8.6 0 interfacial
Ex. 7 separation
Furthermore, the thin conductive film obtained by adding carbon black in a proportion of 12 vol % to a styrene-based elastomer, casting the resultant composition on a releasable film with a bar coater, and drying the coating, as in Comparative Example 6, had a volume resistivity of 0.9 Ωcm, which was lower than in Example 10. However, this film had a moisture permeability as high as 32.0 g/m2/24 hr and a peel strength as low as 0.8 N/m. In addition, the film strength thereof was exceedingly low.
Moreover, as shown in Comparative Example 7, the conductive film produced by adding carbon black in a proportion of 12 vol % to a polyolefin elastomer and forming the resultant composition into film by the same method as in Example 10 has a volume resistivity of 0.9 Ωcm and a moisture permeability of 8.6 g/m2/24 hr. Although this conductive film has a lower resistance and a lower moisture permeability than in Example 10, it has a peel strength of 0 N/m and is inferior to the conductive film of the Example.
Examples 16 to 21 and Comparative Examples 8 to 10
<Production of Conductive Thermoplastic-Resin Laminate Films by Laminating Film B Having Tackiness to at Least One Side of Film A as Base>
(Production of Film A)
A thermoplastic resin and a conductive material were mixed together in each of the proportions shown in Table 5 under Barrier Layers 1 to 7 by means of a twin-screw extruder (extruder temperature, 230° C.).
The mixture prepared was extruded through the die orifice of a single-screw extruder (extruder temperature, 230° C.). Thus, films A described under Barrier Layers were produced.
The films A obtained each had a thickness of 100 μm. The volume resistivity and water vapor permeability of each film are shown in Table 5 under Barrier Layers 1 to 7.
The thermoplastic resin and conductive material shown in Table 5 are as follows.
M142E, manufactured by "Idemitsu Kosan Co., Ltd."; specific gravity, 0.88
2. Styrene-based elastomer
Septon 2002, manufactured by "Kuraray Co., Ltd."; specific gravity, 0.91
Ketjen Black EC600JD, manufactured by "Lion Corp."; specific gravity, 1.5
Artificial graphite powder
UFG-30, manufactured by "Showa Denko K.K."; specific gravity, 2.2
Carbon nanofibers
VGCF, manufactured by"Showa Denko K.K."; specific gravity, 2
(Production of Film B)
An SEPS (Septon 2063, manufactured by "Kuraray Co., Ltd."; specific gravity, 0.88), a carbon black (Ketjen Black EC600JD, manufactured by "Lion Corp."; specific gravity, 1.5), and a tackifier (Arkon P-100, manufactured by "Arakawa Chemical Industry, Ltd."; specific gravity, 0.9) were dispersed in cyclohexane in such amounts that the proportions of the Arkon P-100 and the carbon black were 150 parts by weight and 17 parts by weight, respectively, per 100 parts by weight of the SEPS and that the resultant solid concentration became 15% by weight. Thus, a dispersion was produced.
This dispersion was applied to a base film (polypropylene film which had undergone releasability-imparting treatment; thickness, 50 μm) with a bar coater (#24, "manufactured by Matsuo Sangyo Co., Ltd.") and dried at 80° C. Thus, a base film/conductive tacky layer 1 composite material was obtained.
The conductive tacky layer 1 was peeled from the base film/conductive tacky layer 1 composite material obtained. This conductive tacky layer 1 was examined for thickness and volume resistivity. As a result, the thickness of the conductive tacky layer 1 was found to be 5 μm. The volume resistivity of the film is shown in Table 5 under Tacky Layers 1 and 2.
Resin Conductive
ingredient material Volume Moisture
and ingredient Thickness resistivity permeability
proportion and proportion Tackifier μm Ωcm g/m2/24 hr
Barrier polyolefin carbon black 0 100 1.1 3.3
Layer 1 elastomer 12 vol %
88 vol %
Barrier styrene-based carbon black 0 100 1.5 4.2
Barrier polyolefin artificial 0 100 1.6 1.2
Layer 3 elastomer graphite powder
50 vol % 50 vol %
Barrier styrene-based artificial 0 100 2.4 1.6
Barrier polyolefin carbon 0 100 0.5 3.0
Layer 5 elastomer nanofibers
Barrier styrene-based carbon 0 100 0.7 3.8
Barrier Polyolefin carbon black 0 100 15 5.1
Layer 7 elastomer 5 vol %
Tacky styrene-based carbon black Arkon 5 120 ≧100
Layer 1 elastomer (SEPS) 17 parts by P-100 (unable to
100 parts by weight 150 parts be measured)
weight by weight
Tacky styrene-based carbon black Arkon 100 85 32
Layer 2 elastomer (SEPS) 17 parts by P-100
100 parts by weight 150 parts
The films A shown in Table 5 under Barrier Layers 1 to 6 and the film B which was the tacky layer 1 shown in Table 5 were used in the combinations shown in Table 6 under Examples 16 to 21. With respect to each combination, the films were disposed in the order of base film/film B/film A and united by means of a hot press. The base film was stripped off. Thus, the conductive thermoplastic-resin laminate films shown in Table 6 under Examples 16 to 21 were produced.
The conditions for the hot pressing included a heating temperature of 80° C. and a pressure of 4.9×106 Pa (50 kgf/cm2).
The conductive thermoplastic-resin laminate films obtained each had a thickness in the range of 103-105 μm. The volume resistivities as measured from the film B side and the peel strengths as measured after two sheets of each conductive thermoplastic-resin film were disposed so that the films B faced each other are shown in Table 6 under Examples 16 to 21.
The film A which was the barrier layer 7 shown in Table 5 was united with the film B which was the tacky layer 1 shown in Table 5, in the same manner as in Example 16. Thus, the conductive thermoplastic-resin laminate film shown in Table 6 under Comparative Example 8 was produced.
The conductive thermoplastic-resin laminate film obtained had a thickness of 105 μm. The volume resistivity as measured from the film B side and the peel strength as measured after two sheets of the conductive thermoplastic-resin laminate film were disposed so that the films B faced each other are shown in Table 6 under Comparative Example 8.
The film A having a thickness of 100 μm which was the barrier layer 1 shown in Table 5 was examined as the single-layer state for volume resistivity. Furthermore, the film A was examined for peel strength after two sheets of the film A were disposed so as to face each other. The results thereof are shown in Table 6 under Comparative Example 9.
Comparative Example 10
The film B having a thickness of 100 μm which was the tacky layer 2 shown in Table 5 was examined as the single-layer state for volume resistivity. Furthermore, the film B was examined for peel strength after two sheets of the film B were disposed so as to face each other. The results thereof are shown in Table 6 under Comparative Example 10.
The method used for measuring volume resistivity, method used for measuring moisture permeability, and method for measuring peel strength are the same as those described hereinabove.
Volume perme- Peel
resistivity ability strength
Film A Film B Ωcm g/m2/24 hr N
Ex. 16 barrier tacky 1.2 3.1 5
layer 1 layer 1
Ex. 17 barrier tacky 2.2 4.2 10
Comp. barrier tacky 17 4.9 4
Ex. 8 layer 7 layer 1
Comp. barrier none 1.1 3.3 ≦0.01
Ex. 9 layer 1
Comp. none tacky 85 32 unable to
Ex. 10 layer 2 be measured
because of
breakage of
tacky layer
As shown in Table 6 under Examples 16 to 20, the conductive thermoplastic-resin laminate films according to the invention have a volume resistivity of 0.6-2.6 Ωcm, i.e., 10 Ωcm or lower, and further have excellent water vapor barrier properties, i.e., 1.1-4.2 g/m2/24 hr, and an excellent peel strength, i.e., 2-19 N.
In contrast, the conductive thermoplastic-resin laminate film shown in Table 6 under Comparative Example 8 has a volume resistivity as high as 17 Ωcm and is inferior to those of the Examples.
The film A alone shown under Comparative Example 9 has a peel strength as low as 0.01 N, although excellent in water vapor barrier properties (moisture permeability) and volume resistivity. This film is apt to cause positional shifting between capacitor cells.
Furthermore, it can be seen that the film B alone shown under Comparative Example 10 has a moisture permeability as exceedingly high as 32 g/m2/24 hr although excellent in tackiness.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
This application is based on a Japanese patent application filed on Nov. 18, 2003 (Application No. 2003-387680), a Japanese patent application filed on Mar. 24, 2004 (Application No. 2004-86809), and a Japanese patent application filed on Mar. 29, 2004 (Application No. 2004-95040), the entire contents thereof being herein incorporated by reference.
INDUSTRIAL APPLIABILITY
The invention can provide a conductive thermoplastic-resin film and a conductive thermoplastic-resin laminate film which have excellent conductivity and excellent water vapor barrier properties and/or tackiness and are highly suitable for use as a current collector for electric double-layer capacitors or a current collector for proton-ion polymer batteries.
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Survival in a disastrous situation becomes tough especially if there is lack of food. In most of the disastrous situations, governments and local NGO's try to rescue the trapped persons as soon as possible. What if these agencies are unable to access you immediately? For example, if you live in a remote area where access is difficult because of flood or land sliding then rescue operations would take little time. It is essential to understand the importance of such situations.
The very basic thing everyone should consider is the availability of foods. Proper nutrition is essential to stay alive for a few days. Specialized foods have been processed to enable the survivors to get ready for any situation. We present the best freeze dried food which provides nutrition in difficult days. These foods have been processed by using highly specialized technologies. Don't be worried about the expiry of these foods. You can keep them fresh or utilizable for more than 07 years.
How to store these foods?
As a matter of fact, modern technology has enabled the manufacturers to produce freeze products to be stored for a longer period. Once you purchased these products, it becomes essential to store them according to expert's opinions. This provides a chance to keep these food products viable for a longer duration. All you need to know is the label. Read instructions printed on the labels of these products. It would equip you with basic knowledge and information to make survival easy in tough situations.


Ever since I can remember, I have always had problems with food. When I was a teenager, I was completely anemic and weighed less than 40 kilos (88 lb). Later on, I suffered from hepatitis B and had to spend more than six months in bed. Luckily, I had the help of a very caring and dedicated allopathic doctor at the time, who recommended I abstain from eating meat and dairy products in order to recover and save my life. I won the battle! And very successfully so!
From then on, my goal has been to help people with serious health problems, and that is why, more than two decades ago, I created one of the first centers for alternative therapies and personal growth in Majorca, Bodhana, where I introduced Reflexology and Reiki on the islands. But after a few years, I was bedridden again. For 2 months I suffered from chronic fatigue syndrome and hyperglycemia and, once again, saved my life through food, this time with the macrobiotic diet. Again I survived! After this experience I became a pioneer by expanding my range of activities and creating a massage center by the sea, on the beautiful beach of Illetas.
I continued my training, with many internationally renowned teachers within the realm of health and personal growth, and as re-birther and psychotherapist.During one of my training sessions in Virginia (USA), I bought a book by David Wolfe on raw food. I had no idea what it was, but, I devoured the book in one single night and the next day I searched the Internet to find out more about this amazing concept. I don't believe in coincidences, and when I learned that David Wolf was going to give a lecture in New York the following week, I was there listening to information which literally "blew the lid off my brains" and made a lot of sense to me: "Cooked food is dead and raw food is life".
I became a raw vegan the next day. Two years later, I went back to USA to train at the Hippocrates Health Institute, ranked as the world's number one educational medical health spa, in West Palm Beach, Florida (USA). Since then I have continued to enhance my education as a Raw Food Chef, teacher and instructor, until I sold the Bodhana center four years ago, in order to complete my training as a Raw Food coach, dedicating myself to it with body and soul. I now prepare healthy food, work as private health consultant and chef, and have written a Raw Food book in Spanish. Weighing 14 kilos less than 11 years ago and having reached the "golden age", … it turns out that I have more energy now than when I was 18! I've never felt so full of life. Life is so exciting and stimulating. You can feel like this! This way of eating can change your life forever!
As Health Educator and Coach according to the Hippocrates Health Institute teachings and as Raw Food Chef and Instructor (a Lifestyle Based on the living food principle), my purpose in life is to help those who, like you, are open and ready to learn and increase their awareness to feel peak health, feel better than they could ever have imagined, have a stress-free life style, free of disease, free of pain, loose or gain weight, have radiant skin and shiny hair, rejuvenate and enjoy longevity.
I am also available as a Reiki Master for quality reiki initiations, rebirthing, reflexology,Indian head massage, Hopi ear candling and PSCHY-K treatments.


When you are doing routine planing and you decide it is time to sharpen can you see wear on the plane blade tip?
My style, though not skill, is most similar to Sgain's. I would conclude from his comments that I am sharpening about enough as I sharpen before I would need wax, which I don't use.


<a data-pin-do="embedBoard" href="https://www.pinterest.com/josmith1845/gardening/"data-pin-scale-width="80″ data-pin-scale-height="200″ data-pin-board-width="400″> Follow Jo's board Gardening on Pinterest.
Gardening is fun. Planting is so great for the Earth and there's really no disadvantage to it. I encourage you readers and bloggers to try gardening. If you live in the northern USA, then it's too late for gardening. If you live in Hawaii or Florida or tropical islands, it's not too late to get your gardening on!


A brief look at some of the turning points in the history of the Poole Harbour area.
Once you move inland from the Studland Ferry the land rises to the chalk ridge that runs from Studland to Lulworth forming the backbone of the Isle of Purbeck. The beach at Studland gives way to magnificent cliffs, the start of the so-called Jurassic Coast which stretches across South Dorset and on to the mouth of the River Exe in Devon and spans the entire dinosaur period of history, the Triassic, Jurassic and Cretaceous eras. Fosssils from these times were mostly laid down on the ancient seabed and many can be seen in the local Dorset County Museum. Many of the cliffs have a characteristic slant to them and this, and the presence of fossils, are due to slow but spectacular upheavals in the rocks of the area as they were lifted into their current positions. Walking westwards is truly walking back in time, as the oldest deposits are found at the Devon end of the coastline and the youngest here at the Purbeck end, a mere 140 million years old.
Changes in sea levels have altered the shape of the harbour over the years. In Tudor times, Poole was almost an island.
Purbeck and the Isle of Wight were once joined and Old Harry and the Needles can be seen to have much in common. The Rivers Frome and Piddle join at Wareham and drain much of Dorset. Originally, these joined the Stour and the Avon at Christchurch with all three joining the Hamble to break out into the Channel at Spithead, east of the Isle of Wight. Since the end of the last Ice Age, sea levels have risen dramatically. The sea eventually broke through the chalk ridge, flooding the river valleys and dividing off the Isle of Wight.
Since that time, the shape of the Harbour has changed continuously under the influence of rising sea levels. As recently as 250 BC, with the sea level lower than it is today, Green Island was much nearer to the mainland via Cleavel Point, now beneath the sea of Newton Bay. This crossing was important enough to the local communities for them to have built jetties at Cleavell Point and on Green Island. A structure long thought to be a submerged causeway between Cleavel Point and Green Island has now been revealed as the two arns of a massive Iron Age harbour wall.
Ball Clay, Shale, Ironstone (from which the Agglestone Rock and the Puckstone are formed) and Purbeck stone have been mined in the area since the Bronze Age.
The area has been occupied since pre-historic times. A 2500 year old log boat, recovered from the entrance to the harbour, is on show at Poole Museum and towards the north of Wareham Forest are some iron age earthworks, Woolsbarrow Fort.
Just off the B3351, nestled in a wood, is the Bronze Age Rempstone Stone Circle. On the ridge to the South is Nine Barrow Down and further barrows are found to the east. A stone avenue in a field to the west was destroyed in 1957, but perhaps this area held similar significance in ancient times to the larger, more famous sites such as Avebury.
By 250 BC, there were jetties round the Harbour allowing pottery and jewellery made from polished Kimmeridge shale to be exported from the area. Jetties on Green Island and Cleavel Point (now underwater in Newton Bay) have been found and researched by archaeologists working in the area.
The Romans used Poole Harbour as a supply route for the invasion of Dorset, the land of the Durotriges, shipping men and equipment along the coast from Chichester via a fort at Hamworthy. They found and mined Purbeck Stone.
Traces of their roads exist in the surrounding area such as the remains of the road up to Badbury Rings, evident in Hamworthy and Broadstone. Salt works have been found all around the Harbour. Roman Black Burnished Ware pottery, found all over Britain, and often crucial in dating Roman sites, was apparently all made on the shores of Poole Harbour.
Vikings came up the river to Wareham and settled there briefly until King Alfred defeated them near Arne and drove them out to sea where bad weather destroyed over 100 ships. After invading and sacking the Monastery at Cerne, Canute sailed to Brownsea Island. His spoils from the Abbey at Cerne were said to have been returned later when he became the English King.
In the 1500s, Harry Paye so infuriated the French and Spanish by looting their coastline and shipping that they sent a fleet that sacked Poole, killing his brother and setting fire to the town. Harry's name lives on in our name for the Old Harry Rocks.
In the time of Henry VIII, a blockhouse was built on Brownsea to guard the entrance. The men of Poole had to muster to defend the entrance, and to find available men, a census dating from 1574 lists 296 Poole men required to attend to fight at the Castell of Brownz. This was much resented. The Castle today is quite modern, having suffered two major fires and much remodelling by successive wealthy owners.
The Italian inventor Marconi spent 8 years living at the Haven Hotel and experimenting with wireless telegraphy between Sandbanks, Brownsea and the Isle of Wight and then to the Royal Yacht at Cowes.
Enid Blyton spent much time in Purbeck inspired by the landscape, which she incorporated in her novels for children. Some think that Whispering Island was based on Brownsea and Kirrin Castle was based on Corfe Castle. The railways running across the heaths of the area also inspired her. You can look into this in more detail here.
Wareham has many reminders of its Saxon past in its Saxon Walls, a well preserved set of defence earth works that still make a nearly complete circle around the older part of the town and in the town itself where its old Saxon layout can still be seen.
On the Saxon Walls of Wareham, overlooking the River Piddle, you can still visit the Saxon Church, St Martin on the Walls. It was used as a refuge during a fire that hit Wareham in the eighteenth century. The church commemorates the exploits of Lawrence of Arabia, who settled near Wareham at Clouds Hill on returning to England.
The Priory, said to have been founded by St Aldhelm in the 8th century, operated as a nunnery, although it was sacked and rebuilt several times before the 11th century. It was then taken over by monks until the dissolution. It was rebuilt in the 16th century, much altered over the years, and is now a luxury hotel with beautiful gardens.
The village is dominated by the relatively recently ruined castle, blown up by order of Parliament after capture in 1646. This is the true defensive gateway of the Purbecks, being the only significant gap in the ridge. The cross in the square is Victorian, but the base is said to date back to at least a royal decree of 1381.
William the Conqueror granted land to Longspee and Winchelsea as a reward for their support in the 1066 conquest. Later, because Ower had become such a busy and important place, Edward the first issued a charter authorising the building of a new town. Plans were drawn up, but sadly the Black Death brought it all to a halt. There remain a few cottages at Newton today, south east of the Ower peninsula. Newton Church remained on maps for a long time: an enthusiastic map maker working at the time the town was being planned included the church not realising that it would never be built!
The old part of Poole, close to the Quay, has many pre-Georgian buildings, some of them dating back over a thousand years, see Poole history. Although it was small, Poole was nevertheless a very important link in the trade with Newfoundland from the beginning of the sixteenth century.
The Mansion House, Poole House, West End House, Sir Peter Thompson House, Beech Hurst and Upton Country House were all built by Poole merchants of the Newfoundland trade. The end of the Napoleonic wars brought this time of plenty to a close.
There was an isolation hospital at Baiter at one time.
Poole has now become more important in the area. The output from Poole Pottery, which developed from Carter's Tiles, a business started in Victorian times, and which produced the tiles that lined the London Underground tunnels, became world famous. Gradually, over the last century, although it retains its share of light industry, Poole has become more and more associated with the tourist trade. The town has grown rapidly. The coming of the railway, initially Castleman's Corkscrew via Wimborne, changed the landscape, enclosing and creating Poole Park, crossing the Holes Bay and the mouth of Lytchett Bay.
Poole is now the largest town in the area but quays on the other side of the harbour made that area far busier than it is today. The famous Purbeck stone, a soft stone often used for tombstones, has been quarried for many years even in Roman times. Less well-known is the ball clay, extracted for 2000 years in the area and used for making pottery by the Romans and, for the last few hundred years, sold on for making porcelain and many other important materials. You can find out about these many uses both in the past and up to the present day at this web site about ball clay. Ball clay was exported to Stoke by sea and regarded as "the best clay in the world" by Josiah Wedgwood. In the days before trains and lorries, transporting stone and ball clay was a huge undertaking, requiring quays and jetties as near to the quarries as possible.
To aid the transport of these materials, quays and jetties for ferry crossings were built on the south side of the harbour, at Ower, Middlebere, Goathorn and Redstone Point. Passage houses were built next to the quays for passengers to await the next boat for their crossing and the old houses remain in some of these places today. But the materials still had to be moved from the quarries to the quays and when production in the area was at its height, tramways and plateways were laid to connect the pits and quarries to the jetties. You can still see the route of the Middlebere Plateway on Middlebere Heath and Pikes Tramway across Stoborough Heath and parts of them can now be walked on straight, level footpaths and bridleways.
The current ferry service between Studland and Sandbanks started in 1926 and was then improved from time to time. Further west, the 1920s lift bridge between Poole and Hamworthy is the third in that location. Previously there was a toll-bridge and before that, a rowing ferry.
In the late 20th century, oil was discovered and BP set up a site at Wytch farm. There are now wells at Wytch Farm, Ower and Goathorn representing the largest onshore oil field in Western Europe. The oil-rich seams are a continuous band, passing from Kimmeridge, through Wytch Farm, under much of Britain to the North Sea Oil fields.
The remains of a Tudor ammunition dump are still visible along the shore on Baiter. The Purbeck area saw action during the Civil War mainly centred around Corfe Castle. Lady Bankes, with her husband away fighting with the royalists, defended the castle with a few men until she was betrayed and later Cromwell had an act of Parliament passed allowing him to dynamite the castle so that it could never cause trouble again. At the same time, Poole supported the Roundheads and successfully defended the town with the help of the town ditch and barricade which was near the Hungerford Bridge between the railway and the Old Town.
Along with many others in Dorset, some Wareham residents supported the Monmouth Rebellion and were duly hanged from gallows on the Wareham Walls close to the current car park.
More recently, Wareham was a garrison town in the First World War.
The The Royal Navy Cordite Factory at Holton Heath, built in 1914 supplied ordnance to the Navy during both World Wars. Ordnance was taken from the blast houses by hand pushed rail carts and shipped from a jetty opposite Rockley Point.
Studland Beach was used for exercises during the second World War, particularly during the run-up to D-Day. It was also heavily defended, including a flame defence system, where oil could be pumped into the sea and ignited, a system that was never in fact used.
Decoy areas were set up to try to divert enemy bombers. One on Brownsea Island was successfully used to protect Poole. Locations in Wareham Forest and a location on Arne provided diversions for the Cordite Factory at Holton.
Landing Craft were built at the Dorset Yacht Company and at Bolson's Yard. The Flying Boat Station at Hamworthy with its support network and marine runways made Poole a target for bombing.
Smuggling long played a role in the area, with the most notorious raid being by the Hawkhurst gang, reclaiming tea and brandy impounded in the King's Cellars on Poole Quay, now Poole Museum. Before Bournemouth was developed, the Chines and the heathland behind them made excellent landing places for contraband.
Originally Japanese, Sika deer have made a home for themselves around the Harbour. There are stories of their establishment in Wareham Forest after some of them escaped from Brownsea Island by swimming to Arne in the late 19th century and of another group from Hyde House Park thirty years later. You can read more here about the life of these secretive animals and their place in Dorset.
If you have any further information about the history of this fascinating area it would be great if you would email us.
Page updated 1st August 2016.