text:
We've focused our comments, thus far, on providing equal opportunities for every student.
We haven't touched proposals to make superintendents state employees, rather than employees of the school district who report to the school board.
Actually, that's probably a decent idea. Maybe it would have a side effect that we'd appreciate.
Monday night, the Dover School Board convened in an executive session to renew the contracts of some employees and to "discuss future staffing needs."
Perhaps if superintendents were state employees, they'd be familiar enough with state law to know that school boards (or city council or quorum courts) can't convene in executive session to discuss matters like "future staffing needs."
Executive sessions must refer only to actions regarding specific personnel. Typical executive session topics include hiring, firing, disciplinary action, promotion, demotion and salary.
Renew a contract for a teacher. Fine.
Hire a principal. Fine.
Talk about how many English teachers the district might need in a few years. Nope. That's a discussion that the public has a right to know about. The public has a right to know how its elected leaders feel about English teachers or whatever the subject might be.
One other area that some officials tend to overlook when dealing with executive sessions is that only members of the legislative body, and any employee who may be the topic of discussion, may attend. No attorneys. No advisers. No special guests.
Certainly, executive sessions allow officials to consider relevant personnel matters with candor that they might not extend to a public meeting, but the taxpaying voters deserve to know how these officials arrive at their decisions. That's why executive sessions must meet a high bar for legitimacy.
Dover School Board members didn't reach high enough Monday night.
- Rick Fahr


text:
Natural Gas Pipeline Company Of America
Seventh Revised Volume No. 1
Contents / Previous / Next / Main Tariff Index
Effective Date: 04/18/2008, Docket: RP08-319-000, Status: Effective
Original Sheet No. 399 Original Sheet No. 399 : Pending
(1) S&P and Moody's opinions, watch alerts, and rating
actions and reports, rating, opinions and other actions by Dun and
Bradstreet and other credit reporting agencies will be considered in
determining creditworthiness.
(2) Consistent financial statement analysis will be
applied by Natural to determine the acceptability of Shipper's current and
future financial strength. Shipper's balance sheets, income statements,
cash flow statements and auditor's notes will be analyzed along with key
ratios and trends regarding liquidity, asset management, debt management,
debt coverage, capital structure, operational efficiency and profitability.
(3) Results of bank and trade reference checks and
credit reports must demonstrate that a Shipper is paying its obligations in
a timely manner.
(4) Shipper must not be operating under any chapter of
the bankruptcy laws and must not be subject to liquidation or debt
reduction procedures under state laws and there must not be pending any
petition for involuntary bankruptcy. An exception may be made for a
Shipper who is a debtor in possession operating under Chapter XI of the
Federal Bankruptcy Act if Natural is assured that the service billing will
be paid promptly as a cost of administration under the federal court's
jurisdiction, based on a court order in effect, and if the Shipper is
continuing and continues in the future actually to make payment.
(5) Whether Shipper is subject to any lawsuits or
judgments outstanding which could materially impact its ability to remain
(6) Whether Shipper has or has had any delinquent
balances outstanding for services provided previously by Natural and
whether Shipper is paying and has paid its account balances according to
the terms established in its service agreements (excluding amounts as to
which there is a good faith dispute).
(7) The nature of the Shipper's business and the effect
on that business of general economic conditions and economic conditions
specific to it, including Shipper's ability to recover the costs of
Natural's services through filings with regulatory agencies or otherwise to
pass on such costs to its customers.
(8) Any other information, including any information
provided by Shipper, that is relevant to Shipper's current and future
financial strength and Shipper's ability to make full payment over the term
of the contract.

subset: commoncrawl


text:
With 50 watts from dual 6L6 Class A power tubes, Rivera's Venus 5, 1x12 combo offers two independent channels with 3 band equalization powered by five 12ax7 tubes. The lead channel provides extraordinary gain and sustain while the Super Rhythm channel kicks out oodles of headroom. Add the channel assignable and footswitchable Accutronics spring reverb and you get a spectacular amp for studio and live projects.
Rivera Venus 5 1x12 Features
What started as a simple string and pedal sales catalog has grown exponentially over the past thirty years. The early days were a time where catalogs didn't have much of a presence in the industry, but what began as a college dorm room operation grew rapidly. In 1986 we moved to a full product offering and 64-page catalog, which over the years has grown to 162 pages. Join the AMS family and get your free catalog now!
Copyright © 1996-2017 American Musical Supply, Inc. All rights reserved. American Musical Supply reserves the right to correct pricing and/or product specifications in the event of typographical errors found in our print catalog or on our website. If a product is listed at an incorrect price due to such errors or because of inaccurate information received from a supplier, American Musical Supply shall have the right to refuse or cancel any orders placed, whether or not the order has been confirmed and your credit card charged. If your credit card has already been charged for the purchase and your order is canceled, American Musical Supply will issue a credit to your credit card account in the amount of the charge.


text:
By Naomi Hatch
"It is a sad and happy time at the same time," said Snowflake School District Superintendent Hollis Merrell as he talked at last week's governing board meeting of those retiring from the district.
Merrell recalled that Snowflake Intermediate School Principal Jess Hughes was coaching a football team Merrell played against in high school. "His team won the state championship my senior year," said Merrell.
"Mr. Hughes is an incredible principal," the superintendent continued, noting that sometimes he can't contain himself and has to share ideas with others. "He's always looking for ways to improve. The best compliment I can give him is he's not afraid to change."
Hughes has been in education for 33 years, with 21 of those years in the Snowflake District.
Taylor Elementary School Principal Dennis Evans came to the Snowflake District after college and has been here for 39 years.
"He is our longest tenured employee," said Merrell, who went on to tell some of the things that Evans does with TES students, such as have his hair dyed blue to reward students for big accomplishments.
"He has a school where people enjoy being there, students enjoy being there, teachers enjoy being there. He's put them (students) on their path to success," said Merrell.
Also retiring is Highland Primary School Principal Alma Yates. He will be honored at the May governing board meeting. Plaques will be presented to Claudia Morris, Lorraine Rencher and Marilyn Saline as they each retire.
Merrell said that if you add the total years in education of these principals it is 107. "I don't think we could quantify the lives that these people have touched over the years," he said.
Carol Seigfried, who has been at Snowflake Junior High School for six years, was also honored.
"She's not retiring, just moving to greener pastures," said SJHS Principal Kim Lewis. He offered examples of two math problems she presented in her class on probability. One was a story problem that used the Snowflake football team as an example. "To you it might not seem like a big deal, but when kids see their own names in math problems, they connect like that," said Lewis as he snapped his fingers. "She has been doing this for years."
Seigfried did her student teaching in social studies, and taught language arts and math. Also at the April 11 meeting, the board approved a transfer for Debra Muder from teacher to principal at Taylor Intermediate School, and the hiring of Jeremy Hatch as principal of Taylor Elementary School and Roy Owens as principal of Highland Primary School.
By Naomi Hatch


text:
The DiMarzio Basic Guitar Cables use the same wire and Switchcraft ends as our famous DiMarzio Instrument Cable with the overbraid jacket but with a lower price.
Exceptionally crisp, clear, quiet and durable, they outperform cables costing much more. They've been called the new industry standard. Custom designed low-capacitance American-made copper cable ensures low stage noise and guarantees consistent sound and improved high frequency response. All DiMarzio cables are hand made in their NYC factory.
DiMarzio Basic Instrument Cable Specifications
What started as a simple string and pedal sales catalog has grown exponentially over the past thirty years. The early days were a time where catalogs didn't have much of a presence in the industry, but what began as a college dorm room operation grew rapidly. In 1986 we moved to a full product offering and 64-page catalog, which over the years has grown to 162 pages. Join the AMS family and get your free catalog now!
Copyright © 1996-2017 American Musical Supply, Inc. All rights reserved. American Musical Supply reserves the right to correct pricing and/or product specifications in the event of typographical errors found in our print catalog or on our website. If a product is listed at an incorrect price due to such errors or because of inaccurate information received from a supplier, American Musical Supply shall have the right to refuse or cancel any orders placed, whether or not the order has been confirmed and your credit card charged. If your credit card has already been charged for the purchase and your order is canceled, American Musical Supply will issue a credit to your credit card account in the amount of the charge.


text:
Hole in roof didn't stop church service
Despite a hole in the roof and restrictions on traffic around St. John Lutheran Church in southwest Wadena, the congregation held its regular service Sunday.
The Rev. Stephen Meltzer said it was important for the congregation and other community members to gather despite the devastation throughout town.
"We have members of our congregation who lost their homes, and we felt that it was very import that they were able to come to their house of worship," said George Deiss, a member of the church's board of elders.
Meltzer likened the church service to law enforcement setting up an emergency operating center.
"For God's people it's every bit as important to establish and emergency operating center and this is that place," Meltzer said.
About 175 parishioners attended the services, and members were greeted at the door with a hug from 80-year-old Mazie Mueller. For many, it was the first opportunity to find out how their neighbors fared in the storm, said Mueller, a 60-year member of the church.
Next door, gravestones and trees were upended in the Wadena Cemetery. Mueller said she thought damage inside the church would be worse after seeing the condition of the cemetery.
"I just had to thank God that we're all here, and we're all kind of smiling and happy to see each other," she said.
The message for the service was based on faith in spite of a disaster, Meltzer said.
"Regardless of what happens around us, God still has a plan for us, ... and it's that faith that maintains us," he said.
St. John was the only church damaged in the storm.
What parishioners found Sunday morning is far from the mess that littered the church Thursday night, Meltzer said.
About 40 volunteers worked for about six hours Saturday to remove glass and debris from the fellowship hall and sanctuary.
The storm blew out windows in the fellowship hall, littering the carpet with glass. Winds scattered insulation and debris from outside throughout the sanctuary, Deiss said.
Despite the damage, members at Sunday's service maintained a positive outlook on the disaster.
"Wadena is going to be stronger because of this," Deiss said. "This church is going to be stronger because of it."


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Arava Export Growers is the third largest agricultural export company in Israel, with export sales of about €60 million. It is 50% owned by B. Gaon Holdings and 50% by farmers in the Arava region of Israel. The company exports (organic) peppers, tomatoes, melons, grapes, mangos, herbs, cucumbers, aubergines, watermelons and cut flowers to a large number of export markets, all under the Arava brand name. No recent figures on export quantities are available, but in 2000/2001 Arava Export Growers exported 18,000 tons of fresh produce from more than 200 growers from various regions of Israel (its map does not differentiate between Israel and occupied territory).
Arava is active for instance in the occupied Jordan Valley. The picture below is taken from Arava's website and shows its tomato growing regions which include the Jordan Valley, north of the Dead Sea, which is part of the West Bank. Arava also writes on its website that it exports peppers, herbs, grapes and organic products from the Jordan Valley.
Arava Export Growers is supplied by "Jordan River Herbs", a company owned by farmers from the settlement of Mechola in the occupied Jordan Valley.
Arava Export Growers had a sales office in the UK from 2001 until the end of 2008. A new company, Mill Associates, has taken over the marketing activities of Arava UK. Mill Associates was established by the former UK general manager for Arava. Mill Associates indicated in response to an earlier draft of this report sent to them for comment, that: 'Arava does not supply melons, mangos, cucumbers, aubergine, watermelons or cut flowers into the UK'. This suggests that Arava does export the other export products grown by Arava – peppers, tomatoes, grapes and herbs – to the UK. As indicated above, these products could be grown by Arava's suppliers in the Jordan Valley, which is in the OPTs.
The address of Mill Associates Ltd. is:
Unit 5, The Mill Business Centre
Gringley on the Hill
Nottinghamshire DN10 4RA
United Kingdom
Tel: 01777-818333
E-mail: email@example.com
On its website, Arava states it complies with the Tesco Natures Choice standard, although it is not clear if Arava is actually supplying to Tesco.
UK economic links with Israeli settlements


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RESIDENTS are joining forces to save nearly half of the public toilets on the islands of Arran that are faced with closure.
Talks are at an advanced stage to gift the rundown public loos to the islanders who created a stink over their imminent demise, and are looking to take over their operation.
It comes after North Ayrshire Council announced it was to close all Arran's nine public loos to save £35,000 a year.
Loading article content
But a campaign was launched to save them, as they are seen as vital to a holiday island.
Some of them were understood to have been given a stay of execution for a year to allow community groups to buy and run them.
If an agreement goes through, four of the nine public conveniences would become owned by islanders and run by volunteers.
Bill Calderwood, chairman of Arran Community Council there were positive discussions and added: "It's part of this making sure that Arran is seen as a welcoming and a good destination.
"It's also a good thing for health and safety.
"That's the other thing - there is a requirement on councils to provide dog facilities but not for humans.
"It's a bit ironic for a tourist island to be faced with that."
Under a Community Asset Transfer scheme, ownership of the public toilets at Kilmory, Whiting Bay, Sandbraes and Glen Sannox could pass to local organisations.
Campaigners created a film to help the bid to save the toilets
Craig Hatton, executive director of place at North Ayrshire Council said: "In terms of toilets we really value these facilities but we have a number of competing demands.
"But we're hoping that in the longer term that most or all of these facilities will be transferred through community take-overs to remain open."
It does, however mean that the rest of the public toilets will close, four on March 31, 2017.


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Hüman / / Member Since January 2008
i've got some new pieces up.
stop by and have a look!
You're so very kind, I'm glad you like my arm hair.
Hi I was wondering if you could take a look at my new design "Red Bonzai Sea" your honest thoughts would be greatly appreciated. Looking to network with more artist this year. Thanks


text: How nice of Marks & Spencer to do an advert which doesn't focus on offers, products or how great they are. Instead we get to see the magic of Christmas - just like Magic & Sparkle (M&S) - through clever use of a fairytale book, narrated by that guy from Star Trek (Patrick Stewart). It also stars Will Young (yummy), Baby Spice (sorry, I mean Emma Bunton), that weird looking one from Harry Potter and My Family (Zoe Wanamaker) and June Sarpong (don't really know what she's famous for except being a loudmouth!!). But it doesn't matter that the celebrities aren;'t David Beckham or the new star Jonny Wilkinson, because the advert just gives you a taste of what Christmas is all about. I LOVE IT!


text:
Advanced Skateboarding
Release Date: 26 April 2010 | Certificate: Exempt
£17.89 includes FREE UK Postage (other delivery options available)
Shipping Destinations for this item
UK - Shipping Included
United Kingdom
Europe Zone 1 - £1.29
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Europe Zone 2 - £1.49
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Europe Zone 3 - £1.69
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Australia and Far East Asia - £1.69
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Others - £1.79
Falkland Islands
Sorry, this product is currently unavailable.
In this comprehensive DVD, Nic and Tristan Puehse (aka Skateboarding Twins) demonstrate and explain how to master several advanced tricks. Among the topics covered are: backside airs, 50-50s on rails, disasters, fakie kickflips, ollie transfers, lien airs, heelflips, nose manuals, acid drops, frontside airs, lipslides, kickflip rock to fakies, bonelesses, bomb drops, salflips, one-footed airs, blunt stalls, inverts, gay twists and 360s.
Release Date: 26 April 2010
Certificate: E - Exempt from Certification
Region 2
Sound: Dolby Digital
Main Language: English
For more information and our Delivery Policy see here.
For more information and our Returns Policy see here.
Catalogue No: SVD119


text:
" Author: P.D. James / Genre: Crime / Thriller / Mystery "
* Prices may differ from that shown
Without warning, a final-year Cambridge student leaves and takes a job as a gardener. Eighteen days later he's found hanging by the neck in his cottage. Cordelia Gray, sole proprietor of the Pryde Detective Agency, uncovers long-suppressed family secrets. The full-cast dramatisation of this bestselling novel stars Judi Bowker as Cordelia Gray with Anna Massey as Miss Learning.


text:
Black Mamba
Black Mamba Gloves are designed and manufactured for industrial applications where standard disposable gloves are unable to provide the resilience and performance demanded by the toughest of jobs. Black Mamba gloves work as hard as you do.
Black Mamba Nitrile Workshop Gloves (4 pairs per pack)from: US$7.14In Stock


text:
In Wednesday's general audience, Pope Benedict XVI continued with his series of teachings on the great writers of the Eastern and Western Church by turning his attention today to St. Theodore the Studite, a Byzantine monk from the eighth century. Pope Benedict urged modern day Christians to follow the saint's example to combat poverty and to avoid spiritual self-centeredness.
Pope Benedict XVI began his weekly catechesis by telling the more than 15,000 pilgrims in St. Peter's Square about the early life of the great reformer of monastic life.
St. Theodore, the Pope recounted, was born in 759 to a noble and pious family and entered the monastery at the age of twenty-two. But his life was far from a quiet one.
He vigorously opposed the iconoclastic movement and as a result, was put on trial and imprisoned. He died on November 11, 826 and is a saint both for the Catholic and Orthodox Churches.
Theodore, the Holy Father said, "characteristically insisted on the necessity of order and the monks submission to it." "One of Theodore's basic convictions was that monks, more than others, have a commitment to observe Christian duties with greater rigor and intensity in order to offer a sign, an indication, to all Christians."
Theodore also spoke of poverty, which is "from its outset a renunciation of all personal property, to learn how to live free from material things, in sobriety."
The saint's teaching on poverty can be a lesson for the modern world, explained Benedict XVI. "We must not depend on property, we must learn to do without, we must learn simplicity, austerity, sobriety. Only in this way can we create a society of solidarity that is capable of overcoming the grave problem of global poverty," the Pontiff said.
For Theodore, the Holy Father underscored, the main renunciation is in fact obedience, which he called the "martyrdom of submission."
"Monks are an example to us all of how much we too are in need of this," the Pontiff continued. "Many different currents are urging us towards a dangerous individualism and spiritual haughtiness."
"Society cannot function if everyone only thinks of themselves," Pope Benedict added. "Legality, in other words, submission and obedience to the rules of the common life and the common good, is the only thing that can heal a society, and ego itself, from the pride of being at the center of the world."
"For Theodore the Studite, one important virtue, equal to the virtues of obedience and humility, was 'philergia', that is, love for work," Benedict XVI said. Theodore defined humility as "the criteria to test personal devotion" and "did not, then, allow monks, under the pretext of prayer or contemplation, to dispense themselves from work, which is in fact the means to discover God."
"People who are fervent in work are also fervent in their spiritual obligations." "A consequence merits mention: the wealth accumulated by community work was not destined for the monks but for the poor," the Pope expounded. "We all must learn from this."
The Holy Father concluded by warning of the "numerous perils that today threaten the unity of the shared faith and push us towards a dangerous kind of spiritual individualism." He added," It is necessary to work to defend and develop the perfect unity of the Body of Christ, a unity in which the peace of order and sincere personal relationships in the Spirit can come together harmoniously."


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18530 Woodfield Rd
Gaithersburg, MD 20879
(301) 990-6868
Visited: November 28, 2009
Whenever I heard the words "Silver Spoon" I immediately think of a very young Rick Schroder in the very popular 80's show of the same name. Imagine my surprise when years ago my good friends told me that we were going to a restaurant called Silver Spoon. Immediately I wondered if they had an arcade with long ago retired games like Galaga, Pac-man or Zaxxon or if there was a train that ran through the middle of the restaurant that patron could take a ride on. Zippy, none of that...no Ricky Shroder, no fabulous mansion, not even a single arcade game.
Walking into Silver Spoon I was greeted by a very simple layout with a modest number of tables. Although Silver Spoon is a restaurant, it doesn't appear to be a traditional restaurant as there is a counter where you order your food and then seat yourself. If you visit it for yourself, don't let the decor fool you; the food is legit and good.
I was pleasantly surprised to learn that Silver Spoon served some really tasty Indian/Pakistani fare which since that first visit has always left me satisfied. Every trip to Silver Spoon has ended with a full stomach and not too big of a dent in the wallet. The prices are very reasonable and the food is made fresh; a true value for the dollar. If you've never been to Silver Spoon just know that the wait time for food may be a bit longer than normal if you order off the menu, but know that whatever you order is made fresh as soon as you place your order.
So with all these positive notes, why the 3.5 star rating? Well let me tell you that my old friend Silver Spoon let me down a bit after my last visit....
On my last trip, I was a bit disappointed because the wife and our friends decided to be a bit adventurous by trying the buffet. BIG DISAPPOINTMENT! The quality of the food was sub-par and I guess the reason I was really disappointed was due to the fact that in the past the food ordered off the menu is always well made. The buffet food seemed thrown together, not of the best quality and it really didn't represent the true potential of the Silver Spoon chefs. The only saving grace of the buffet was the Tandoori grilled chicken which was flavorful and juicy. The final nail in the coffin was the chocolate pudding. I love chocolate so I was traumatized by chocolate pudding that had a spoiled milk taste. Yeah, very very bad.... That in itself knocked two stars off Silver Spoon's rating...but my past experiences and great food really prevented me from dipping under 3.5 stars.
So what have we learned boys and girls? You MUST stay away from the buffet but definitely order off of the menu. Grab your friends, loved ones and pass your time waiting for your delicious food by sipping a mango lassi and having some great conversations....and laugh until the mango lassi comes outta your noses. :-)
Tuesday, December 1, 2009
Silver Spoon
Posted by Antonio at 8:19 PM
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text:
Singers Keith Urban, Usher and Natasha Bedingfield (l to r) announced to the media ON 9/3/08 that they will perform at the NFL opening kickoff 2008 in New York City on September 4, 2008. (UPI Photo/Ezio Petersen)
United Press International is a leading provider of news, photos and information to millions of readers around the globe via UPI.com and its licensing services.
With a history of reliable reporting dating back to 1907, today's UPI is a credible source for the most important stories of the day, continually updated - a one-stop site for U.S. and world news, as well as entertainment, trends, science, health and stunning photography. UPI also provides insightful reports on key topics of geopolitical importance, including energy and security.


text:
Im worried that Im not going to cut strips straight, anyone have one of these, have you tried one, what do you think of it even if you havent used it?
Welcome to the Quilting Board!
Im worried that Im not going to cut strips straight, anyone have one of these, have you tried one, what do you think of it even if you havent used it?
??????What toy?
did you forget to attach something? :wink:
I probably have it what ever it is. :D
you can cut strips straight..it just takes practice, and maybe a non skid ruler...they make a ruler with rough patches on the bottom..called creative grids..if you can only afford one, get the 4.5 x 18.5
most LQS's sell them also.
or you can get o'lipfa, it has an actual lip on it, to help line up and keep in on the cutting mat.
you can use a coupon, and get it from Joanns and maybe michaels crafts sells them.
the gizmo your referring to, the machine? save your money..heard more bad than good.
I had a miserable time getting perfect cut strips. I bought the Shape Cutter, I still messed up some strips. I bought the Alto2 Cutting Sytem, never have gotten the same size in mulitple cuts from that. I decided to just buy jelly rolls and not cut strips. Ha. I bought the Accuquilt Go die cut machine and strip die. WooHoo! perfect cut strips every time! Of course if I want a size strip I don't have the die for then it's back to hit and miss. But most strips I need are 2 1/2 or 1 1/2 and now there is a 3 1/2 die.
my friend just ordered the one you have..too much money for me! but i will bet she is going to love it!
the one i thought she was referrring to, is the one they are selling at Joanns..i heard it is a pain to run..i think there is a u tube on it...
The single biggest thing that has made cutting strips easier for me is putting little sandpaper circles on the bottom. Your ruler will not move with those on there, and it's much easier to cut the strips, so long as you measure carefully. I found the little sandpaper circles at Joann -- one of the best purchases I've made!
your right! i have gotten them at home depot also..i put them on a few of my other rulers..
i also put them on the little screw driver i have for getting the sewing plate off..you know, it is silver and flat..?
Don't quite know what to make of the toy. It seems to be invisible at the moment. LOL
Don't need another toy! Don't use most of the ones I already have!
What toy? I can always use another toy. Please post a pic so I can drool over it.


text:
Indicate by check mark whether the registrant by furnishing the information contained in this Form is also thereby furnishing the information to the Commission pursuant to Rule 12g3-2(b) under the Securities Exchange Act of 1934.
Publicly-held Company
Corporate Taxpayer's ID (CNPJ/MF): 02.558.115/0001-21
Corporate Registry (NIRE): 33 300 276 963
TIM Participações SA ("Company") (BM&FBOVESPA: TIMP3; NYSE: TSU) announces to its shareholders and the market in general that, In response to "Ofício GAE 3598/13 from BM&FBOVESPA", requesting explanation on the recent oscillation on the stock price and volume traded, the Company believes that last variations on its stock price might be related the public communications attachments (which follow in their original versions), published today, 24th September 2013, by the shareholders of Telco SpA ("Telco"), which owns 22.4% of Telecom Italia SpA ("TI"), the indirect parent of the Company and Telefónica S.A., became aware about recent changes in the composition of the share capital of Telco.
"Assicurazioni Generali S.p.A. ("AG"), Intesa Sanpaolo S.p.A. ("IS") and Mediobanca S.p.A. ("MB" and together with AG and IS, the "Italian Shareholders") inform that on the date hereof have entered into an amendment agreement with Telefónica S.A. ("TEF") with respect to the shareholders agreement concerning Telco S.p.A. ("Telco") for the purposes, among others, of the recapitalization and the refinancing of the company (the "Agreement").
The Agreement, which will be published in abstract in accordance with the applicable laws and will be deposited with the Companies Register, provides for:
1) a first phase, to be executed on the date hereof; and
2) a second phase, to be executed subject to the obtainment by TEF of all the authorizations of the competent telecommunication and antitrust authorities.
The expiration date of the shareholders agreement remains unchanged as of 28th February 2015.
A. Share capital increase of Telco S.p.A.
On the date hereof, TEF will subscribe a share capital increase of Telco, for an overall amount of Euro 324 million, to be paid in cash, on the basis of an evaluation of the shareholding in Telecom Italia owned by Telco equal to Euro 1.09 per share.
For the purposes of such share capital increase, the company will issue exclusively Class C share without voting rights, which may be converted by TEF – subject to the conditions indicated under paragraph D. below – in voting shares, belonging to the same class of shares already owned by TEF (Class B shares).
Telco will use the proceeds arising from the share capital increase in order to immediately reimburse, for the same amount, the financial debt that will be due in November 2013.
The outstanding bank debt of Telco will be entirely refinanced up to maximum Euro 700 million by Mediobanca and Intesa Sanpaolo in the same portion, through a new loan at market conditions. Following the entire subscription of the share capital increase by TEF, the share capital of Telco will be allocated as follows:
% share capital
% voting share capital
Generali Group
30,6% represented by Class A shares
Intesa Sanpaolo
11,6% represented by Class A shares
11,6% represented by Class A shares
46,2% represented by Class B shares
Until the possible conversion of the non voting shares subscribed by TEF into voting shares, the governance rights of each of the parties will remain unchanged, as currently in force.
B. Acquisition of a portion of the bonds owned by the shareholders
Simultaneously with the execution of the share capital increase, TEF will purchase, at their par value, from the Italian Shareholders – pro quota – a portion of the bonds issued by Telco, therefore the quota of the bonds owned by TEF after the acquisition will be equal to 70% of the entire amount, while the remaining 30% will be allocated among AG (17%), IS (6,5%) and MB (6,5%).
The consideration will be represented by ordinary shares of TEF (owned by the same TEF), listed at the stock exchange of Madrid, with an evaluation of Euro 10.86 per share. Such shares will be transferrable on the market, within certain agreed daily limits and after the expiration of a lock-up period of 15 days.
C. Further capital increase of Telco
TEF has undertaken to subscribe another capital increase of Telco, to be paid in cash, for an overall amount of Euro 117 million, by issuing shares without voting rights (Classe C shares) and subject to the terms and conditions of the first capital increase referred to under paragrapgh A. above.
Following the execution of this second capital increase, conditional upon the obtaining by TE of all regulatory and anti-trust authorizations, TEF's shareholding in Telco will reach up to 70% of the capital, without amending the governance.
D. Conversion of Class C shares and governancee
Starting from 1° January 2014, conditional upon the obtaining by TE of all regulatory and anti-trust authorizations (including those in Brazil and Argentina), TEF shall have the right to convert, also in more tranches up to a shareholding of 64,9% of the voting capital of the company - the Class C shares, without voting right, into Class B shares with voting right.
In case TEF's shareholding - as a consequence of the conversion - exceeds the 50% of the voting rights, Telco's and Telecom Italia's governance shall be amended as follows:
(i) as far as Telco is concerned:
- the board of directors shall continue to be composed by 10 members,
- the Italian Shareholders shall appoint 5 directors and TEF the remaining 5;
- the quorum of the shareholders' meeting set forth in the by-laws currently in force shall not be amended;
(ii) as far as modalities for the filing of the list for the appointment of the directors of Telecom Italia, the parties agreed that number of directors to be appointed shall not be lower than 13 and that, excluding the directors to be appointed by the minority shareholders' list, the Italian Shareholders shall have the possibility to indicate the first 2 names of the list, while the remaining directors shall be indicated half by the Italian Shareholders and half by TEF.
E. Call Option
Starting from 1 January 2014, TEF shall have the right (Call Option) to purchase in cash all Telco's shares owned by the Italian Shareholders, against a purchase price to be determined on the basis of the evaluation of Telco's shares in Telecom Italia at the higher of (i) Euro 1.10 (one point ten) and (ii) the average closing price of the TI's shares registered on the Milan stock exchange during the 30 (thirty) trading days preceding the exercise of the Call Option.
The exercise of the Call Option shall be conditional upon the obtaining by TEF of all regulatory and anti-trust authorizations.
In case of exercise of the Call Option, TEF shall be obliged to purchase, at a nominal value, all the outstanding bonds issued by Telco and owned by the Italian Shareholders against a purchase price to be paid 50% (fifty per cent) in cash and , at TEF's discretion, 50% (fifty per cent) in cash and/or TEF's shares, on the basis of the same terms set forth under paragraph B. above.
F. Demerger
Each of Telco's shareholders will maintain the right to have Telecom Italia's shares attributed directly, thus withdrawing from the shareholders agreement, by the demerger of Telco, to be requested during a first window between 15 and 30 June 2014 and a second window between 1° and 15 February 2015.
Consistently with the shareholders agreement currently in force, also the demerger shall be conditional upon the obtaining of all regulatory and anti-trust authorizations.
Milan 24 September 2013"
General Secretary and
Secretary to the Board of Directors
TELEFÓNICA, S.A. as provided in article 82 of the Spanish Stock Market Act (Ley del Mercado de Valores), hereby reports the following
Telefónica and the remaining shareholders of the Italian company Telco, S.p.A. (which holds a capital stake of 22.4 % of the voting share capital of Telecom Italia S.p.A.) have reached an agreement by virtue of which:
• As of today, Telefónica has subscribed for and paid out a capital increase in Telco, S.p.A., through the contribution of 323,772,468 euros in cash, receiving in return non-voting shares of Telco, S.p.A. As a result of this capital increase, the interest held by Telefónica in the voting share capital of Telco, S.p.A. remains unchanged (i.e. 46.18 %, as Telefónica currently holds), although its interest in the total share capital of Telco, S.p.A. is increased to 66%. The current governance at Telco, S.p.A.'s level remains unaffected, including the obligation by Telefónica of abstaining from participating or influencing in any decisions which could affect the markets in which both Telefónica and Telecom Italia S.p.A. are present.
Telco, S.p.A. will use the proceeds received from the capital increase to reduce its banking debt.
• Subject to receiving any required anti-trust and telecommunications approvals (including in Brazil and Argentina),
Telefónica will subscribe for and pay out a second capital increase in Telco, S.p.A., through the contribution of 117,227,532 euros in cash and receiving in return non-voting shares of Telco, S.p.A. As a result of this second capital
increase, the interest of Telefónica in the voting share capital of Telco, S.p.A. will remain unchanged (i.e. 46.18 %, as
Telefónica currently holds), although its interest in the total share capital will be then increased to 70%.
Telco, S.p.A. will use the proceeds received from the second capital increase to partially repay its notes.
• Starting from January 1, 2014, subject to receiving any required relevant anti-trust and telecommunications approvals
(including in Brazil and Argentina), Telefónica may convert all or a portion of the non-voting shares in Telco, S.p.A. held by Telefónica, reaching a maximum of 64.9 % of the voting share capital of Telco, S.p.A.
• The Italian shareholders of Telco, S.p.A. have granted to Telefonica a call option to acquire all of their shares in Telco, S.p.A., whose exercise is subject to receiving any required anti-trust and telecommunications approvals (including in Brazil and Argentina). The call option may be exercised by Telefonica starting from January 1, 2014 while the Shareholders Agreement remains in effect, except (i) between June 1,2014 and June 30, 2014 and between January 15, 2015 and February 15, 2015, and (ii) during certain periods, in case the Italian shareholders Telco, S.p.A. request the demerger of Telco, S.p.A.
The purchase price of the shares, payable in cash, will be based on the equity of Telco, S.p.A. at the end of the month
prior to the closing. For this purpose, the value of the shares in TelecomItalia S.p.A. held by Telco, S.p.A. will be valued at the higher of: (i) 1,10 euros per share of TI, and (ii) the average closing trading price of the 30 days prior to the call option exercise notice.
• As of today, Telefónica will acquire from the remaining Telco, S.p.A.'s shareholders 23.8% of the non-convertible notes issued by Telco, S.p.A., in exchange of 39,021,411 Telefónica's treasury shares, which represent 0.9 % of its share capital. In this respect, the remaining Telco, S.p.A.'s shareholders have committed: i) to refrain from selling the aforementioned shares during the next 15th business days, and ii) to assume some restrictions that, in case of sale, ensure an orderly sale of such shares.
• Telefónica has assumed a standstill obligation under which Telefónica commits not to buy shares in Telecom Italia S.p.A. except if a third party acquires a relevant stake (10% or higher) in the aforementioned company.
Madrid, 24 September 2013"
Rio de Janeiro, September 25th, 2013.
TIM Participações
Rogerio Tostes
Investor Relations Officer
Pursuant to the requirements of the Securities Exchange Act of 1934, the registrant has duly caused this report to be signed on its behalf by the undersigned, thereunto duly authorized.
|Date: September 25, 2013
|/s/ Rogério Tostes
|Name: Rogério Tostes
|Title: IRO
This press release may contain forward-looking statements. These statements are statements that are not historical facts, and are based on management's current view and estimates offuture economic circumstances, industry conditions, company performance and financial results. The words "anticipates", "believes", "estimates", "expects", "plans" and similar expressions, as they relate to the company, are intended to identify forward-looking statements. Statements regarding the declaration or payment of dividends, the implementation of principal operating and financing strategies and capital expenditure plans, the direction of future operations and the factors or trends affecting financial condition, liquidity or results of operations are examples of forward-looking statements. Such statements reflect the current views of management and are subject to a number of risks and uncertainties. There is no guarantee that the expected events, trends or results will a ctually occur. The statements are based on many assumptions and factors, including general economic and market conditions, industry conditions, and operating factors. Any changes in such assumptions or factors could cause actual results to differ materially from current expectations.


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Complaint Review: Midwest Center for Stress and Anxiety
- Midwest Center for Stress and Anxiety
12300 Wilshire Boulevard, Suite 325
Los Angeles, California
- Phone: 1-866-771-9858
- Web: www.stresscenter.com
- Category: TV Advertisements
Midwest Center for Stress and Anxiety Page https://store.midwestcenter.com/takeyourlifeback says you may return the product at any time during the trial period. This is a lie Los Angeles California
Company web site https://store.midwestcenter.com/takeyourlifeback states:
You will not be charged today for any portion of Midwest Center Naturals Sleep & Relaxation supplements or for Shipping & Handling - the trial is completely risk-free. You will have fourteen (14) days to try the supplements in your home. After your fourteen (14) day risk-free trial, you will entered into Midwest Center Naturals's membership program and will be shipped an additional ninety (90) day supply and be billed at the preferred rate of $24.95 + $3.95 USD Shipping & Handling per month. You may cancel your subscription at any time by calling Midwest Center for Stress and Anxiety's customer service team at + 1(866) 282-8894.
I called the number listed above on a Saturday (my trial period ended on a Sunday) and received no answer. [continued below]....
I returned the product without any Return Authorization Number and cancelled my credit card to avoid incurring any additional charges from this company. About 2 weeks later I received a phone call demanding that I pay the $69.99 (not $170.00) restocking fee or that my file would be turned over to collections which would like have a significant negative impact on my credit rating, which I have spent my entire life working on and currently sits at around 820.
I refused to be extorted out of $69.99 over a threat of having my credit damaged when the company did not honor their end of the agreement. If they state that I may cancel my subscription "at any time" then I expect someone to be available to provide a Return Authorization Number "at any time" Interestingly, the company's sales department is open for business on the weekends, why is the customer support department closed?
Based upon the number of search results that are returned by a simple google search of the three words midwest center scam it would appear that I am not the only person that has been dissatisfied with the level of service provided.
Engaging in this sort of business practice is contemptible and even worse, it targets people that are already anxious or depressed. I am not too worried though because in my experience what goes around comes around, Karma truly is a B*%&$...
Does your business have a bad reputation?Corporate Advocacy Program™Fix it the right way.
Set the record straight:Arbitration Program
This report was posted on Ripoff Report on 03/26/2014 07:24 AM and is a permanent record located here: http://www.ripoffreport.com/reports/midwest-center-for-stress-and-anxiety/los-angeles-california-90025/midwest-center-for-stress-and-anxiety-page-httpsstoremidwestcentercomtakeyourlifeba-1133738. The posting time indicated is Arizona local time. Arizona does not observe daylight savings so the post time may be Mountain or Pacific depending on the time of year. Ripoff Report has an exclusive license to this report. It may not be copied without the written permission of Ripoff Report. READ: Foreign websites steal our content
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text:
One of my many pet hobby horses is how much more mature I generally find the champagnes in the US compared to supposedly the same cuvée in the UK. I came across the most dramatic example last weekend.
A couple of weeks ago in London a friend with a great cellar served a bottle of Krug Rosé before dinner. It was amazing. So much the polar opposite of the rather austere state of the Krug Grande Cuvée current in Britain at the moment (see below), being very voluptuous and soft and fruity – almost strawberry like but with the lightest of touches. Really a sort of beguiling feather tickling the palate. It even looked slightly like the palest strawberry juice imaginable, still with the merest hint of blue in it.
Last weekend another generous host here in New York, another very knowledgeable wine lover, chose to serve us Krug Rosé as an aperitif before a delicious dinner cooked by the new chef at Gramercy Tavern. Knowing how he sources his wines, I suspect this was current stock rather than a long-treasured bottle. The wine was unrecognisable: much more orange than pink although still very very pale and, as he sniffed the first glass, he said "ah yes, slightly maderised the way the Brits like it". This wine was bone dry, quite chewy, relatively severe though obviously very 'serious' and deep-flavoured.
Is it perhaps that the champagne distribution chain in New York has many more links than its British counterpart? So the wine is much older by the time it reaches the consumer? I would be very surprised if our London friend had plucked his bottle off a shelf that morning – especially since his cellar is stuffed with top quality champagne.
Or is it the famous semi torna viagem effect (see Madeira) on shipping champagne across the Atlantic? Would shipping it west to east freshen it up again? OK, silly idea, but an observable effect I promise.
FYI here's a recent tasting note on Krug Grande Cuvée tasted blind, in London:
Krug, Grande Cuvée Champagne 17 Drink 2008-14
Copper. Some greenness on the nose – though lots of complexity too. Oddly enough there is almost a hint of something toasty too. This is almost like a liqueur – a tincture/essence of champagne rather than the frothy, exuberant drink itself. You need to like oak to like this wine. Not really zesty enough? Certainly an 'intellectual' wine… Obviously a very different wine from the rest, but is it more pleasurable to drink…?


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A new model for calculating global goal reserves created by Dave Rutledge, chair of Caltech's engineering and applied science division, shows that previous estimates may overstate, by hundreds of billions of tons, the amount of economically recoverable coal left in the ground.
Rutledge estimates that the total amount humans will extract, including all past mining, is only 662 billion tons. Far less that the previous best guess from the World Energy Council of 850 billion tons still available for mining
Rutledge presented his findings in San Francisco this week at the annual meeting of the American Geological Union.
Basing his new model on historical examples of fossil fuel exhaustion, Rutledge notes the consistency with which governments fail to accurately estimate their own fossil fuel reserves. "The record of geological estimates made by governments for their fossil fuel estimates is really horrible. And the estimates tend to be quite high. They over-predict future coal production."
As examples Rutledge noted the precipitous decline in British coal reserves after its 1913 peak, and the U.S. peak oil production of 1970, "controversially predicted" by M. King Hubbert in 1956 (and who was one of the first to warn of the unsustainability of fossil fuels starting in the '40's).
Methods of estimation need updating
The estimates presented by Rutledge's calculations have yet to be validated, but the National Research Council's Committee on Coal Research, Technology, and Resource Assessments to Inform Energy Policy (a mouthful) concur with the general criticisms he makes.
While they still think there's more coal in the ground than Rutledge's model suggests, they warn that estimates of U.S. coal reserves aren't as high as previously thought and that methods of estimating recoverable reserves should be updated. A 2007 report from the committee states: "Present estimates of coal reserves are based upon methods that have not been reviewed or revised since their inception in 1974, and much of the input data were compiled in the early 1970's. Recent programs to assess reserves in limited areas using updated methods indicate that only a small fraction of previously estimated reserves are actually mineable reserves."
Good news for the climate – sort of
Coal is the wildcard in climate change. Specifically, how much we humans end up burning to generate electricity, the biggest driver of anthropogenic climate change. And if the estimates for coal reserves presented by Rutledge are accurate, there will be far less of it to burn and, thus, less potential CO2 emissions.
Stanford ecologist Ken Caldeira said of the new study, "Every estimate of the ultimate coal resource has been larger. But if there's much less coal than we think, that's good news for climate."
While it may be good news, it's wildly optimistic (and irresponsible) to assume that we could or should continue to develop and burn coal unabated. Even if Rutledge's numbers are correct, and humanity decides to burn all the coal available (along with other fossil fuels), atmospheric concentration of CO2 will likely rise to at least (or "only") 460 parts per million. While a far cry from some of the gloomier scenarios of possible concentrations of 500, 700, even 1000 PPM set forth by organizations like the IPCC (who believe global coal reserves could be 5 times as much as Rutledge's estimate), it is still too much. Many climate scientists now say that global CO2 levels should stabilize at 350 PPM to avoid the worst consequences of climate change. Current levels are now around 380 PPM.
Phasing it out vs. using it up
Even if there is far less coal than previously thought, it's foolhardy to think we could just "use it up" and everything will be alright. Pushker Kharecha, a scientist at NASA's Goddard Institute for Space Studies sums it up well: "Coal emissions really need to be phased out proactively – we can't just wait for them to run out – by the year 2030. There is more than enough coal to keep CO2 well above 350 ppm well beyond this century."
EIA report shows decline in coal production
The annual long-term forecast recently issued from the Energy Information Agency projects 46 gigawatts of coal-generated power by 2030, down from 104 gigawatts from last year's forecast. This year utility companies have cancelled construction on 13 coal-fired plants.
Certainly coal will remain a dominant player for power generation for years to come, but with rising concern about global warming and anticipation of federal emissions targets spurred by president-elect Obama's call for an 80% reduction in emissions over 1990 levels by 2050, it won't much matter if Rutledge's numbers are right or not. Any way you look at it, burning coal is an unsustainable energy policy.
A recent study conducted by the consulting firm Delloitte show only 17% of 50 senior oil and gas executives believe fossil fuels will be the most sustainable source of fuel in 25 years. 23% think fossil fuel will be the cheapest. The report shows that most industry leaders believe that within 25 years renewable energy will provide the most sustainable and cheapest source of fuel. Sure, we still may have to endure silly animations of little chunks of coal dressed in holiday attire singing the praises of "clean" coal, but we all know better. Whether there is 850 billions tons left, or less than 662, the transition away from coal has already begun. Time will tell if it is fast enough.
Read more on the EIA long-term energy forecast
Read more about clean coal's "reality check" on Jeff Siegel's excellent post last week.


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|Publication number
|Publication type
|Application number
|Publication date
|19 Feb 1985
|Filing date
|24 Feb 1983
|Priority date
|13 May 1977
|Fee status
|Also published as
|Publication number
|Heinz Grunert, Fritz Hahn, Ulrich Rall, Klaus Schumann, Milan J. Schwuger, Heinz G. Smolka
|Original Assignee
|Henkel Kommanditgesellschaft Auf Aktien
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (7), Non-Patent Citations (2), Referenced by (4), Classifications (15), Legal Events (6)
|External Links: USPTO, USPTO Assignment, Espacenet
(M.sub.2 O).sub.x.Al.sub.2 O.sub.3.(SiO.sub.2).sub.y
(M.sub.2 O).sub.x.Al.sub.2 O.sub.3.(SiO.sub.2).sub.y
0.7-1.1M.sub.2 O.Al.sub.2 O.sub.3.1.3-3.3SiO.sub.2.
0.7-1.1Na.sub.2 O.Al.sub.2 O.sub.3.>2.4-3.3SiO.sub.2.
0.7-1.1Na.sub.2 O.Al.sub.2 O.sub.3.>3.3-5.3SiO.sub.2.
0.7-1.1M.sub.2 O.Al.sub.2 O.sub.3.1.3-2.4SiO.sub.2.0.5-5.0H.sub.2 O
(M.sub.2 O).sub.x.Al.sub.2 O.sub.3.(SiO.sub.2).sub.y
0.7-1.1M.sub.2 O.Al.sub.2 O.sub.3.1.3-3.3SiO.sub.2.
0.7-1.1Na.sub.2 O.Al.sub.2 O.sub.3.>2.4-3.3SiO.sub.2.
0.7-1.1Na.sub.2 O.Al.sub.2 O.sub.3.>3.3-5.3SiO.sub.2.
0.7-1.1M.sub.2 O.Al.sub.2 O.sub.3.1.3-2.4SiO.sub.2.0.5-5.0H.sub.2 O
This application is a continuation of U.S. patent application Ser. No. 102,787, filed Dec. 12, 1979 now abandoned, which in turn is a continuation of U.S. patent application Ser. No. 903,598, filed May 8, 1978 now abandoned.
For the purpose of improving the fastness of dyes or prints on textile material, it is customary to effect an after-treatment, usually designated "soaping", following the dyeing or printing process. Alkaline salts, such as sodium carbonate, are frequently used for this soaping process in addition to anionic and/or nonionic surface-active compounds or tensides. Loosely adhering dye is thereby either washed out by the soap from the fiber or it is more strongly fixed, thus leading to an increase in the washing fastness and rubbing fastness of the dyed textile material. This increased fixing of the dye arises from the agglomeration of individual molecules of dye to form molecular associations. Substances such as carboxymethyl cellulose or builders, such as are used in washing agents, do not improve the fastness of the dyes, or do not improve it to an adequate extent. In contrast to conventional domestic washing methods, the processing waters used in the textile industry, that is in the dyeing baths, rinsing and soaping liquors, are usually pre-softened.
An object of the present invention is the development of an improvement in the process of dyeing or printing textile materials comprising subjecting textile material to the action of aqueous dye solutions or suspensions at elevated temperatures, followed by soaping with soaping agents and recovery of the dyed or printed textile materials, the improvement consisting essentially of employing a fine-particulate, water-insoluble alkali metal aluminosilicate, containing bound water, of the formula
(M.sub.2 O).sub.x.Al.sub.2 O.sub.3.(SiO.sub.2).sub.y
wherein M represents an alkali metal, x is an integer from 0.7 to 1.5 and y is an integer from 0.8 to 6, said aluminosilicates having an average particle size in the range of from 0.1 to 25μ and a calcium binding power of from 20 to 200 mg CaO/gm of anhydrous active substance measured at 22° C. according to the Calcium Binding Power Test Method set out in the specification, as an auxiliary soaping agent.
This and other objects of the invention will become more apparent as the description thereof proceeds.
It has now been found that the conventional soaping process employed in dyeing or printing textiles can be considerably improved by using fine-particulate, water-insoluble alkali metal aluminosilicates, preferably combined with anionic and/or nonionic surface-active compounds. The following advantages are then obtained:
1. The fastness of the dyes and prints, particularly the washing and rubbing fastness, is distinctly improved particularly in the case of dyes which are known to be critical.
2. The frequently practised addition of highly alkaline compounds, such as sodium carbonate, can be dispensed with.
3. The quantity of surface-active compound conventionally used for soaping can be considerably reduced when using the substances in accordance with the invention.
4. Compared with the standard method, particularly when using sodium carbonate, the liquors and waste waters of the soaping process are less highly alkaline and contain only small quantities of electrolytes. This has a favorable effect on the quality of the waste water.
5. Owing to the calcium binding capacity of the alkali metal aluminosilicates, trouble caused by variations in the hardness of the processing waters can be eliminated.
6. The soaping process can be shortened and water for rinsing can be saved.
7. The bleeding or running of the background shade of the print is at the same time reduced or avoided when using the substances in accordance with the invention.
The subject of the invention is the use, as auxiliary soaping agents for dyes and prints on textile material, of fine-particulate, water-insoluble alkali metal aluminosilicates of the general formula
(M.sub.2 O).sub.x.Al.sub.2 O.sub.3.(SiO.sub.2).sub.y,
in which M represents an alkali metal ion, preferably a sodium ion, x represents a number of from 0.7 to 1.5, y represents a number of from 0.8 to 6, preferably 1.3 to 4, which aluminosilicates have a particle size of from 0.1 to 25μ, preferably 1 to 12μ, and a calcium binding capacity of 20 to 200 mg CaO/gm of anhydrous active substance at 22° C. The determination of the calcium binding power is described before the examples.
More particularly, the present invention relates to the improvement in the process of dyeing or printing textile materials comprising subjecting textile material to the action of aqueous dye solutions or suspensions at elevated temperatures, followed by soaping with soaping agents and recovery of the dyed or printed textile materials, the improvement consisting essentially of employing a fine-particulate, water-insoluble alkali metal aluminosilicate, containing bound water, of the formula
(M.sub.2 O).sub.x.Al.sub.2 O.sub.3.(SiO.sub.2).sub.y
wherein M represents an alkali metal, x is an integer from 0.7 to 1.5 and y is an integer from 0.8 to 6, said aluminosilicates having an average particle size in the range of from 0.1 to 25μ and a calcium binding power of from 20 to 200 mg CaO/gm of anhydrous active substance measured at 22° C. according to the Calcium Binding Power Test Method set out in the specification, as an auxiliary soaping agent.
The alkali metal aluminosilicates, to be used according to the present invention, can be produced synthetically in a simple manner, for example, by reaction of water-soluble silicates with water-soluble aluminates in the presence of water. For this purpose, aqueous solutions of the starting materials can be mixed with one another, or a component present in a solid state may be reacted with the other component present in the form of an aqueous solution. The desired aluminosilicates are also obtained by mixing the two components, present in a solid state, in the presence of water. Alkali metal aluminosilicates can also be produced from Al(OH)3, Al2 O3 or SiO2 by reaction with alkali metal silicate solutions or aluminate solutions respectively. Finally, substances of this type are also formed from the melt, although, owing to the high melting temperatures required and the necessity of converting the melt into finely distributed products, this method appears to be less interesting from an economic viewpoint.
The alkali metal aluminosilicates and their preparation are described in U.S. Pat. No. 4,071,377, as well as in U.S. patent application Ser. No. 458,306, filed Apr. 5, 1974, now abandoned in favor of its continuation Ser. No. 800,308, filed May 25, 1977, now abandoned. These alkali metal aluminosilicates as produced by precipitation, or converted to an aqueous suspension in a finely distributed state by other methods, may be converted from the amorphous state into the aged or crystalline state by heating to temperatures of from 50° to 200° C. The amorphous or crystalline alkali metal aluminosilicate, present in an aqueous suspension, can be separated from the remaining aqueous solution by filtration and can be dried at temperatures of, for example, 50° to 800° C. The product contains a greater or smaller quantity of bound water according to the drying conditions. Anhydrous products are obtained by drying for 1 hour at 800° C. However, the hydrous products are preferred, particularly those obtained when drying at 50° to 400° C., particularly 50° to 200° C. Suitable products can have, for example, water contents of approximately 2% to 30%, usually approximately 8% to 27%, relative to their total weight.
The precipitation conditions can contribute to the formation of the desired small particle sizes of from 1 to 12μ, the intermixed aluminate and silicate solutions, which may also be introduced simultaneously into the reaction vessel, are subjected to high shearing forces by, for example, intensively agitating the suspension. When crystallized alkali metal aluminosilicates are produced (these are preferably used in accordance with the invention), the formation of large, possibly interpenetrating crystals, is thus prevented by slow agitation of the crystallizing compound.
Nevertheless, undesired agglomeration of crystal particles can occur during drying, so that it may be advisable to remove these secondary particles in a suitable manner by, for example, air separators. Alkali metal aluminosilicates obtained in a coarser state, and which have been ground to the desired grain size, can also be used. By way of example, mills and/or air separators, or combinations thereof, are suitable for this purpose.
Preferred products are, for example, synthetically produced crystalline alkali metal aluminosilicates of the composition
0.7-1.1M.sub.2 O.Al.sub.2 O.sub.3.1.3-3.3SiO.sub.2,
in which M represents an alkali metal cation, preferably a sodium cation. It is advantageous if the alkali metal aluminosilicate crystallites have rounded corners and edges.
If it is desired to produce the alkali metal aluminosilicates with rounded corners and edges, it is advantageous to start with a preparation whose molar composition lies preferably in the range
2.5-6.0M.sub.2 O.Al.sub.2 O.sub.3.0.5-5.0SiO.sub.2.60-200H.sub.2 O
wherein M has the meaning given above and, in particular, signifies the sodium ion. This preparation is crystallized in a conventional manner. Advantageously, this is effected by heating the preparation for at least 1/2 hour to 70° to 120° C., preferably to 80° to 95° C., under agitation. The crystalline product is isolated in a simple manner by separating the liquid phase. If required, it is advisable to re-wash the products with water, and to dry them, before further processing. Even when working with a preparation whose composition differs only slightly from that stated above, one still obtains products having rounded corners and edges, particularly when the difference only relates to one of the four concentration parameters given above.
Furthermore, fine-particulate water-insoluble alkali metal aluminosilicates may also be used in the method of the invention which have been precipitated and aged or crystallized in the presence of water-soluble inorganic or organic dispersing agents. Products of this type are described in U.S. patent applications Ser. No. 503,467, filed Sept. 5, 1974, now abandoned; Ser. No. 763,667, filed Jan. 28, 1977, now abandoned; and Ser. No. 811,964, filed June 30, 1977, now U.S. Pat. No. 4,126,574. They are obtainable in a technically simple manner. Suitable water-soluble organic dispersing agents are surface-active compounds, non-surface-active-like aromatic sulfonic acids and compounds having a complex-forming capacity for calcium. The said dispersing agents may be introduced into the reaction mixture in an optional manner before or during precipitation, and, for example, they may be introduced in the form of a solution or they may be dissolved in the aluminate solution and/or silicate solution. Particularly satisfactory effects are obtained when the dispersing agent is dissolved in the silicate solution. The quantity of dispersing agent should be at least 0.05 percent by weight, preferably 0.1 to 5 percent by weight, based on the total amount of precipitate obtained. The product of precipitation is heated to temperatures of from 50° to 200° C. for 1/2 to 24 hours for the purpose of ageing or crystallization. By way of example, sodium lauryl ether sulfate, sodium polyacrylate, hydroxyethane diphosphonate and others may be mentioned from the large number of dispersing agents which may be used.
Compounds of the general formula
0.7-1.1Na.sub.2 O.Al.sub.2 O.sub.3.>2.4-3.3SiO.sub.2
constitute a special variant, with respect to their crystal structure, of the alkali metal aluminosilicates to be used in accordance with the invention. The possibility of their use as auxiliary soaping agents does not differ from that of the other alkali metal aluminosilicates which have been mentioned.
Compounds of the formula
0.7-1.1Na.sub.2 O.Al.sub.2 O.sub.3 >3.3-5.3SiO.sub.2
constitute a further variant of the fine-particulate, water-insoluble alkali metal aluminosilicates to be used in accordance with the invention. The production of such products is based on a preparation whose molar composition lies preferably in the range
2.5-4.5Na.sub.2 O.Al.sub.2 O.sub.3.3.5-6.5SiO.sub.2.5.0-11.0H.sub.2 O.
This preparation is crystallized in a conventional manner. Advantageously, this is effected by heating the preparation for at least 1/2 hour to 100° to 200° C., preferably to 130° to 160° C., under vigorous agitation. The crystalline product is isolated in a simple manner by separation of the liquid phase. If required, it is advisable to wash the products with water, and to dry them at temperatures of from 20° to 200° C., before further processing. The dried products thus obtained still contain bound water. When the products are produced in the manner described, one obtains very fine crystallites which come together to form spherical particles, possibly to form hollow balls having a diameter of approximately 1 to 4μ.
Furthermore, alkali metal aluminosilicates suitable for use in accordance with the invention are those which can be produced from calcinated (destructured) kaolin by hydrothermal treatment with aqueous alkali metal hydroxide. The formula
0.7-1.1M.sub.2 O.Al.sub.2 O.sub.3.1.3-2.4SiO.sub.2.0.5-5.0H.sub.2 O
corresponds to the products, M signifying an alkali metal cation, particularly a sodium cation. The production of the alkali metal aluminosilicates from calcinated kaolin leads, without any special technical expense, directly to a very fine-particulate product. The kaolin, previously calcinated at 500° to 800° C., is hydrothermally treated with aqueous alkali metal-hydroxide at 50° to 100° C. The crystallization reaction thereby taking place is generally concluded after 0.5 to 3 hours.
Commercially available, elutriated kaolins predominantly comprise the clay mineral kaolinite of the approximate composition Al2 O3.2SiO2.2H2 O and which has a layer structure. In order to obtain the alkali metal aluminosilicates, to be used in accordance with the invention, therefrom by hydrothermal treatment with alkali hydroxide, it is first necessary to destructure the kaolin, this being effected to best advantage by heating the kaolin to temperatures of from 500° to 800° C. for two to four hours. The X-ray amorphous anhydrous metakaolin is thereby produced from the kaolin. In addition to destructuring the kaolin by calcination, the kaolin can also be destructured by mechanical treatment (grinding) or by acid treatment.
The kaolins usable as starting materials are light-colored powders of great purity; of course, their iron content of approximately 2000 to 10,000 ppm Fe is substantially higher than the values of from 20 to 100 ppm Fe in the alkali metal aluminosilicates produced by precipitation from alkali metal silicate and alkali metal aluminate solutions. This higher iron content in the alkali metal aluminosilicates produced from kaolin is not disadvantageous, since the iron is firmly bedded in the form of iron oxide in the alkali metal aluminosilicate lattice and is not dissolved out. A sodium aluminosilicate having a cubic, faujasite-like structure is produced during the hydrothermal action of sodium hydroxide on destructured kaolin. Production of such alkali metal aluminosilicates from destructured kaolin with a low iron content are described in U.S. patent application Ser. No. 819,666, filed July 28, 1977, now U.S. Pat. No. 4,089,429.
Alkali metal aluminosilicates, usable in accordance with the invention, may also be produced from calcinated (destructured) kaolin by hydrothermal treatment with aqueous alkali metal hydroxide with the addition of silicon dioxide or a compound producing silicon dioxide. The mixture of alkali metal aluminosilicates of differing crystal structure, generally obtained thereby, comprises very fine-particulate crystal particles having a diameter of less than 20μ, and 100% of which usually comprises particles having a diameter of less than 10μ. In practice, this conversion of the destructured kaolin is effected preferably with aqueous sodium hydroxide and water glass. A sodium aluminosilicate J is thereby produced which is known by several names in the literature, for example, molecular sieve 13×or zeolite NaX (see O. Grubner, P. Jiru and M. Ralek, "Molecular Sieves", Berlin 1968, pages 32, 85-89), when the preparation is preferably not agitated during the hydrothermal treatment, at all events when only low shearing energies are used and the temperature preferably remains at 10° to 20° C. below the boiling temperature (approximately 103° C.). The sodium aluminosilicate J has a cubic crystal structure similar to that of natural faujasite. The conversion reaction may be influenced particularly by agitating the preparation, at elevated temperature (boiling heat at normal pressure or in an autoclave) and greater quantities of silicate, that is, by a molar preparation ratio SiO2 :Na2 O of at least 1, particularly 0.1 to 1.45, such that sodium aluminosilicate F is produced in addition to, or instead of, sodium aluminosilicate J. Sodium aluminosilicate F is designated "zeolite P" or "type B" in the literature (see D. W. Breck, "Zeolite Molecular Sieves", New York, 1974, page 72). Sodium aluminosilicate F has a structure similar to the natural zeolites gismondine and garronite and is present in the form of crystallites having an externally spherical appearance. In general, the conditions for producing the sodium aluminosilicate F and for producing mixtures of J and F are less critical than those for a pure crystal type A.
The soaping process is performed by using the fine-particulate alkali metal aluminosilicates in the known soaping process following the dyeing process. The alkali metal aluminosilicates are thereby used preferably in combination with surface-active compounds or tensides, particularly anionic and nonionic tensides. Suitable anionic tensides are primarily higher molecular weight sulfates or sulfonates having 8 to 18 carbon atoms, such as primary and secondary alkyl sulfates, alkyl sulfonates or alkylaryl sulfonates, preferably alkylphenyl sulfonates. Suitable nonionic tensides are, for example, the adducts of from 5 to 30 mols of ethylene oxide onto higher fatty alcohols, fatty acids or fatty amines having 8 to 18 carbon atoms, and alkylphenols having 8 to 18 carbon atoms in the alkyl. The anionic and nonionic tensides can be used to advantage in the mixture; however, the soaping process can be conducted in their absence.
Approximately 0.5 to 1 gm/l of tensides are used in the known soaping process in addition to 0.5 to 1.5 gm/l of alkaline salts. On the other hand, in the case of the soaping process in accordance with the invention, only 0.15 to 1.0 gm/l of tensides and 0.3 to 1.5 gm/l of alkali metal aluminosilicates are required. The joint use of alkaline salts is not required. This results in a less expensive soaping process without a decrease in effectiveness.
The use of fine-particulate, water-insoluble alkali metal aluminosilicates has proved to be advantageous for the after-treatment of dyes on different natural and synthetic fibers, and when dyeing or printing with a wide variety of dyes, insofar as an after-soaping process is customarily used. Special advantages have ensued in the treatment of dyes on cellulose fiber material such as cotton, optionally mixed with synthetic fibers, when using naphthol dyes, sulfur dyes and vat dyes, and when dyeing synthetic fiber material, such as polyester fibers, with dispersion dyes. The textile material may be present in the form of yarns, woven fabrics or knitted fabrics and the like. The soaping process is performed intermittently or continuously in a conventional manner on the machines and apparatus used in the textile industry.
The initially described advantages relative to the conventional soaping process are obtained by using, in accordance with the invention, the fine-particulate, water-insoluble alkali metal aluminosilicates as auxiliary soaping agents. In particular, attention may again be drawn to the improvement in the fastness properties, the saving of tensides and salts, and the improvement in the quality of the waste water. The alkali metal aluminosilicates in the form of a dry powder can readily be converted to stable dispersions by stirring them into water or solutions containing dispersing agents, and can be satisfactorily handled in this form. They can be combined with the surfactants used in the soaping process, and, if required, with further conventional additives such as low molecular weight, polyglycol ethers, protein hydrolysates, pine oil or the like, to form stable suspensions which, for use, are to be diluted, without difficulty, with water.
The following preparations and examples are illustrative of the practice of the invention without being limitative in any manner.
The silicate solution was added to the aluminate solution under vigorous agitation in a vessel having a capacity of 15 liters. Agitation was effected at 3000 r.p.m. by means of an agitator having a dispersing disc. The two solutions were at room temperature. An X-ray amorphous sodium aluminosilicate was formed as a primary product of precipitation with an exothermic reaction. After agitating for 10 minutes, the suspension of the precipitation product was transferred to a crystallizer and, for the purpose of crystallization, remained in the crystallizer for 6 hours at 90° C. under agitation (250 r.p.m.). The mother liquor was drawn off from the crystal sludge and the filtration residue was washed with deionized water until the washing water flowing off had a pH value of approximately 10. Therefore the washed filtration residue was dried as specified. Instead of the dried sodium aluminosilicate, the suspension of the crystallization product or the crystal sludge was also used to produce the auxiliary soaping agents. The water contents were determined by heating the pre-dried products to 800° C. for 1 hour. The sodium aluminosilicates, washed or neutralized to the pH value of approximately 10, and then dried, were subsequently ground in a ball mill. The grain size distribution was determined by means of a sedimentation balance.
The calcium binding power of the aluminosilicates was determined in the following manner:
1 gm of aluminosilicate (based on the anhydrous active substance) was added to 1 l of an aqueous solution containing 0.594 gm of CaCl2 (=300 mg CaO/l=30° dH) and adjusted to a pH value of 10 with diluted NaOH. The suspension was then vigorously agitated for 15 minutes at a temperature of 22° C. (-2° C.). The residual hardness x of the filtrate was determined after filtering off the aluminosilicate. The calcium binding capacity was calculted therefrom in mg CaO/gm AS in accordance with the formula: (30-x).10. For short hand purposes the above procedure is hereinafter referred to by the Calcium Binding Power Test Method.
When the calcium binding capacity is determined at higher temperatures, for example, at 60° C., far better values are found than when it is determined at 22° C.
______________________________________Conditions for producing sodium aluminosilcate A:______________________________________Precipitation: 2.935 kg of aluminate solution of the composition: 17.7% Na.sub.2 O, 15.8% Al.sub.2 O.sub.3, 66.6% H.sub.2 O 0.15 kg of caustic soda 9.420 kg of water 2.445 kg of a 28.5% sodium silicate solution of the composition 1 Na.sub.2 O.6.0 SiO.sub.2, freshly prepared from com- mercially available water glass and slightly alkali- soluble silicic acidCrystallization: 6 hours at 90° C.Drying: 24 hours at 100° C.Composition: 0.9 Na.sub.2 O.1 Al.sub.2 O.sub.3.2.04 SiO.sub.2. 4.3 H.sub.2 O (= 21.6% H.sub.2 O)Degree of crystallization: Fully crystalline.Calcium binding power: 170 mg CaO/gm active substance.______________________________________
The particle size distribution, determined by sedimentation analysis, resulted in a mixture range of the particle size distribution curve at 3 to 6μ.
The sodium aluminosilicate A exhibits the following interference lines in the X-ray diffraction graph:
______________________________________d values, photographed with Cu--K.sub.α radiation in Å I______________________________________ -- 12.4 -- 8.6 7.0 -- 4.1 (+) -- 3.68 (+) 3.38 (+) 3.26 (+) 2.96 (+) -- -- 2.73 (+) -- 2.60 (+)______________________________________
It is quite possible that all these interference lines will not appear in the X-ray diffraction graph particularly when the aluminosilicates are not fully crystallized. Thus, the most important d values for characterizing these types have been characterized by a "(+)".
______________________________________Conditions for producing sodium aluminosilicate B:______________________________________Precipitation: 7.63 kg of an aluminate solution of of the composition 13.2% Na.sub.2 O; 8.0% Al.sub.2 O.sub.3 ; 78.8% H.sub.2 O; 2.37 kg of a sodiuum silicate solution of the composition 8.0% Na.sub.2 O; 26.9% SiO.sub.2 ; 65.1% H.sub.2 O;Preparation ratio in mol: 3.24 Na.sub.2 O; 1.0 Al.sub.2 O.sub.3 ; 1.78 SiO.sub.2 ; 70.3 H.sub.2 O;Crystallization: 6 hours at 90° C.;Drying: 24 hours at 100° C.;Composition of the dried 0.99 Na.sub.2 O.1.00 Al.sub.2 O.sub.3.1.83 SiO.sub.2.product 4.0 H.sub.2 O; (= 20.9% H.sub.2 O)Crystalline form: Cubic with greatly rounded corners and edges;Average particle 5.4μdiameter:Calcium binding powder: 172 mg CaO/gm active substance.______________________________________Conditions for producing sodium aluminosilicate C:______________________________________Precipitation: 12.15 kg of an aluminate solution of the composition 14.5% Na.sub.2 O; 5.4% Al.sub.2 O.sub.3 ; 80.1% H.sub.2 O; 2.87 kg of a sodium silicate solu- tion of the composition 8.0% Na.sub.2 O; 26.9% SiO.sub.3 ; 65.1% H.sub.2 O;Preparation ratio in mol: 5.0 Na.sub.2 O; 1.0 Al.sub.2 O.sub.3 ; 2.0 SiO.sub.2 ; 100 H.sub.2 O;Crystallization: 1 hour at 90° C.;Drying: Hot atomization of a suspension of the washed product (pH 10) at 295° C.; Content of solid substance in the suspension 46%;Composition of the dried 0.96 Na.sub.2 O.1 Al.sub.2 O.sub.3.1.96 SiO.sub.2.product: 4 H.sub.2 O;Crystalline form: Cubic with greatly rounded corners and edges; Water content 20.5%;Average particle 5.4μdiameter:Calcium binding power: 172 mg CaO/gm active substance.______________________________________
Conditions for producing potassium aluminosilicate D:
The sodium aluminosilicate C was produced in the first instance. After the mother liquor had been drawn off, and the crystalline mass had been washed to the pH value 10 with demineralized water, the filtration residue was suspended in 6.1 l of a 25% KCl solution. The suspension was heated for a short time to 80° to 90° C., and was then cooled, filtered off again and washed.
______________________________________Drying: 24 hours at 100° C.;Composition of the dried 0.35 Na.sub.2 O.0.66 K.sub.2 O.1.0 Al.sub.2 O.sub.3product: 1.96 SiO.sub.2.4.3 H.sub.2 O; (water content 20.3%)______________________________________
______________________________________Conditions for producing sodium aluminosilicate E:______________________________________Precipitation: 0.76 kg of aluminate solution of the composition: 36.0% Na.sub.2 O, 59.0% Al.sub.2 O.sub.3, 5.0% water 0.94 kg of caustic soda; 9.94 kg of water; 3.94 kg of a commercially available sodium silicate solution of the composition: 8.0% Na.sub.2 O, 26.9% SiO.sub.2, 65.1% H.sub.2 O;Crystallization: 12 hours at 90° C.;Drying: 12 hours at 100° C.;Composition: 0.9 Na.sub.2 O.1 Al.sub.2 O.sub.3.3.1 SiO.sub.2. 5 H.sub.2 O;Degree of crystallization: Fully crystalline.The maximum range of the particle size distribution curve at 3 to6μ .Calcium binding power: 110 mg CaO/gm active substance.______________________________________
The aluminosilicate E exhibited the following interference lines in the X-ray diffraction graph:
______________________________________d-values, photographed with Cu--K.sub.α radiation in______________________________________Å14.4--8.8----4.4--3.8--------2.882.79--2.66--______________________________________
______________________________________Conditions for producing sodium aluminosilicate F:______________________________________Precipitation: 10.0 kg of an aluminate solution of the composition: 0.84 kg NaAlO.sub.2 + 0.17 kg NaOH + 1.83 kg H.sub.2 O; 7.16 kg of a sodium silicate solution of the composition 8.0% Na.sub.2 O, 26.9% SiO.sub.2, 65.1% H.sub.2 O;Crystallization: 4 hours at 150° C.;Drying: Hot atomization of a 30% suspension of the washed product (pH 10);Composition of the dried 0.98 Na.sub.2 O.1 Al.sub.2 O.sub.3.4.12 SiO.sub.2.product: 4.9 H.sub.2 O;The particles were of spherical shape; the average diameter ofthe balls was approximately 3 to 6μ .Calcium binding power: 132 mg CaO/gm active substance at 50° C.______________________________________
______________________________________Conditions for producing sodium aluminosilicate G:______________________________________Precipitation: 7.31 kg aluminate (14.8% Na O, 9.2% Al.sub.2 O.sub.3, 76.0% H.sub.2 O) 2.69 kg silicate (8.0% Na.sub.2 O, 26.9% SiO.sub.2, 65.1% H.sub.2 O);Preparation ratio in mol: 3.17 Na.sub.2 O, 1.0 Al.sub.2 O.sub.3, 1.82 SiO.sub.2, 62.5 H.sub.2 O;Crystallization: 6 hours at 90° C.;Composition of the dried 1.11 Na.sub.2 O.1 Al.sub.2 O.sub.3.1.89 SiO.sub.2,product: 3.1 H.sub.2 O (= 16.4% H.sub.2 O);Crystalline structure: Mixed structural type in the ratio 1:1;Crystalline form: Rounded crystallites;Average particle diameter: 5.6μ.Calcium binding power: 105 mg CaO/gm active substance at 50° C.______________________________________
Conditions for producing sodium aluminosilicate H produced from kaolin:
1. Destructuring Kaolin
In order to activate the natural kaolin, samples of 1 kg were heated to 700° C. in a Schammote crucible for 3 hours. The crystalline kaolin Al2 O3.2SiO2.2H2 O was thereby converted to the amorphous metakaolin Al2 O3.2SiO2.
2. Hydrothermal treatment of metakaolin
The alkali solution was placed in an agitating vessel and the calcined kaolin was added under agitation at temperatures between 20° and 100° C. The suspension was brought to the crystallization temperature of 70° to 100° C. under agitation, and was maintained at this temperature until the crystallization operation had terminated. The mother liquor was subsequently drawn off and the residue was washed with water until the washing water draining off had a pH value of from 9 to 11. The filter cake was dried and was subsequently crushed to a fine powder or was ground to remove the agglomerates produced during drying. This grinding process was omitted when the filtration residue was further processed in a wet state or when the drying operation was performed by means of a spray dryer or a flow dryer. Alternatively, the hydrothermal treatment of the calcined kaolin can be performed in a continuous operation.
______________________________________Preparation: 1.65 kg of calcined kaolin 13.35 kg of 10% NaOH, mixed at room temperature;Crystallization: 2 hours at 100° C.;Drying: 2 hours at 160° C. in a vacuum drying cabinet;Composition: 0.88 Na.sub.2 O.1 Al.sub.2 O.sub.3.2.14 SiO.sub.2. 3.5 H.sub.2 O (= 18.1% H.sub.2 O);Crystalline structure: Mixed structural type like Na alumino- silicate G, although in the ratio 8:2.Average particle 7.0μdiameter:Calcium binding power: 126 mg CaO/gm active substance.______________________________________
Conditions for producing sodium aluminosilicate J produced from kaolin:
The destructuring of the kaolin and the hydrothermal treatment were effected in the same manner as in the case of H.
______________________________________Preparation: 2.6 kg of calcined kaolin, 7.5 kg of 50% NaOH, 7.5 kg of water glass, 51.5 kg of deionized water, mixed at room temperature;Crystallization: 24 hours at 100° C., without agitation;Drying: 2 hours at 160° C. in a vacuum drying cabinet;Composition: 0.93 Na.sub.2 O.1 Al.sub.2 O.sub.3.3.60 SiO.sub.2. 6.8 H.sub.2 O (= 24.6% H.sub.2 O);Crystalline structure: Sodium aluminosilicate J in accord- ance with above definition, cubic crystallites;Average particle diameter 8.0μCalcium binding power: 105 mg CaO/gm active substance.______________________________________
(A) Mixtures of equal parts of the adduct of fatty alcohol C10-16 +9.5 mols of ethylene oxide and the linear alkylsulfate C12-18, Na or NH4 salt
(B) Mixtures of equal parts of the adduct of fatty alcohol C10-16 +11 mols of ethylene oxide and C12 alkylbenzene sulfonate, Na salt.
A dyeing with 2.6% of C.I. Reactive Orange 20 on precleaned cotton tricot was soaped in a launderometer both in accordance with the standard method and, in accordance with the method of the present invention, with the joint use of alkali metal aluminosilicate (Al-silicate).
Conditions: soft water 0°-0.5° dH, 10 balls, 15 minutes at 90° C., rinsed 3×60 seconds, liquor ratio 1:30.
The washing fastness was determined in accordance with DIN 54 010/54 011, and the rubbing fastness was determined in a dry state in accordance with DIN 54 021. The results are reported in Table I.
TABLE I______________________________________ Washing Rubbing pH of the fastness Fastness liquor DIN 54010 din 54021 dry______________________________________1.5 gm/l Tenside II A 10.5 3 3-41.0 gm/l sodium carbonate1.5 gm/l Tenside II A -- 3 3-41.0 gm/l sodiumtripolyphosphate0.5 gm/l Tenside II A 8.5 5 4-50.5 gm/l Al-silicate I A0.5 gm/l Al-silicate I A 8.6 4 4______________________________________ Fastness: 1 = slight 5 = very good
Corresponding results were also obtained with the sodium aluminosilicate I B.
In a works test,
(a) pre-cleaned cotton tricot/stretch polyamide, dyed with 3.5% C.I. Reactive red 147,
(b) cotton tricot, roughened (pre-cleaned), dyed with 2.20% C.I. Reactive Orange 20 and 0.05% C.I. Reactive Red 42,
(c) cotton tricot (pre-cleaned), dyed in the same manner as (b) were soaped in a reel machine both in accordance with the standard method and in accordance with the method of the present invention.
Conditions: soft water 0°-0.5° dH, 20 minutes at 95° C., liquor ratio 1:20. After soaping, the material was hot-rinsed once (90° C., 5 minutes) and cold-rinsed once. the fastness was determined in the same manner as in Example 1 and reported in Table II.
TABLE II______________________________________ Washing fastness fastness DIN 54010/54011 DIN 54021 dry______________________________________Dyeing (a)1 gm/l Tenside IIA 60° C.; 3-4 3-4 95° C.; 30.75 gm/l Tenside II A 60° C.; 5 4-50.75 gm/l Al-silicate I C 95° C., 4-5Dyeing (b)1 gm/l Tenside II B 60° C.; 3-4 2-3 95° C.; 30.5 gm/l Tenside II B 60° C.; 4-5 50.5 gm/l Al-silicate I D 95° C. 4-5Dyeing (c)1 gm/l Tenside II A 60° C.; 3-4 3 95° C.; 30.5 gm/l Tenside II A 60° C.; 5 4-50.5 gm/l Al-silicate I A 95° C.; 4-5______________________________________ Fastness: 1 = slight 5 = very good
In contrast to the reactive dyes dealt with in Example 2, Indanthrene® dyes have very good fastness which lies between 4-5 and 5. Thus, there is no further increase by adding aluminosilicates when soaping.
However, the soaping process can be shortened by the use of the aluminosilicates, and at the same time it is possible to save water.
A cotton tricot (pre-cleaned) was dyed with
(a) 3% C.I. Vat Blue 20
(b) 2.8% C.J. Vat Green 2
in a works test and was soaped in a reel machine both in accordance with the standard method and in accordance with the method of the present invention with the joint use of Na Al-silicate. In the latter case, it was possible to achieve a considerable saving of time and water.
Soaping in accordance with the standard method:
2 gm/l Tenside II A,
30 minutes at 90°-95° C., subsequently rinsed twice.
Soaping in accordance with the method of the present invention:
1 gm/l Tenside II A
1 gm/l Na Al-silicate I B
15 minutes at 90°-95° C., subsequently cold-rinsed once.
The fastness obtained by the method in accordance with the invention corresponded at least to that of the standard method.
In a laboratory test, cotton fabric (pre-cleaned) was dyed by the foulard method with
(a) Priming: 14.0 gm/kg of fabric of C.I. Acoic Coupling Component 2. Development: 48.5 gm/kg of fabric of C.I. Acoic Coupling Component 35.
(b) Priming: 14.0 gm/kg of fabric of C.I. Acoic Coupling Component 20. Development: 43.5 gm/kg of fabric of C.I. Acoic Coupling Component 35 and was subsequently soaped as set forth in Table III.
TABLE III______________________________________ pH Washing Rubbing of the fastness fastness liquor DIN 54010 DIN 54021 dry______________________________________Dye (a)2 gm/l Tenside II B 10.3 3-4 41 gm/l Sodium Carbonate2 gm/l Tenside II B 10.0 3 41 gm/l SodiumTripolyphosphate0.5 gm/l Tenside II B 8.3 4-5 4-50.5 gm/l Al-silicate I A0.5 gm/l A-silicate I A -- 4 4Dye (b)1.5 gm/l Tenside II A 10.1 3 41 gm/l Sodium Carbonate0.5 gm/l Tenside II A 8.3 4-5 4-50.5 gm/l Al-silicate I B______________________________________ Fastness: 1 = slight 5 = very good
Corresponding results were obtained when the tests were repeated with the Al-silicates I G and I H.
In a works test, 200 kg of cotton tricot 1/l (precleaned) were dyed in a reel machine with a liquor ratio 1:20 with
1.44% C.I. Reactive Green 12
1.80% C.I. Reactive Yellow 64
and were subsequently rinsed and soaped.
(a) conventional soaping method
After dyeing, the material was cold-rinsed for 10 minutes, hot-rinsed for 15 minutes, soaped with 2 gm/l of washing agent for 30 minutes (95° C.), rinsed with overflow for 20 minutes, and then hot- and cold-rinsed again for 10 minutes.
(b) After-soaped in accordance with the method of the present invention
Cold-rinsed with overflow for 10 minutes, hot-rinsed for 15 minutes, soaped at 90° C. for 30 minutes with
1 gm/l Tenside II B
1 gm/l Al-silicate I D
and subsequently cold-rinsed for 10 minutes.
It was possible to reduce the period of treatment, and also to reduce the consumption of water and energy by approximately 30% when performing the rinsing and soaping processes by the method in accordance with the invention. The fastnesses as reported in Table IV were obtained:
TABLE IV______________________________________ Rubbing fastness Washing fastness DIN 54021 DIN 54010/54011 Dry Wet______________________________________(a) Conventional soap- 5 4ing method60° C. 495° C. 3-4(b) Method in accordance 5 4with the invention60° C. 4-595° C. 4______________________________________
Material: 4000 m polyester woven material (print: black with white background).
Printing color: 150 gm of palanil black GEL®/kg printing paste (palanil black GEL® is not included in the Color Index).
Thickening: Thickening agent combination (such as Diaprint® types).
After-soaping process in a continuous washing machine in a vat with 6 compartments with reels and a preceding roller.
(a) Work is carried out in the following manner by the known soaping process:
______________________________________Roller vat: Cold with overflow______________________________________1st washing compartment: 1 gm/l washing agent, cold2nd and 3rd washing 1 gm/l washing agentcompartments: 1 gm/l sodium hyposulfite 2 ml/l caustic soda 38° Be Temperature 80° C.4th washing compartment: 1 gm/l sodium hyposulfite 2 ml/l caustic soda 38° Be Temperature 80° C.5th washing compartment: Rinsing bath 25° C.6th washing compartment: Rinsing bath with overflow 25° C.Total washing and rinsing time = 15 minutes______________________________________
(b) Continuous after-soaping process in accordance with the method of the present invention, the washing agent used hitherto being replaced by
0.25 gm/l Tenside II A
0.25 gm/l Al-silicate I A
in the 2nd and 3rd washing compartments.
Compared with the method known hitherto, a substantially brighter white background was obtained by the method in accordance with the invention, with at least equal fastnesses and a reduced concentration of washing agent.
The preceding specific embodiments are illustrative of the practice of the invention. It is to be understood, however, that other expedients known to those skilled in the art or disclosed herein, may be employed without departing from the spirit of the invention or the scope of the appended claims.
|Cited Patent
|Filing date
|Publication date
|22 Apr 1968
|27 Apr 1971
|Virginia Chemicals Inc
|Method for thermofixation dyeing of polyester/cotton fabric in a mixture of vat/disperse dye
|23 Dec 1969
|15 Aug 1972
|Ciba Geigy Ag
|Process for after-washing freshly dyed textile material
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|Henkel Kommanditgesellschaft Auf Aktien
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|Henkel Kommanditgesellschaft Auf Aktien
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|10 Apr 1979
|Henkel Kommanditgesellschaft Auf Aktien
|Method of washing textiles and composition containing inorganic silicates and polycarboxylates and/or polyphosphonates
|Title not available
|2 Oct 1975
|8 Apr 1976
|Henkel & Cie Gmbh
|Verfahren und vorrichtung zum maschinellen waschen und reinigen von festen werkstoffen unter verwendung phosphatarmer oder phosphatfreier wasch- und reinigungsmittel
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|Citing Patent
|Filing date
|Publication date
|22 Dec 1992
|3 Jan 1995
|Apollo Chemical Company
|Liquid alkali for soaping off reactive dyes
|1 Sep 1993
|15 Aug 1995
|Teijin Limited
|Method of dyeing a synthetic fiber-material and dyed synthetic fiber material
|9 Dec 1996
|19 May 1998
|Clariant Finance (Bvi) Limited
|Finishing of textile fibre materials
|31 Jul 1998
|3 Feb 1999
|Sybron Chemie Nederland B.V.
|Process for washing off dyed tectile
|U.S. Classification
|8/442, 8/137, 8/532
|International Classification
|Cooperative Classification
|European Classification
|10 Sep 1984
Owner name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN (HENKEL KG
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:GRUNERT, HEINZ;HAHN, FRITZ;RALL, ULRICH;AND OTHERS;REEL/FRAME:004297/0748
Effective date: 19780503
|5 Aug 1988
|Fee payment
Year of fee payment: 4
|3 Aug 1992
|Fee payment
Year of fee payment: 8
|24 Sep 1996
|Maintenance fee reminder mailed
|16 Feb 1997
|Lapse for failure to pay maintenance fees
|29 Apr 1997
|Expired due to failure to pay maintenance fee
Effective date: 19970219


text:
©2006 William W. Johnstone; (P)2007 Recorded Books
"A very good series of books"
Yes , and I intend to next, I like that Smoke is on his own and has to use his trades that were taught to him by Preacher. Great Book
When Sally took care of the deputy.
Yes , he does a great job
When Smoke got out of jail
Great Book
"Good read"
It was a good read. The only problem I found was the ending was a little lame.
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