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I frankly didn't think President Obama had it in him. His recent clash with GOP leaders over the so-called Bush tax cuts was a masterstroke of political maneuvering. He was, of course, helped greatly with the approach taken by Senate Minority Leader Mitch McConnell, Kentucky Republican; Sen. Jon Kyl, Arizona Republican; and incoming House Speaker John A. Boehner, Ohio Republican, who kicked away all the leverage gained with a November trouncing of the Democrats at the ballot box.
They agreed to a one-sided deal, in which the Democrats gave up almost nothing and got in return some $200 billion in new spending, a resurrected death tax, as well as extending supposed "one-time" tax credits to people who don't pay income taxes. And they made the deal three weeks before the end of the lame-duck session, allowing Democrats to queue up all the pet legislation (Dream Act, Disclose Act, card check) they want to pass to satisfy the fringe-left political base that they serve.
To make matters worse, Mr. Obama has been portrayed as making a Clintonesque move to the center when, in fact, he hasn't moved an inch from the far-left Marxist positions that are at his core. He is now better positioned than ever to battle the incoming GOP House of Representatives. Their wish to put the brakes on or actually cut spending just got that much harder because of what the outgoing Congress is doing.
The sad fact of this whole debacle is it could have been easily avoided with the exercise of some common sense. Mr. McConnell should have slow-played the tax cuts to the end of lame-duck session, filibustering everything to the last minute. Even if no deal is reached by year's end, no problem. Let the new Congress deal with it and make whatever deal is reached retroactive to Jan. 1.
It's better to pay a little more for a couple of weeks if need be and get a better deal in the long run without all the added spending than to accept a flawed deal now and give the Democrats two to three weeks to ram through their destructive legislation.
Lexington, Ky.
© Copyright 2015 The Washington Times, LLC. Click here for reprint permission.


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Maple Hill Farm Inn
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Road Trips: Bath & Brunswick; Augusta & Freeport
... where you can find wonderful deals if you are willing to buy duffel personalized with "Buddy," as Marette was happy to do!
We toured the state capital, passing Governor LaPage in the hallway and listening briefly to Bobby Kennedy fire up the anti-vaxers by disputing scientific data. And then we went on a scavenger hunt to find: a funny portrait of George Washington and fossils buried somewhere in the capital. We won! Well, it wasn't a contest but we did ...
Day 77 Gloucester To Wiscasset, Maine Mile: 4,020
... with old friends in Brunswick for the night. After the good byes, I got totally lost trying to find my way out of the city.
Eventually, I was back on track and pedaling to our planned lunch destination in Bath, Maine. I met Maura at Bath's harbor overlooking the Kennebec ...
Day 9: Up to Maine
... two canards at a small field in the middle of nowhere. It reminded me of running into the NASA atmospheric Long-EZ in Northern Alberta one day many years back.
Val met us at the field, along with her dad and her son. Val had been my first serious girlfriend in high school, and her dad the only father to insist on meeting me before I could date his daughter. Funny how intimidated I was by him at the time, and now I realize that he is just ...
Not long to go!
... time round I really wasn't well so I wanted to get a room of my own for the night until Helen said she'd like to as well. So we pitched in together and bought a double room for $65 which considering what you got was pretty cheap! We had a double bed each as well as a nice bathroom and a tv! So good. Tuesday morning we headed off to a village outlet we were told we would be spending the day at. I was still pretty sleepy - probably because ...
Camp Life in Maine USA
... big rides (I just stuck to the log flumes!). Later in the afternoon you can enjoy a cold drink looking out onto the beach listening to the live music being played by the beach.
All in all I would recommend Maine as family holiday destination as many people rent houses and villas by the lake and I also recommend going to a camp in Maine as it is so scenic and peaceful and pretty. You won't find another state like it :)
Carlie x

subset: commoncrawl


text:
A Dream Come True
Dale wanted to see his daughter get married, but he had a pain that wouldn't go away. He went to the emergency room. By the end of the night, he had hemorrhaged two units of blood. It turned out he had a tumor in his … Continue reading


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South Royalton family welcomes first baby of new yearStaff Report | January 03,2013
RANDOLPH - Sara Bowen and fiancé Shawn Sedor of South Royalton were the first to welcome a baby in the new year at Gifford Medical Center in Randolph.
Bowen gave birth to daughter, Kaydence Sedor, on Jan. 2 at 10:29 p.m. A gorgeous and healthy Kaydence weighed in at 7 pounds 12 ounces and is 20 ½ inches long.
She is the couple's second child. Two-year-old Cassidy Sedor was also born at Gifford.
The family was excited to have the first baby of the new year. "It's really cool, actually," said Bowen.
But they were more excited with the newest member of their family, regardless of her birth date.
"I'm lost for words. I love my kids. They're amazing. (There's) nothing better than to have kids," said Bowen, who was originally due to give birth on Dec. 28.
"I'm just glad that she's healthy. We are lucky to have this blessing in our life," Sedor said.MORE IN This Just InRehearsing for an opera is like training for a marathon, says international performing artist... Full Story
POULTNEY — A nonprofit organization is eyeing about 200 '"deadbeat... Full Story
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...I have developed a special trust and bond with each of my students which is primary basis for my success with them. I have taught Dyslexia students at both the middle and high school levels. More specifically, I have taught Dyslexia students in the RESA Phycho Educational Program in Georgia for 5 years.
Dallas, GAView Tutor
...It is powerful, flexible, and beautiful. It will do so much more than add a column of figures. If you struggle with formatting a cell, I can help you make Excel do what you want it to do.
Rome, GAView Tutor
...In math and science, there can be several paths to arriving at the answer needed. Over the years I've picked up several methods that have worked for those I've helped. Visual aids, worksheets, lectures, one-on-one tutoring are all helpful with retaining and learning material.
Carrollton, GAView Tutor
...My tutoring method generally involves having the student work the problems out him/herself, while I provide direction as needed. The student will not learn if I just show him/her how to do every problem, without allowing him/her to make & correct their own mistakes. The only way for a student t...
Acworth, GAView Tutor
...I've been a regular user of all versions of QB since, both for myself and for a wide variety of clients helping them to setup and manage basic bookkeeping tasks for small and medium sized companies, and migrating them to small business accounting packages and in some cases mid-market accounting a...
Acworth, GAView Tutor


text: Home Recipes Kids Recipes Kids Snacks Share: Kids Snacks Check out these healthy recipes for kids snacks, including popcorn, nachos, empanadas, chicken wings, fries, pretzels, trail mix, kabobs, elephant ears, pinwheels, flat bread, cheese puffs, fruit snacks, pizza pockets, apple dip and more. Recipe Spotlight Kid-Size Ghost Pizzas These individual pizzas are super cute and made with simple ingredients. Now that's what I call party food! —Polly Coumos, Mogadore, Ohio View Kid-Size Ghost Pizzas Recipe More Kids Snacks Sort: Highest Rated Alphabetical Newest < prev | ... | 6 | 7 | 8 | 9 | 10 | ... | next > Lemonade Stand Snack Lemonade Stand Snack Dot Nickerson from Cincinnati, Ohio shares a munchable mix that's a breeze to toss together. View Recipe Mini Burgers with the Works Mini Burgers with the Works I started preparing these mini burgers several years ago as a way to use up bread crusts accumulating in my freezer. They're delicious. —Linda Lane, Bennington, Vermont View Recipe Mini White Pizzas Mini White Pizzas "I make these savory pizzas in advance and freeze them. Then I can bake them whenever I need a quick appetizer or snack. They are so delicious!" Jocelyn Hook, Swoyersville, Pennsylvania View Recipe Advertise with us ADVERTISEMENT Nuts and Bolts Nuts and Bolts Since I was a child, we've made buckets of this mix each Christmas for everyone. These days, though, I fix it for just about any occasion.—TaNauna Bunch, Grand Centre, Alberta View Recipe Odds 'n' Ends Snack Mix Odds 'n' Ends Snack Mix Cayenne pepper packs some punch in this crunchy blend of cereal, crackers, pretzels and peanuts from Terry Kuehn of Waunkee, Wisconsin. Although it makes a big batch, you might have to make more at halftime! View Recipe Peanut Caramel Corn Peanut Caramel Corn A sweet, crunchy, lighter alternative to traditional caramel corn, this can't-stop-eatin'-it treat won't stick to fingers or teeth! Wonderful for gifts, too. —LOIS WARD, PUSLINCH, ONTARIO View Recipe Popcorn Nut Treat Popcorn Nut Treat You need five ingredients to make this special snack mix featuring popcorn, cereal and nuts. The pairing of salty nuts and sweet honey is delicious. View Recipe Reuben Appetizers Reuben Appetizers Each year, I collect appetizer recipes to make for the annual Christmas party we throw for friends and family. These tidbits are always a big hit. —Pat Bohn, Oregon City, Oregon View Recipe Stuffed Potato Ghosts Stuffed Potato Ghosts These hearty and yummy treats are easier to make than a normal stuffed potato and are a perfect appetizer. The fingerlings are so small and tender that they'll disappear in a flash!—Taste of Home Test Kitchen View Recipe Sweet & Salty Popcorn Sweet & Salty Popcorn There's nothing like making memories with grandkids in the kitchen and seeing their excited, happy faces while they help. — Diane Smith, Pine Mountain, Georgia View Recipe Bacon-Tomato Quesadillas Bacon-Tomato Quesadillas Kids of all ages will go crazy for these appetizers that taste like a BLT. They're crisp on the outside...and ooey, gooey and oh-so-good inside!—Virginia Warner, Carson City, Nevada View Recipe < prev | ... | 6 | 7 | 8 | 9 | 10 | ... | next > Advertise with us ADVERTISEMENT Advertise with us ADVERTISEMENT


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To print a page in the RCW, use your browser's normal print functions (Ctrl-P on a PC, Command-P on a Mac, or File > Print on either). The resulting printed page will show just the content and not the banner at the top, the left-side navigation, or the footer links. To see how the page will look before you print it, use your browser's Print Preview.
Every insurer shall keep full and adequate accounts and records of its assets, obligations, transactions, and affairs.
[1947 c 79 § .05.28; Rem. Supp. 1947 § 45.05.28.]


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Can't Let Go
Taking the M&E Community with you
Perhaps it's natural: Twitter tweets are tiny by design, and optimized for the small device. So it's highly appropriate for the Mobile & Embedded Community to adopt Twitter as a means of keeping its members and friends in the loop.
As Roger Brinkley explains, the Mobile & Embedded Community has joined twitter, with the account name mobile_embedded. "Community Leaders will post snippets on our travels and other events that are happening in the community. We will also post highlights from the community front page and other sources. Community members or other interested Mobile, Media, & Embedded developers could allow us to follow their happening with their twitter accounts. Keep us up on the professional happenings of others. Let us know about a JUG meeting or what you are working on. If we get enough information flowing I will see if we can get the RSS feed published on the M&E; community main page."
Also in Java Today,
The Aquarium notes GlassFish's support for HTTP compression, and a good explanation about how to set it up: "GlassFish supports HTTP Compression and
Shing Wai
in detail how to
configure compression, compressionMinSize, compressableMimeType and noCompressionUserAgents.
This feature will be enabled in next month's
GlassFish v3 Prelude release."
John Ferguson Smart has announced the free release of his book JSF Jumpstarter. "The JSF Jumpstarter book is a short (67 pages), tutorial introduction to JSF, suitable for new JSF developers. If you need to get up to speed quickly with JSF, this book may be able to help you.
The good news is, this book has now been released into the public domain - in other words, you can now download it for free!
In a short 65 pages, this book teaches you how to build dynamic web sites in Java using JavaServer Faces, using a hands-on, practical approach. Little or no prior experience in web development is necessary (though a bit of Java knowledge would help)."
Jean-Francois Arcand previews the next version of Grizzly in today's Weblogs, writing
Onedoteightdotsix is out: A speedy Grizzly is out again! "This week we have released our latest monster version, which is 1.8.6. 1.8.6 is the foundation for GlassFish v3 and Sailfin...and many many new application! And we tested that one like a crazy Grizzly!"
Christian Frei announces
Jazoon Rookies - Europe's first Young JAVA Developer Speaker's Competition
Jazoon Rookies is Europe's first ever young Java developer speaker's competition which will be held during Jazoon'09 in Zurich, Switzerland from 22 25. June 2009. Get more information on jazoon.com.
Finally, Kohsuke Kawaguchi says that
Installing Hudson on Windows just got even easier. "Windows make it very hard to run an ordinary program as a service, so Erik had to write a rather long description of how to achieve this. In Hudson 1.254, I implemented a new feature so that Hudson can install itself as a Windows service with a few mouse clicks, complete with a restart of Hudson."
This week's Spotlight is on
the SDN's latest Ask The Experts session, focusing on OpenSSO. "The OpenSSO project is designed to provide an open and extensible identity services infrastructure that simplifies the deployment of transparent single sign-on (SSO) as a security component in a network environment. The project is the open source counterpart of OpenSSO Enterprise 8.0 (formerly Sun Access Manager), Sun's premier access management, identity federation, and web services solution. Got a question about OpenSSO? Post it during this session and get answers from four key members of Sun's identity and access management team: Rajeev Angal, Aravindan Ranganathan, Dilli Dorai, and Qingwen Cheng."
In today's Forums,
romanz explains ME file access in
Re: how to use file:// protocol to access directory. "To access anything in the device file system via file:// protocol, JSR-75 FileConnection is used. The JSR is able to restrict file system access, i.e. not show the entire directory structure to Java applications. Typically, the first thing a MIDlet should do before attempting to access any directory (after verifying that JSR-75 is present), is a call to javax.microedition.io.file.FileSystemRegistry.listRoots(), which tells what virtual file system roots are accessible to the application. For an example of FileConnection usage, you can check the FileBrowser MIDlet in PDAPDemo suite from Sun Java Wireless Toolkit (version 2.5.2 is available at http://java.sun.com/products/sjwtoolkit/download.html). For more details on the FileConnection API, please see the specification at http://www.jcp.org/en/jsr/detail?id=75"
kawaiimomo warns against willy-nilly use of
System.gc() in ME apps, as explained in
Re: Does system.gc() really help your app to get more efficient? "Any j2me experienced programmer/guru will tell you not to use gc() as the kvm is wise enough to know when it needs to call gc. In many MIDlets I've done I used System.gc() a lot, just in places such as after loading a big amount of images, data, or after performing any operation that would leave _a lot_ of objects that were ready to being collected. It will probably make the app slower, but you can avoid OutOfMemoryExceptions (for a larger period of time at least)."
denizoguz wants opinions on whether or not to use
JMC on a real project. "We think to use JMC in a several million dolar project. In this project mpeg4 and telemetry data are contained in a transport stream. Java application will display elementary data on video and allow some operations like zoom, chaning contrast etc. on the video file. Target operating system is Windows. I know JMC is preview stage now but we have more than 6 months to complete the project and 1.0 release is very close. Do you think that it is risky?"
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Carp Lake News
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|Publication number
|Publication type
|Application number
|Publication date
|Dec 5, 1995
|Filing date
|May 27, 1994
|Priority date
|May 28, 1993
|Fee status
|Also published as
|Publication number
|Masanobu Kudoh, Hidehiko Haneishi
|Original Assignee
|Kansai Paint Co., Ltd.
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (11), Referenced by (14), Classifications (11), Legal Events (6)
|External Links: USPTO, USPTO Assignment, Espacenet
This invention relates to a novel aqueous resin dispersion. More particularly, the invention relates to an aqueous resin dispersion which is capable of forming a coating excelling in such properties as weatherability and corrosion resistance and is suitable, in particular, for use in cationic electrodeposition paint compositions.
As an aqueous resin dispersion for cationic electrodeposition paint compositions, a composition composed of an epoxy-polyamine resin formed by a reaction of an epoxy resin with an active hydrogen-containing amino compound, and a blocked polyisocyanate compound which is blended as a curing agent, has already been put to practical use. While coating formed of this composition excels in corrosion resistance, it still has the defect of insufficient weatherability.
In order to improve the weatherability, modification of the epoxy resin with a polyester resin, polyether resin, acrylic resin or the like has been tried. While those attempts more or less succeeded in improving the weatherability, they give rise to another problem that the characteristic corrosion resistance of epoxy resin is decreased.
In particular, in the attempts to modify the epoxy resin with an acrylic resin, to cause the modification reaction to a sufficient extent is itself difficult due to poor compatibility of these two components, and furthermore the resultant modified product shows the deficiency of high viscosity.
The present inventors have engaged in concentrative studies with the view to develop an aqueous resin composition which can form a coating excelling in both corrosion resistance and weatherability, and now discovered that the above object can be accomplished by using, for modifying the epoxy resin, a specific acrylic resin whose molecular weight distribution region is controlled to be within a narrow range. The present invention is thus completed.
Thus, according to the present invention, an aqueous resin dispersion which comprises, as the chief component, an acrylic-modified epoxy-polyamine resin composed of:
(A) a bisphenolic epoxy resin containing at least two epoxy groups per molecule; and following components (B) and (C) which are bound to at least a part of said epoxy groups:
(B) an acrylic resin having on the average at least one functional group which is capable of reacting with said epoxy group, the molecular weight distribution of said acrylic resin as expressed by weight average molecular weight (Mw)/number average molecular weight (Mn) being within the range of 1-1.2; and
(C) an active hydrogen-containing amino compound;
is provided.
Hereinafter each of the above components constituting the aqueous resin dispersion of the present invention is explained in further details.
Bisphenolic epoxy resin (A):
Bisphenolic epoxy resin (A) is a low or high molecular weight compound having at least two epoxy groups per molecule. In particular, such a diglycidyl ether of bisphenol, which is obtained by a condensation reaction between a bisphenolic compound and epihalohydrin, for example, epichlorohydrin, readily forms a coating excelling in flexibility and corrosion resistance ann, therefore, is preferred.
Typical examples of bisphenolic compounds useful for the preparation of epoxy resin (A) include bis(4-hydroxyphenyl)-2,2-propane, bis(4-hydroxyphenyl)-1,1-ethane, bis(4-hydroxyphenyl)-methane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, bis(4-hydroxyphenyl)-1,1-isobutane, bis(4-hydroxy-3-t-butylphenyl)-2,2-propane and the like.
Of those epoxy resins (A) formed from such bisphenolic compounds, a bisphenol A-derived diglycidyl ether which is represented by the formula below is particularly preferred, because it gives a coated film excelling in flexibility and corrosion resistance: ##STR1## (in which q stands for a number of 2 to 20).
As the epoxy resin (A), furthermore, a product obtained upon etherification reaction of the excess amount of a diglycidyl ether of bisphenol, a condensation reaction product of a bisphenolic compound with epihalohydrin, with still another bisphenolic compound, can also be advantageously used.
Preferred epoxy resin (A) to be used in the present invention generally has a number average molecular weight ranging from about 310 to about 10,000, more preferably from about 320 to about 6,000, inter alia, from about 320 to about 2,000. Furthermore, its epoxy equivalent is within the range of from about 155 to about 5,000, preferably from about 160 to about 3,000, and still more preferably from about 160 to about 1,000.
Acrylic resin (B):
Acrylic resin (B) useful for the present invention has per molecule, on the average at least 1, preferably 1-2, functional groups which are reactive with the epoxy groups of above-described epoxy resin (A); and has the molecular weight distribution expressed by weight average molecular weight (Mw)/number average molecular weight (Mn) within a range of 1 to 1.2. As such functional groups reactive with the epoxy groups, for example, carboxyl, hydroxyl, unsubstituted or mono- or di-substituted amino and mercapto groups, etc. may be named.
Such acrylic resin (B) includes, for example, copolymers of polymerizable unsaturated monomers (a) having such functional groups capable of reacting with epoxy groups as above-named and other unsaturated monomers (b) copolymerizable therewith. Here the monomer (a) is a compound having at least one each of such functional group reactable with epoxy group as above-named and a polymerizable, unsaturated bond, per molecule. Examples of such monomers (a) include α,β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid; hydroxyalkyl esters of (meth)acrylic acid such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate; and mono- or di-alkylaminoalkyl esters of (meth)acrylic acid such as 2-(dimethylamino)ethyl acrylate and 2-(dimethylamino)-ethyl methacrylate.
whereas, as other unsaturated monomers (b) which are copolymerizable with these monomers (a), for example, the following may be named: alkyl or cycloalkyl esters of (meth)acrylic acid such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, n-butyl(meth)acrylate, isobutyl(meth)acrylate, tert-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, cyclohexyl(meth)acrylate, n-octyl(meth)acrylate, lauryl(meth)acrylate, dodecyl(meth)acrylate, stearyl(meth)acrylate, etc; alkoxyalkyl esters of (meth)acrylic acid such as methoxybutyl(meth)acrylate, methoxyethyl(meth)acrylate, ethoxybutyl(meth)acrylate, etc.; aralkyl esters of (meth)acrylic acid such as benzyl(meth)acrylate, etc.; glycidyl(meth)acrylate or adducts of hydroxyalkyl esters of (meth)acrylic acid with monocarboxylic acid compounds such as of captic acid, lauric acid, linoleic acid, oleic acid and the like; adducts of (meth)acrylic acid with monoepoxy compounds such as "CARDURA� E10" (manufactured by Shell Chemical Co.); and vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene, p-tert-butylstyrene, etc.
Copolymerization of above monomers (a) and (b) can be carried out by, for example, anionic polymerization, cationic polymerization, group-transfer polymerization (cf. GB-A-2102818) or the like. In particular, when 1,1-bis(trimethylsiloxy)-2-methyl-1-propene is used as an initiator in group-transfer polymerization method, the molecular terminals automatically become carboxyl groups, and furthermore all the molecules come to have only one carboxyl group. This polymerization method, therefore, is particularly preferred.
The ratio of said monomer (a) to the monomer (b) is not critical, so long as the resulting acrylic resin (B) comes to have, on the average, at least one functional group per molecule which is reactive with epoxy group. Whereas, generally it is preferred to use 0.1-10 wt %, in particular, 1-5 wt %, of monomer (a) and 99.9-90 wt %, in particular, 99-95 wt %, of monomer (b), based on the total weight of the two monomers. While the acrylic resin (B) preferably has at least 1, more preferably 1-2, functional groups per molecule which are reactable with epoxy groups, it is permissible that molecules having none of such functional group and those containing two or more functional groups are concurrently present in the resin, the number of the functional groups being, on the average, at least 1, preferably 1-2, per molecule.
Number average molecular weight (Mn) of acrylic resin (B) is subject to no critical limitation, but normally preferred range is from about 1,500 to about 5,000, more preferably from about 2,300 to about 5,000, most preferably from about 3,000 to about 5,000. It is important for acrylic resin (B) to have a molecular weight distribution, which is expressed as weight average molecular weight (Mw)/number average molecular weight (Mn), of 1-1.2, in particular, 1-1.1. When the molecular weight distribution of acrylic resin (B) is greater than 1.2, compatibility of acrylic resin (B) and epoxy resin at high molecular weight region is reduced, and the formed acrylic-modified epoxy resin solution comes to have undesirably high viscosity.
Active hydrogen-containing amino compound (C):
The active hydrogen-containing amino compound useful for the present invention contains at least 1, preferably 1-4 active hydrogen atoms which are reactable with epoxy groups. Such compounds include aliphatic, alicylic or aromatic-aliphatic primary or secondary amines, alkanolamines, their modification products, tertiary amine salts, and the like. As such active hydrogen-containing amino compounds, for example, the following may be named:
(1) compounds derived from amine compounds containing one secondary amino group and at least one primary amino group, such as diethylenetriamine, hydroxyethylaminoethylamine, ethylaminoethylamine, methylaminopropylamine and the like, whose primary amino group(s) is(are) converted into aldimine, ketimine, oxazoline or imidazoline, by a reaction under heating with ketone, aldehyde or carboxylic acid, at temperatures of, for example, 100�-230� C.;
(2) secondary monoamines such as diethylamine, diethanolamine, di-n- or iso-propanolamine, N-methylethanolamine, N-ethylethanolamine and the like;
(3) secondary amino group-containing compounds formed by adding monoalkanolamines such as monoethanolamine and dialkyl(meth)acrylamide by means of Michael addition reaction;
(4) compounds derived from alkanolamines such as monoethanolamine, neopentanolamine, 2-aminopropanol, 3-aminopropanol, 2-hydroxy-2'-(aminopropoxy)ethylether, and the like, whose primary amino group is converted into ketimine; and
(5) salts of tertiary amines such as dimethylethanolamine, triethylamine, trimethylamine, triisopropylamine, methyldiethanolamine, etc., with such organic acids as acetic acid, butyric acid, etc.
Acrylic-modified epoxy-polyamine resin:
The acrylic-modified epoxy-polyamine resin useful for the present invention is obtained by binding acrylic resin (B) and active hydrogen-containing amino compound (C) with a part or whole of the epoxy groups of above-described epoxy resin (A). Methods of reacting above components are subject to no critical limitation, but any methods known per se may be employed. Specifically, those methods exemplified below can be adopted:
1) An epoxy resin (A) is caused to react simultaneously with an acrylic resin (B) and active hydrogen-containing amino compound (C).
2) A part of epoxy groups in an epoxy resin (A) are first caused to react with an acrylic resin (B), and then a part or whole of the remaining epoxy groups in the same resin (A) are caused to react with an active hydrogen-containing amino compound (C).
3) First a part of epoxy groups in an epoxy resin (A) are caused to react with an active hydrogen-containing amino compound (C) and then a part or whole of the remaining epoxy groups in the same resin (A) are caused to react with an acrylic resin (B).
4) A part of epoxy groups in a diglycidyl ether of bisphenol for preparing epoxy resin (A) are caused to react with an acrylic resin (B), the remaining epoxy groups are further caused to react with a bisphenolic compound, and then the resin is caused to react with an active hydrogen-containing amino compound (C).
Of the above, the method 2) is the most preferred.
The reaction of epoxy groups in epoxy resin (A) with the functional groups of acrylic resin (B) can be conducted under heating at about 60� C.-about 200� C. for about an hour-about 24 hours, in the absence of catalyst or in the presence of such a catalyst as, for example, a tertiary amine such as triethylamine, tributylamine, dimethylbenzylamine, etc.; or a quaternary ammonium salt such as tetrabutylammonium benzoate, tetrabutylammonium bromide, etc.
The reaction of active hydrogen-containing amino compound (C) with epoxy groups of epoxy resin (A) can be carried out, for example, at temperatures ranging from about 30� C. to about 160� C., for about 1 to about 5 hours.
The reaction ratio among the components of epoxy resin (A), acrylic resin (B) and active hydrogen-containing amino compound (C) is variable over a wide range according to individual usages intended. Whereas, it is generally preferred to use, based on the sum weight of epoxy resin (A) and acrylic resin (B), 16-90 wt %, in particular, 35-80 w %, and most preferably 50-70 wt %, of acrylic resin (B). Furthermore, active hydrogen-containing amino compound (C) is preferably used in such an amount as will make the amine value of resultant acrylic-modified epoxy-polyamine resin in the range of 15-100, in particular, 15-70, and most preferably, 15-47.
Thus formed acrylic-modified epoxy-polyamine resin normally is preferred to have a number average molecular weight within a range of 1,000-20,000, in particular, 1,700-12,000, and most preferably, 2,400-4,000.
The acrylic-modified epoxy-polyamine resin preferably contains primary hydroxyl groups. While the range of such primary hydroxyl equivalent is not critical, normally preferred range is 400-700, in particular, 400-625, and most preferably, 400-550. Active hydrogen-containing functional groups such as primary hydroxyl groups originating from acrylic resin (B) and active hydrogen-containing amino compound (C) and secondary hydroxyl groups, which are present in epoxy resin (A), are useful as reactive functional groups with a cross-linking agent.
Said acrylic-modified epoxy-polyamine resin may also be reacted with such reaction reagent as a tertiary amine salt, monocarboxylic acid, secondary sulfide salt, monophenol and monoalcohol, for controlling dispersibility of the resin in water or improving smoothness of its coated film.
Furthermore, it is also possible to introduce into the acrylic-modified epoxy-polyamine resin such crosslinking functional groups as blocked isocyanate groups, β-hydroxycarbamate groups, α,β-unsaturated carbonyl groups, or N-methylol groups, to impart internal (self)crosslinking ability to the resin.
Above reactions with the reagents and introduction of crosslinking functional groups may be conducted before adding an active hydrogen-containing amino compound (C) to the acrylic-modified epoxy resin.
The resultant acrylic-modified epoxy-polyamine resin can be used concurrently with an external cross-linking agent. As useful external crosslinking agent, compounds having at least 2 crosslinking functional groups per molecule, for example, blocked polyisocyanate, β-hydroxycarbamic acid ester of polyamine, maronic acid derivatives, methylolated melamine, methylolated urea, etc. can be named. The blend ratio (solid ratio) between the acrylic-modified epoxy-polyamine resin and such external crosslinking agent is not strictly limited, while normally a range of 100/0-60/40, in particular, 85/15-75/25, is preferred.
Above-described acrylic-modified epoxy-polyamine resin in accordance with the present invention can be formed into an aqueous resin dispersion, by dissolving or dispersing it in an aqueous medium.
Aqueous resin dispersions of the acrylic-modified epoxy-polyamine resin can be prepared, for example, by protonating amino groups in the resin with a water-soluble organic acid such as formic, acetic, or butyric acid, and the like, to cause dissolution or dispersion of the resin in an aqueous medium.
The amount (neutralization number) of the acid used for said protonation cannot be strictly defined, but normally a range of about 5-about 40 KOH mg number, in particular, 10-20 KOH mg number, per gram of the solid resin, is preferred for favorable electrodeposition characteristics. Thus obtained aqueous resin dispersion is particularly suited for use for cationic electrodeposition paint, to which pigment, solvent, curing catalyst, surfactant, etc. may optionally be added as occasion demands.
Above-described aqueous resin dispersion of the present invention can provide, when applied onto an object, a coating excelling in weatherability, and furthermore, in corrosion resistance and in appearance as well, because the acrylic-modified epoxy-polyamine resin therein has been modified with an acrylic resin having the specific, narrow molecular weight distribution and consequently compatibility of the epoxy resin and acrylic resin in the coating is high.
It is now discovered, furthermore, that combined use of said acrylic-modified epoxy-polyamine resin component with non-ionic film-forming resin component excelling in weatherability, such as acrylic resin, polyester resin and the like, provides resin compositions capable of forming a coating of still more improved weatherability and corrosion resistance, which are particularly useful for cationic electrodeposition paint.
According to the present invention, therefore, further a resin composition comprising
(I) the above-described acrylic-modified epoxypolyamine resin, and
(II) non-ionic, film-forming resin at a ratio of: resin (I): resin (II)=15:85-95:5 (by weight),
which is particularly suitable for use in cationic electrodeposition paint, is provided.
It is important and indispensable for resin (II) to be used in this resin composition that it is non-ionic, viz., it does not contain any functional group (e.g., carboxyl group or amino group) which forms cationic group upon neutralization with acid. It is desirable that this resin (II) is substantially not reactive with resin (I), while it may react with such a crosslinking agent as above-named. More specifically, acrylic resins, polyester resins, polyester-modified resins and silicone-modified resins which particularly excel in weatherability are conveniently used, the most preferred being acrylic resins.
Hereinafter such resins which are conveniently used as resin (II) are explained in further detail.
As non-ionic acrylic resins, those products obtained through homo- or co-polymerization, which is carried out in the manner known per se, of one or more of acrylic monomers such as alkyl esters of (meth)acrylic acid, e.g., methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, propyl(meth)acrylate, 2-ethylhexyl(meth)acrylate; hydroxyalkyl esters of (meth)acrylic acid, e.g., hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate; or of such acrylic monomer or monomers used as the chief component, in optional combination with one or more of other unsaturated monomers, which are suitably selected according to the desired physical properties, such as styrene and derivatives thereof (for example, α-methylstyrene), (meth)acrylonitrile, butadiene, etc. can be used.
The non-ionic acrylic resin (II) suitably has a number average molecular weight in a range of about 3,000-about 100,000, preferably from about 3,500-about 75,000, more preferably from about 4,000 to about 50,000. Furthermore, when the acrylic resin (II) is caused to contain hydroxyl groups as the functional group, it reacts with a polyisocyanate compound which is a cross-linking agent for the resin (I), to be crosslinked and cured.
Non-ionic polyester resins which can be used as the resin (II) include the products of condensation polymerization, which is carried out in the manner known per se, of polybasic acid component such as, for example, phthalic acid and acid anhydride thereof, isophthalic acid, terephthalic acid, trimellitic acid and acid anhydride thereof, pyromellitic acid and acid anhydride thereof, hexahydrophthalic acid and acid anhydride thereof, succinic acid, adipic acid, pimelic acid, sebacic acid, brasylic acid and the like; with polyol component such as ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, 1,6-hexanediol, trimethylolpropane, glycerin, pentaerythritol, tricyclodecane dimethanol and the like. In that occasion, molecular weight of the product may be controlled by using as a terminal blocking agent, for example, benzoic acid, p-t-butylbenzoic acid, etc.
Thus obtained polyester resin can generally have a number average molecular weight within a range of from about 300 to about 50,000, preferably from about 2,000 to about 20,000.
It is also feasible to use as the resin (II) a blend of aforesaid acrylic resin and the polyester resin. Furthermore, polyester-modified (grafted) acrylic resins or acrylic-modified (grafted) polyester resins can be synthesized by combining earlier described starting materials, and such modified resins can also be used as said resin (II). (In the present specification, they are collectively referred to as "polyester-modified resin".)
Non-ionic silicone-modified resins useful as said resin (II) include base resins such as above-described acrylic resins, polyester resins or alkyl resins, etc. which are modified with silicone resins. In those modified resins, the amount of silicone resins used is not more than 50 wt %, preferably 3-45 wt %, of the total resins. When the silicone resin content exceeds 50 wt %, inter-layer adhesion between the paint composition formed with the use of such silicone-modified resin and the finish coating thereon is liable to be degraded, and the resin (I) and resin (II) completely separate into two layers, the adhesion of the two layers tending to be aggravated.
silicone resins to be used for modifying the base resins are normally organopolysiloxane resins having number average molecular weight ranging from about 500-about 2,000, and at least 2 reactive groups such as hydroxyl, alkoxy and the like, per molecule, example of which including Z-6018(product of Dow Corning; molecular weight=1,600), Z-6188 (product of Dow Corning; molecular weight=650), Sylkyd 50, DC-3037 (product of Dow Corning), KR-216, KR-218, KSP-1 [products of Shin-etsu silicone K.K.], TSR-160, TSR-165 [products of Tokyo Shibaura Denki K.K.], SH5050, SH6018, SH6188 [products of Toray silicone K.K.].
Silicone-modified resins can be prepared by co-condensing above-described silicone resins with a base resin having hydroxyl groups and/or carboxyl groups, e.g., acrylic resin, polyester resin, alkyd resin or the like, at aforesaid use ratio, by the method known per se.
The resin compositions of the present invention can be prepared by dispersing and/or dissolving above-described resin (I) and resin (II) in an aqueous medium, by a method known per se. Aqueous liquid dispersions of above resin compositions can be prepared, for example, by 1 mixing a solution of said resins (I) and (II) in a water-miscible organic solvent, with water and an acid, e.g., a water-soluble organic or inorganic acid such as acetic acid, formic acid, butyric acid, phosphoric acid, sulfuric acid, etc., to neutralize the whole system to form an aqueous bath; or 2 dispersing resin (I) in an aqueous medium, neutralizing the system with an acid to form an aqueous bath, and forcedly dispersing in the aqueous bath a water-miscible organic solvent-solution of resin (II) using a homogenizer or the like. In the aqueous dispersions prepared by either of above methods 1 and 2, particles of resin (II) are dispersed in the aqueous medium with high stability by the virtue of the neutralization product of resin (I), and the dispersions exhibit excellent storage stability over prolonged periods.
For preparing above resin compositions, either of resin (I) and resin (II) may be a single resin or a combination of two or more resins. Such resin (I) and resin (II) can be blended at the following weight ratios ranging:
______________________________________ resin (I):resin (II) = 15:85-95:5, preferably 50:50-90:10, most preferably 60:40-85:15.______________________________________
At blend ratios outside the above-specified range, it becomes generally difficult to obtain a multi-layered coating having an effective concentration gradient, and both weatherability and corrosion resistance of the coating tend to be lowered.
It is also permissible to add to the resin compositions of the present invention, besides above-described resins (I) and (II), coloring pigments, anti-corrosive pigments, extender and other additives, which are normally used in the field of paints, optionally as necessity demands.
The amount (neutralization number) of the acid to be used for the neutralization (protonation) practiced in the above-described preparation of aqueous dispersions of the resin compositions cannot be strictly defined. Whereas, normally a range of about 5-about 40 KOH mg number, in particular, 10-20 KOH mg number, per gram of the solid resin component, is preferred for favorable electrodeposition characteristics. Thus obtained aqueous dispersions are particularly suitable for use with paints for cationic electrodeposition coating. In such occasions, pigments, solvents, curing catalysts, surfactants, etc. may be added to the dispersions as necessity demands.
Electrodeposition coating:
As the methods and apparatuses for practicing electrodeposition coating using said aqueous resin dispersions or resin compositions provided by the present invention, those methods and apparatuses known per se in the art of electrodeposition coating can be used. In such occasions, it is desirable to use the object to be coated as cathode, and a stainless steel or carbon plate, as anode. Useful electrodeposition coating conditions are not particularly limited, but generally it is desirable to effect the electrodeposition under such conditions as: bath temperature, 20�-30� C.; voltage, 100-400 V (preferably 200-300 V); current density, 0.01-3 A/dm2 ; electrification time, 1-5 minutes; polar area ratio (A/C), 2/1 to 1/2; inter-polar distance, 10-100 cm; and under agitation.
The coating deposited on the object to be coated is washed, and can be cured by baking at about 140� C.-about 180� C.
Hereinafter the present invention is explained more specifically by the following working examples, in which percents are by weight.
Into a flask equipped with a stirrer, thermometer, nitrogen inlet tube and a reflux condenser, 700 g of bisphenol A diglycidyl ether having an epoxy equivalent of 190, 192 g of bisphenol A and 13.5 g of dimethylbenzylamine were added and allowed to react at 110� C. until the epoxy group concentration reached 2.24 mmol/g. To the resultant epoxy resin (A) [number average molecular weight, 1025; epoxy equivalent, 539], 2670 g of an acrylic resin (B) which was synthesized by group-transfer polymerization and had a carboxyl group at one of the chain terminals [monomeric composition: 2-(trimethylsiloxy) ethyl methacrylate/butyl methacrylate/2-ethylhexyl methacrylate/methyl methacrylate=34/32/23/11 (%); number average molecular weight (Mn), 3628; Mw/Mn=1.10; acid value of the resin, 15.5] and 515 g of ethylene glycol monobutylether were added, and allowed to react at 110� C. until the epoxy group concentration decreased to 0.380 mmol/g and acid value of the resin became 0. Then the system was cooled down to 100 � C., at which point 117 g of diethanolamine (C) was added to the system and allowed to react at 100� C. until all of the epoxy groups disappeared. The system was then diluted with ethylene glycol monobutylether until the solid component occupied 75% of the system, to provide an acrylic-modified epoxy-polyamine resin (1) having a primary hydroxyl equivalent of 505 and an amine value of 18.6.
Into the same reactor as the one used in Example 1, 700 g of bisphenol A diglycidyl ether having an epoxy equivalent of 190, 192 g of bisphenol A and 13.5 g of dimethylbenzylamine were added and allowed to react at 110� C. until the epoxy group concentration reached 2.24 mmol/g. To the resultant epoxy resin (A) [number average molecular weight, 1025; epoxy equivalent, 539], 2694 g of acrylic resin (B) which was synthesized by group-transfer polymerization and had a carboxyl group at one of the terminals [monomeric composition: 2-(trimethylsiloxy)ethyl methacrylate/butyl methacrylate/methyl methacrylate=37/51/12 (%); number average molecular weight (Mn), 3404; Mw/Mn=1.13; acid value of the resin, 16.5] and 592 g of ethylene glycol monobutyl ether were added. The system was allowed to react at 110� C. until the epoxy group concentration decreased to 0.342 mmol/g and acid value of the resin became 0. The system was then cooled and when the temperature went down to 100� C., 111 g of diethanolamine (C) was added thereto, followed by the reaction at 100� C. until all of the epoxy groups disappeared. The system was diluted with ethylene glycol monobutyl ether to a solid content of 75%, to provide an acrylic-modified epoxy-polyamine resin (2) having a primary hydroxyl equivalent of 483 and an amine value of 17.7.
Into the same reactor as the one used in Example 1, 700 g of bisphenol A diglycidyl ether having an epoxy equivalent of 190, 192 g of bisphenol A and 13.5 g of dimethylbenzylamine were added and allowed to react at 110� C. until the epoxy group concentration reached 2.44 mmol/g. To the resultant epoxy resin (A) [number average molecular weight, 1025; epoxy equivalent, 539], 2381 g of an acrylic resin which was synthesized through ordinary radical polymerization and had carboxyl group(s) at the terminal(s) [monomeric composition: 2-hydroxyethyl methacrylate/styrene/2-ethylhexyl methacrylate/butyl methacrylate=20/40/30/5 (%); polymerization initiator, azobis-n-pentannoic acid; number average molecular weight (Mn), 7120; Mw/Mn=11.8; acid value of the resin, 14.3] and 599 g of ethylene glycol monobutyl ether were added, and allowed to react at 110� C. until the epoxy concentration was decreased to 0.426 mmol/g. Then the system was cooled down to 100� C., at which point 121 g of diethanoiamine (C) was added and allowed to react at 100� C. until all the epoxy groups disappeared. The reaction system was then diluted with ethylene glycol monobutyl ether to have a solid content of 75%. Thus an acrylic-modified epoxy-polyamine resin (3) having a primary hydroxyl equivalent of 602 and an amine value of 20.6 was obtained.
The resins obtained in the foregoing Examples 1 and 2, and Comparative Example 1 were each blended with methyl ethyl ketoxime-blocked isophorone diisocyanate at such ratios that the blocked isocyanate groups became equivalent to the primary hydroxyl groups in the acrylic-modified epoxy-polyamine resin. Furthermore, per 100 g of the solid in each of the resin compositions, 1 g of polypropylene glycol (manufactured by Sanyo Chemical Industries, Ltd., Sunnix PP 4000), 0.82 g of formic acid and 1 g of lead acetate were added. Each system was heated to 40� C., into which deionized water was gradually added under stirring to form an aqueous dispersion. Thus, stable emulsions with 30% solid resin component were obtained. Per 100 g of the solid resin in each of the emulsions, 3 g of basic lead silicate, 13 g of titanium white, 0.3 g of carbon, 3 g of clay, 2 g of dibutyltin oxide and 1 g of non-ionic surfactant (commercial name: Noigen 142B, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) were added, and each system was subjected to a ball mill operation to cause dispersion of the pigment until the particle sizes were reduced to no greater than 10 microns, followed by dilution with deionized water to the solid resin content of 15%.
Thus obtained three diluted paints were used in cationic electrodeposition coating on untreated steel plates at a bath temperature of 28� C. and voltage of 250 V for 3 minutes. The plates were then baked at 170� C. for 20 minutes to provide enamel-coated panels. Weatherability and corrosion resistance of the resultant panels were measured with the results as shown in Table 1.
The measurement methods of the weatherability and corrosion resistance as indicated in Table 1 are as follows.
(*1) Weatherability
Above coated panels were further painted with a clear top paint (Magicron 7000, product of Kansai Paint Co., Ltd.) to provide weatherability test panels. The test panels were subjected to repeated test cycles composed of 20 hours' exposure to Sunshine Weathermeter (test temperature, 63��3� C.; spray time cycle, 12 minutes in 60 minutes; humidity, 50�5%) and 2 hours' 40� C. warm water dipping. At the end of each cycle the painted plates were given a cross-cut and peeled with a cellophane tape. Whereby adhesion between the electrodeposited coating and the clear top paint layer was evaluated. When nearly no peeling of the clear top occurred, the adhesion was evaluated as ◯, and when the peeling occurred in wide scale around the cross-cut, X. The weatherability evaluation is expressed by the number of testing hours until the X evaluation occurred.
(*2) Corrosion resistance (resistance to salt spray)
The electrodeposition-coated plates were entered with cross-cuts, and tested in the manner following JIS Z2871. After 480 hours, the cross-cut portions were peeled off by means of a cellophane tape and width of the peeled portion was measured.
TABLE 1__________________________________________________________________________ Comparative Example 1 Example 2 Example 1__________________________________________________________________________Base resin acrylic-modified epoxy- 75 75 75 polyamine resin solid component (g)Curing agent methyl ethyl ketoxime 25 25 25 blocked isophorone diisocyanate solid component (g)Performance condition of painted good good poorof painted surfacefilm (visual observation) weatherability (*1) at least at least at least 600 hours 600 hours 600 hours corrosion resistance (*2) 1 mm 1 mm 10 mm__________________________________________________________________________
(preparation of non-ionic acrylic resin)
______________________________________ (parts)______________________________________1 Butyl cellosolve 262 80% Polyester monomer ("FM-3X" made by Daicel Chemical Industries, Ltd.) 37.53 Styrene 404 Hydroxyethyl methacrylate 255 n-Butyl methacrylate 56 AIBN (azobisisobutyronitrile) 47 Butyl cellosolve 58 Azobisdimethyl valeronitrile 0.59 Cellosolve 23______________________________________
The component 1 was heated to 130� C., and at said temperature components 2 to 6 were added to the system dropwise, which consumed 5 hours. Then the system was maintained at 130� C. for 2 hours, followed by dropwise addition of components 7 and 8 over 2 hours at 130� C., and 2 hours' standing at 130� C. Further the component 9 was added and the system was cooled. Thus a solution of a non-ionic acrylic resin having a number average molecular weight of about 5,000 was obtained, with a solid content of 62%.
The acrylic-modified epoxy-polyamine resin (I) as obtained in above Example 1 and the non-ionic acrylic resin (II) as obtained in Example 4 were blended with methyl ethylketoxime blocked isophorone diisocyanate at such a ratio that the blocked isocyanate groups became equivalent to the primary hydroxyl groups in the resins (I) and (II). Furthermore, per 100 g of the solid component in the resin composition, 1 g of polypropylene glycol ("Sunnix PP 4000" manufactured by Sanyo Chemical Industries, Ltd.), 0.82 g of formic acid and 1 g of lead acetate were added. Under heating to 40� C. with agitation, deionized water was slowly added to the system to form an aqueous dispersion. Thus a stable emulsion with solid resin content of 30% was obtained. Per 100 g of the solid resin component in the emulsion, 3 g of basic lead silicate, 13 g of titanium white, 0.3 g of carbon, 3 g of clay, 2 g of dibutyltin oxide and 1 g of non-ionic surfactant (commercial name: "Noigen 142B", product of Daiichi Kogyo Seiyaku Co.) were added to the emulsion, and the pigment was dispersed in a ball mill until its particle size was reduced to no greater than 10 microns. The emulsion was further diluted with deionized water to make the solid resin content 15%. The blend ratio between the resin (I) and resin (II) was varied for each run as indicated in Table 2, while other conditions were unchanged.
Thus obtained cationic electrodeposition paint compositions were used in cationic electrodeposition coating on unreacted steel plates at a bath temperature of 28� C. and voltage of 250 V for 3 minutes. The plates were then baked at 170� C. for 20 minutes to provide enameled coated panels. Weatherability and corrosion resistance of the panels were measured in the same manner as described in Example 3. The results are also shown in Table 2.
TABLE 2__________________________________________________________________________ Comparative Example Example 5 6 7 2 3__________________________________________________________________________Resin (I) 67 52 38 7 75Resin (II) 8 23 37 68 0Crosslinkingagent 25 25 25 25 25Performance ofcoatingCondition ofcoated surface ◯ ◯ ◯ X ◯Weatherability 700 H< 800 H< 800 H< 800 H< 600 H<Corrosionresistance 1.0 mm 1.0 mm 1.5 mm 10.0 mm 1.0 mm__________________________________________________________________________
|Cited Patent
|Filing date
|Publication date
|Oct 18, 1982
|Jul 3, 1984
|Toyo Ink Manufacturing Co.
|Aqueous coating resin composition
|Dec 27, 1983
|Feb 26, 1985
|Chu Shaw C
|Aqueous coating compositions and process for their preparation from epoxy acidic acrylic polymer and polyfunctional amine
|Sep 6, 1983
|Mar 5, 1985
|E. I. Du Pont De Nemours And Company
|Low temperature curing coating composition
|Mar 20, 1991
|Dec 17, 1991
|Kansai Paint Co., Ltd.
|Thermosetting resin composition
|Sep 10, 1987
|Aug 11, 1992
|Shell Oil Company
|Heat-curable polyepoxide-(meth)acrylate ester compositions
|Aug 13, 1990
|May 18, 1993
|Nissan Motor Co., Ltd.
|Cationic electrodeposition paint composition containing colloidal silica-containing gelled particulate
|Jul 10, 1992
|Dec 14, 1993
|Toyo Ink Manufacturing Co., Ltd.
|Water based coating composition
|Aug 31, 1990
|Feb 1, 1994
|Basf Lacke & Farben Ag
|Coating agents of acrylic copolymer and polyester with tertiary amino groups and epoxy resin
|Nov 18, 1985
|Jun 4, 1986
|E.I. Du Pont De Nemours And Company
|Low temperature curing maintenance coatings
|Title not available
|Title not available
|Citing Patent
|Filing date
|Publication date
|Aug 16, 1995
|Apr 14, 1998
|Kansai Paint Co., Ltd.
|Cationic electrodepositable coating composition and coating method using the same
|Jan 12, 1998
|Oct 20, 1998
|Kansai Paint Co., Ltd.
|Cationic electrodepositable coating composition and coating method using the same
|Oct 9, 1997
|Nov 24, 1998
|Kansai Paint Company, Ltd
|Aqueous coating composition for exterior surface of can
|Jul 9, 1997
|Feb 29, 2000
|Kansai Paint Company, Limited
|Cationic electrodeposition coating composition
|Dec 7, 1999
|Apr 9, 2002
|Reichhold, Inc.
|Hindered amine adducts for polyurea systems
|Sep 25, 2001
|Nov 11, 2003
|Henkel Corporation
|Autodeposition compositions
|Jul 14, 2003
|Nov 21, 2006
|Henkel Kommanditgesellschaft Auf Atkien (Henkel Kgaa)
|Corrosion resistant films based on ethylenically unsaturated monomer modified epoxy emulsions
|Jan 24, 2005
|Apr 3, 2007
|Martin Melchiors
|Low-solvent, OH-functional dispersions
|Jul 30, 2004
|Jun 17, 2008
|Henkel Kommanditgesellschaft Auf Aktien
|Coatings with enhanced water-barrier and anti-corrosive properties
|Jul 30, 2004
|Mar 24, 2005
|Henkel Corporation
|Coatings with enhanced water-barrier and anti-corrosive properties
|Jan 24, 2005
|Jul 28, 2005
|Bayer Materialscience Ag
|Low-solvent, OH-functional dispersions
|Jan 14, 2005
|Sep 9, 2009
|Low-solvent, oh-functional dispersions (II)
|Sep 25, 2002
|Apr 3, 2003
|Henkel Kgaa
|Autodeposition compositions
|Jan 14, 2005
|Aug 4, 2005
|Bayer Materialscience Ag
|Low-solvent, oh-functional dispersions (ii)
|U.S. Classification
|523/409, 525/528, 525/530, 525/529, 525/423, 525/533, 525/107, 525/119
|International Classification
|Cooperative Classification
|European Classification
|May 27, 1994
Owner name: KANSAI PAINT CO., LTD., JAPAN
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KUDOH, MASANOBU;HANEISHI, HIDEHIKO;REEL/FRAME:007016/0007
Effective date: 19940517
|Jun 1, 1999
|Fee payment
Year of fee payment: 4
|May 7, 2003
|Fee payment
Year of fee payment: 8
|Jun 18, 2007
|Maintenance fee reminder mailed
|Dec 5, 2007
|Lapse for failure to pay maintenance fees
|Jan 22, 2008
|Expired due to failure to pay maintenance fee
Effective date: 20071205


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Hülya Avşar (born Malakan on 10 October 1963 in Edremit, Balıkesir) is a popular Kurdish-Turkish actress, pop folk singer, businesswoman, columnist, fashion designer, magazine editor, professional tennis player, and former beauty pageant titleholder. She is also a television personality who served as a coach and judge for the first two seasons of The Voice from 2011 through 2013.
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Clock Suckers
A group of slackers stumble across a time machine...
I Love Egg
This series of cartoons is undeniably cute and inventive!
From Guitar Hero to Black Friday, Shamoozal's got it covered!
Theres a time collapse in the Mushroom Kingdom, and only Marios and Luigis can save it!
Baby Mario's life is in your hands, choose how he should die!
The Mario Brothers shows their "hot stuff" in this movie.
We've even got bloopers for the Gameboy version!
This cartoon never gets to the actual fight, but oh is it good!
Things are not going Donkey Kong's way. He needs a chill pill!
Losing on Super Mario Bros has caused this guy to lose his temper... and his TV screen.
Part two of Mario's Jump In, the fan flick on Rise of the Mushroom Kingdom!
Mario goes crazy in this 10 sec. super fast movie with System Of A Down music. HARDCORE.
If interactivity is your thing, check out these scene-creators!
Mario finds Luigi in his Mansion. Unfortunately it turns bad for the green one!
Fans of our SCAT collection should enjoy this poo-poo related film!


text:
July 27, 2014 - August 2, 2014
This week we are in 2 Zones:
Zone 5: The Living Room
Zone 1: The Entrance, Front Porch and Dining Room
July Habit: Swish & Swipe
August Habit: Laundry
Zone 5: Mission #1 Monday
We are going to be in Zone 5 for four days this week. This is the Living Room and Family Room.
We are going after the hidden clutter in these rooms. Take a look around you and see what is laying around that is really clutter but, because you have become so used to it being there you don't see it as clutter. Have you purged those magazines and books lately? How about the videos, DVD's and CD's? Are they strewn in piles all over that because they belong in these rooms you don't see them anymore? Your mission for today is to set your timer for 15 minutes and go after the "hidden" clutter in these rooms. You will be amazed at how much neater the rooms look when you tackle this.
Do not get obsessed and take apart the whole room. This is about progress NOT perfection. Just tackle one thing at a time!
Zone 5: Mission #2 Tuesday
Yesterday we went after the "hidden" clutter in the Living Room and the Family Room. Today you are going after the trash. Now you may think you have no trash in these rooms but look under the couch and the chairs. Lift up the cushions and check out what seems to magically get swallowed up in the couch. Check under the end tables and the coffee table. Set your timer for 15 minutes and grab a trash bag and start tossing. You will be surprised at how fast you can do this mission. I bet you all will have time left to spare! Be careful not to lift things that are too heavy and awkward on your mission.
Ask for help if you need it! Zone 5: Mission #3 Wednesday
Today is the day we go after that "stuff" that gets left in the Living Room and the Family Room. The shoes, jackets, laundry baskets etc. Set your timer for 15 minutes and go after the things that need to be put away. Deliver them to the proper homes and get back to the rooms and check them again.
Do not get sidetracked when you are putting something away in another room and start picking up that room. Example if you are taking shoes to your room don't get sidetracked by stopping and straightening something in the bedroom. Put away what you need to and go back to the Zone rooms. If you notice that you need to straighten in another room that you have made a delivery to, then review your schedule and see if you can go to that room for a 5 minute room rescue. If you do not have time then look ahead to your schedule and try to figure out when you can get there!
This is not all or nothing! This is all about BabySteps and being proud of the small things that we can accomplish!
Zone 5: Mission # 5 Thursday
Today is our last day in the Living Room!
Let's have a detailed vacuuming session. This means to vacuum the room, making sure to get up against the baseboards and to get under the furniture. Please be careful that you don't hurt yourself trying to move furniture. If it is too difficult to get under the couch or chairs then just try to get as close to the base of the furniture as you can. Don't forget the corners!
Have fun and don't get sidetracked!
Zone 1: Mission #1 Friday
We are only in Zone 1 for one day this week; let's make the most of it! Zone 1 is the Front Porch, the Entrance Area and the Dining Room.
Today we are going to go on a Trash hunt! Set your timer for 15 minutes and spend 5 minutes in each area. Start with the front porch and gather up whatever needs to be tossed. Got to the entrance area next, look for the junk mail, newspapers, etc., that seems to accumulate here. Toss! Next head into the Dining Room, grab anything that is really trash but you just haven't noticed it. The stray napkins, magazines, junk mail, old school papers etc. You all know what seems to pile up! Go get it and toss it!
Have Fun! Remember this is only 5 minutes in each area, do not get sidetracked or obsessed!


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Weekend Menu Planning: Keep Cool with Smoothies
By Kalyn Denny on July 16, 2010
BlogHer Original Post
Many spots in the northern hemisphere have been experiencing record-high temperatures for the last few weeks, even climbing above 100F in places like New York City. Even if it's not quite that hot where you live, it's hard to get enthusiastic about cooking on the hottest days of the summer. Fruit or vegetable smoothies can fill in as a meal when it's too hot to cook, and if they're made with ice, smoothies can help you cool off as well.
What's a smoothie? Wikipedia defines smoothies as "a blended, chilled, and sometimes sweetened beverage made from fresh fruit or vegetables." The definition goes on to say that smoothies can contain chocolate, crushed ice, frozen fruit, honey, or frozen yogurt, and they sometimes feature healthful add-ins such as soy milk, whey powder, green tea, herbal supplements, or nutritional supplements. Smoothies are popular for breakfast, but they can taste good any time of day, especially in the summer.
Of course, you can make up your own smoothie recipes easily enough just by adding some ingredients to your blender and giving it a whirl. But to get you started with some ideas, here are a few smoothie combinations from food bloggers that can help you beat the heat.
Photo of Pineapple Orange Smoothie
from Sweetnicks
Cate at Sweetnicks has been focused on clean eating, and her family's favorite Pineapple Orange Smoothie has frozen banana and frozen pineapple as well as two kinds of juice.
Photo of Banana Pineapple Smoothie
from Sarah's Cucina Bella
At Sarah's Cucina Bella, Sarah has been having fun cooking with her kids, and when they make smoothies, Sarah lets the kids choose their own flavors. For herself, Sarah made a Banana Pineapple Smoothie, with coconut water adding a special twist.
Photo of Berry Banana Smoothies
from Simply Recipes
There's no doubt that banana is a favorite smoothie ingredient, but I especially love the sound of Berry Banana Smoothies from Simply Recipes. This post also has a lot of good ideas in the comments for more smoothie combinations from Simply Recipes' readers.
Photo of Cherry Soy Yogurt Smoothie
from Fat Free Vegan Kitchen
When she wanted a vegan breakfast that her daughter would eat, Susan at Fat Free Vegan Kitchen came up with a Cherry Soy Yogurt Smoothie recipe that looks like a winner. Susan used frozen cherries, but when fresh summer cherries are available, they'd be great in this.
Photo of Cranberry, Banana, and Honey Smoothie
from Food Blogga
You may not think of cranberries as a smoothie ingredient, but the Cranberry, Banana, and Honey Smoothie from Food Blogga looks like it would be great any time of year. You can make this with frozen cranberries if they aren't in season.
Photo of Green Smoothie from A Veggie Venture
Finally, at A Veggie Venture, Alanna admits that she didn't expect to like Green Smoothies when she tried them, but is surprised to find that more often than not, she likes the combinations that include one or two leaves of swiss chard.
Ten More Smoothies to Keep You Cool
Blueberry Yogurt Smoothie ~ from The Pioneer Woman Cooks
Blueberry Acai Smoothie ~ from Healthy Happy Life
Watermelon Smoothie ~ from Home Cooking Rocks
Strawberry Shortcake Smoothie (and Tips for Nutritious Smoothies) ~ from Mostly Eating
Raspberry-Banana-Pineapple-Coconut Smoothie ~ from Gluten Free Easily
Cherry Fruit Smoothie ~ from Amanda's Cookin'
Chocolate Peanut Butter Smoothie ~ from Ginger Lemon Girl
Summer Breakfast Smoothie ~ from Just Hungry
Raspberry, Lime, and Mint Smoothie ~ from The Perfect Pantry
How to Make a Green Smoothie ~ from Ultimate Money Blog
Do you like making smoothies? If you've got good ideas for smoothie combinations, we'd love to see your recipe or a recipe link in the comments.
(Every week on BlogHer, we spotlight five recipes with a common theme for a feature called Weekend Menu Planning, hoping one of them might make it onto the menu at your house. You can find previous recipes shared by checking the Weekend Menu Planning Archives or clicking the tag Weekend Menu Planning.)
Kalyn Denny also blogs at Kalyn's Kitchen where she's focused on creating low-glycemic recipes using fresh ingredients. When it's hot outside, Kalyn loves to make Mango Lassi.
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How does visual studio link files to their corresponding designer.cs files? I have a strange situation that's occurred with both the DataSet designer and also the L2S DBML designer where it's ignoring the DataSet.Designer.cs and has created and used a DataSet.Designer1.cs instead. How can I switch it back?
Thanks to Zendar's suggestion, this is what I did:
Re-opening and building the solution in Visual Studio confirmed this worked. Thanks Zendar!
Information about related files is written in project files (*.csproj). This may fix problem:
Alternative would be to try to change information in *.csproj file and then to rename Designer1 to Designer in all places it occurs. I did not try this, but it may work.


text: The iBall i342MV Headphones have an over-the-head design that offers enhanced noise cancellation. For users' comfort, these headsets have soft ear-pads and an adjustable headband. The headphones feature a 27 mm driver unit for high-quality sound. The 3.5 mm stereo jack makes these headphones work with a number of devices like PCs and Laptops. The built-in microphone allows the headphones to be used for audio and video chatting. The volume controller of these headphones allow users to adjust the volume as per need.


text:
Was the General Assembly *trying* to make us angry?
Expand Messages
- Why does our state legislature need to be in session for almost six
months out of every year? It's wasteful, and expensive, especially
when we supposedly had a more than 1/2 Billion dollar budget crisis!
And judging by their performance this year, they could have wrapped
up all of the "must do" legislation and adjourned in about 3-4 weeks
and still accomplished everything in a more thoughtful and transparent
fashion with sufficient time to actually have public hearings, debates,
and waiting periods on every bill like their rules require.
Instead, they wasted the first 5-1/2 months of the session on trivial
matters and then jammed all of the real work into the last week--mostly
the last two days. They ignored the House & Senate Rules that they pass
merely so that they can hold them up and say "See, the legislative
process is transparent and open to the public".
From January 12th to June 17th they passed seven actual bills (a total
of 11 pages of legislation), and 52 non-binding resolutions honoring
various persons or organizations, and recognizing various events or
causes, from "Bisphenol A Exposure" to "Poppy Month".
Then in the last week & a half of the session, when it was much too
late to follow the House & Senate Rules (that were written to ensure
that legislators had adequate time to read each bill and debate its
impact and that the people could voice their opinions and concerns)
they got down to the dirty work of passing lots of ill-considered
bills--56 of them on June 22-29. And on the last day they went hog-wild
and passed another 91 bills! There is no way any of them had a clue what
they were voting for most of the time on the 30th.
Yet, even during that mad rush, they still found the time for another
22 resolutions, including my personal favorite, HCR 59 "Dwarf Awareness
And to top it all off, as one of their last actions of the session, they
voted to ratify the 17th Amendment to the U.S. Constitution! Regardless
of what you think of the 17th Amendment (Popular Election of U.S. Senators)
this was a complete waste of time & taxpayer dollars because it already
had the necessary 3/4th of the states and was adopted in 1913! Why was
this so urgent? After 97 years, one might think this pointless vote could
afford to wait until next year, if not forever...
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Brand: Erie
This product was discontinued by the manufacturer.
Submittal Sheet
Voltage, or volts, is a measurement of the difference between two electric fields (in heating terms, the difference between the Earth's electrical field and the electricity running through your wires).
Zones are the number of areas that you want to control independently of each other. If two rooms can be controlled together, they can be one zone; if they need to be controlled separately, they should be separate zones.
120v Single Zone Relay (DPDT)
The SR100 series zone control relay incorporates a double pole/double throw relay to control a circulator and a boiler operating control in a single zone hydronic heating system.
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The All Pro Aquatic Weight-A-Band is aquatic exercise bands with a plus. They are specifically designed for water workouts. This is a 2 lb set with 1 lb of weight in each handle for additional resistance, and a comfort foot cushion. Not just tubing... you have to try it to believe it! Waterproof yellow vinyl grip handles and comfort foot cushion for ultimate comfort. Work upper body unilaterally and bilaterally. Develop strength, endurance, stroke technique, and improved flexibility. Instructions and carry bag included.
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Chrysler Expands Ram 1500 Tradesman to Include Bigger Cabs
Ram also announced that the Ram 1500 Tradesman would be available in Crew Cab and Quad Cab models to complement the regular-cab Ram 1500 Tradesman models already on sale. The Ram 1500 Tradesman was a value-priced package for half-ton trucks for small business, construction, and commercial fleet uses.
The Ram 1500 Tradesman is powered by a 310-horsepower 4.7-liter V-8 FFV engine. Chrysler says the engine cranks out 330 lb-ft of torque, can tow up to 7700 pounds, and is rated 20 mpg highway. The 390-horsepower 5.7-liter Hemi V-8 is optional. The Hemi ups the ante with 407 lb-ft of torque. Both engines are mated to a six-speed automatic transmission.
Ram 1500 Tradesman models also get unique steel wheels and a factory-applied sprayed-in bedliner. Models equipped with the 4.7-liter V-8 come with the RamBox cargo system including lighted, lockable storage for tools and adjustable tie downs. Other features include a Class IV receiver hitch and four- and seven-pin trailer connectors.
Also available is the Ram 1500 Tradesman HD. The HD version of the half-ton truck is available only as a two-wheel-drive, long-bed, regular cab pickup. It has a towing capacity of 11,500 pounds, and a payload of 3125 pounds.
Source: Chrysler
2015 Ram 1500 SpecificationsVIEW ALL
|Fair Market Price
|Editors' Overall Rating
|27 City / 25 Highway
|Horse Power
|305 hp @ 6,400 rpm
|269 ft lb of torque @ 4,175 rpm


text:
I read this post the other day and it got me thinking
Mountain Bike Dynamo Light!
I havent tried riding at night in the desert yet on the Moonlander but will soon. It makes sense to avoid the brutal sun of the daylight. For some of the multiday trips it would be urber cool to be able to travel at night without the hassle of batteries.
But obviously a fat bike front hub dynamo is going to be URBER niche.........isnt it?
Results 1 to 22 of 22
Thread: Front hub dynamo for a fat bike?
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With 1.7 million freelancers, we'll match you with the perfect talent.
The client has made the following changes to the job.
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a different location.
Need market research on consumer spend, sites they visit, purchases made and on what products and services, time spent on these sites, how big these respective markets are in the following categories:
Health and Wellness
Food and Nutrition
Beauty and Fashion
Fitness and Exercise
Upscale Spas and Retreats
Sites that are similar to this would include: Gilt.com, Spafinder, Wahanda, InnerRewards, NYMag, MakeUpAlley, etc..
Added 3 JAN 2010, 12:45 PM EST
What we need is to determine market size and market opportunity on the internet for the Health and Wellness space including: Spas, Yoga, Personal Trainers, Food and Nutrition, Acupuncture, Chiropractic Services, Pilates, Day Spas, Retreat/Wellness Spas (Canyon Ranch)
Added 4 JAN 2010, 11:31 AM EST
What I Need Done:
I need market size in US $$, on how big the Health and Wellness Space is in both the US and Worldwide. Specifically, need information on A...
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Abhishek Verma to battle for gold in Archery World CupPublished Date : Friday, August 14th, 2015Time posted: 10:23 am By - Wroclaw (Poland), (IANS) On a day when most Indian archers failed to live up to expectation, Abhishek Verma kept his arrows on target to romp into the men's individual compound ... Mangalorean, 2 months ago
Archery World Cup: India men, women finish second in recurve ranking round - Mangalorean, 2 months ago
Arrow Dynamics: Silver for Women at Worlds
NEWDELHI: The agony of heartbreak. That's what the Women in Blue mustve felt. They took a shot at history, but their best fell short by a whisker. Such is life! With a year to go for the Olympic Games, the trio of Deepika Kumari, Rimil Buriuly and ...New Indian Express, 2 months ago
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