text:
|Publication number
|Publication type
|Application number
|Publication date
|21 Oct 1986
|Filing date
|1 Mar 1985
|Priority date
|1 Mar 1984
|Fee status
|Also published as
|Publication number
|Eberhard Esselborn, Jurgen Fock
|Original Assignee
|Th. Goldschmidt Ag
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (3), Referenced by (10), Classifications (11), Legal Events (6)
|External Links: USPTO, USPTO Assignment, Espacenet
R.sup.1 CH.sub.2 O--(C.sub.2 H.sub.4 O--).sub.n (C.sub.3 H.sub.6 O--).sub.m
R.sup.1 CH.sub.2 O--(C.sub.2 H.sub.4 O--).sub.n (C.sub.3 H.sub.6 O--).sub.m
R.sup.1 CH.sub.2 O--(C.sub.2 H.sub.4 O--).sub.n (C.sub.3 H.sub.6 O--).sub.m CH.sub.2 CHR.sup.3 CH.sub.2 --SO.sub.3 X
1. Field of the Invention
The invention relates to sulfonated polyoxyalkylene ethers of 1,2- or 1,3-diols, their preparation and use.
2. Description of the Prior Art
German Offenlegungsschrift No. 30 25 807 describes a process for the preparation of polyethers with retention of at least two free hydroxyl groups on the starter alcohol, the hydroxyl groups being separated from each other by, at most, three carbon atoms and the hydroxyl groups at the ends of the polyether chain being optionally reversibly blocked, yet stable to the conditions of acetal or ketal splitting, wherein
(a) an oxirane of formula: ##STR2## in which R1 represents a hydrogen radical or, optionally, a halogenated hydrocarbon group with 1 to 30 carbon atoms or the --CH2 OR2 group, in which R2 represents an alkyl or alkenyl group, the R1 groups within the polymeric molecule being the same or different, is added by addition reaction to a trihydric or multihydric alcohol, in which at least two hydroxyl groups are acetalized or ketalized;
(b) the hydroxyl group of the polyether monool obtained is blocked by reaction with a monofunctional compound which is reactive with respect to this hydroxyl group and stable to the conditions of acetal or ketal splitting; and
(c) the acetal or ketal is then split by the action of an acid.
In accordance with the disclosed process, the blocking of the hydroxyl group of the polyether monool obtained in step (a) can be achieved by reaction with a hydrocarbon halide. If allyl chloride or methallyl chloride is used as the hydrocarbon halide, compounds are obtained having a terminal olefinic double bond, at which further addition reactions can be carried out. Such compounds can be used in many ways. Particularly, such compounds can be used as modifying components in the preparation of polyurethanes or polyesters because of their hydroxyl groups in the 1,2- or 1,3-position of the starter alcohol.
Those compounds which have terminal polar groups are also of great interest, especially those which are stable to hydrolysis.
We have discovered novel compounds having the above characteristics and having a combination of structural elements which make possible their use as diol components in polyaddition reactions, in which they can be used by themselves or proportionally in addition to other polyols. More particularly, such compounds have the formula
R.sup.1 CH.sub.2 O--(C.sub.2 H.sub.4 O--).sub.n (C.sub.3 H.sub.6 O--).sub.m CH.sub.2 CHR.sup.3 CH.sub.2 --SO.sub.3 X
in which
R1 is ##STR3## R2 is CH3 --, C2 H5 --, or C3 H7 --, R3 is H-- or CH3 --,
X is H--, alkali metal or ammonium ion,
n is 0 to 100,
m is 0 to 50, and
n+m is not less than 1.
The compounds are liquid or waxy compounds depending on their oxyethylene and/or oxypropylene content. Their water solubility or water dispersibility is also a function of the oxyethylene or oxypropylene content.
The inventively prepared compounds have three structural elements which determine their properties:
1. The linear macromolecule has two reactive hydroxyl groups at one end which are linked to the starter alcohol and to which alkylene oxide is added by addition reaction;
2. The chain of the macromolecule is formed by oxyethylene and/or oxypropylene units; and
3. The polar SO3 X group, linked directly to carbon, is at the end of the macromolecule opposite to that holding the starter alcohol.
We have also discovered a method for preparing the inventive compounds wherein a compound having the formula HSO3 X is added in a known manner by a free radical reaction in the presence of catalysts and, optionally, at an elevated temperature, to compounds having the formula
R.sup.1 CH.sub.2 O--(C.sub.2 H.sub.4 O--).sub.n (C.sub.3 H.sub.6 O--).sub.m CH.sub.2 CHR.sup.3 ═CH.sub.2.
The starting compounds having allyl or methallyl groups are prepared according to the teachings of German Offenlegungsschrift No. 30 25 807. Starting compounds may be glycerin, trimethylolethane, trimethylolpropane or trimethylolbutane. In this process, firstly, two hydroxyl groups of the compounds are converted over a period of time at room temperature and in the presence of a drying agent into the corresponding acetal or ketal groups in an acid catalyzed reaction with an aldehyde, such as, for example, formaldehyde, acetaldehyde, propionaldehyde and butyraldehyde, or with a ketone, such as, for example, acetone, methyl ethyl ketone and methyl isobutyl ketone, so that only one reactive hydroxyl group is retained. This hydroxyl group is reacted by an addition reaction in the presence of a basic catalyst, such as, potassium or sodium methylate, under a pressure of 1 to 6 bar and at temperatures of 90� to 120� C. under nitrogen with ethylene oxide and/or propylene oxide in amounts such that the conditions for the subscripts n and m as well as for the sum of n+m are fulfilled. The polyoxyalkylene ether obtained is reacted under nitrogen at 80� to 120� C., and with removal of the hydrogen gas or the methanol with an alkali metal, such as, sodium or potassium or their alcoholates, such as, sodium or potassium methylate to form the corresponding alkali polyether. The alkali salt is then reacted with allyl or methallyl halide at 70� to 100 � C., the alkali halide formed is removed by filtration, and finally, the acetal or ketal is split by the action of an acid, such as, hydrochloric acid, sulfuric acid or phosphoric acid at about 80� C. By such a procedure, the starting material required for the inventive process is obtained.
The preparation of the starting compounds can be represented by the following reaction equations: ##STR4##
The reaction of this allyl and/or methallyl derivative with a compound having the formula HSO3 X is accomplished in a known manner. The addition reaction is described, for example, in Houben-Weyl "Methoden der organischen Chemie" (Methods of Organic Chemistry)., Vol. IX, page 380. Preferably, ammonium hydrogen sulfite is used. The radical addition proceeds in high yield in the presence of atmospheric oxygen and, if necessary, at moderately elevated temperatures up to 40� C. The addition reaction can be followed by the decrease in the concentration of double bonds as reflected in the iodine number, as well as by means of the elementary sulfur determination by the Carius method. The inventive process therefore proceeds according to the following reaction outline: ##STR5##
Sulfurous acid or an acidic alkali salt of sulfurous acid, especially sodium hydrogen sulfite, may also be used instead of ammonium hydrogen sulfite. Metal hydrogen sulfites, other than the alkali salts, are also usable, but generally are not employed because of their low solubility.
Because of their structure elements, the inventive compounds are particularly suitable for the preparation of modification of polyesters or polyurethanes. The properties of the polymeric polyaddition products, especially the properties of the surfaces, are affected in a desirable manner by these compounds. For example, it has surprisingly turned out that the adhesive properties of curable polyurethane-based adhesives are improved considerably, if the inventive compounds are used as the only polyol components or as a part of the polyol components. Moreover the combined shear and tensile strength and the floating roller peel strength of bonded sheets of aluminum are significantly improved.
The preparation of the inventive compounds, as well as the technical effects achievable through the use of the inventive compounds are described in greater detail in the following example.
Potassium methylate (7 g) is dissolved at 80� C. in 174 g (approximately 1 mole) of 2,2-dimethyl-5-ethyl-hydroxymethyl-1,3-dioxane in a reactor equipped for forced circulation. After it is carefully flushed with pure nitrogen, the reactor is heated to 110� C. and a mixture of 440 g (approximately 10 moles) of ethylene oxide and 440 g (approximately 7.6 moles) of propylene oxide is added at a rate, such that the internal temperature of the reactor does not exceed 120� C. and the pressure 3 bar. After all of the alkylene oxide has been passed into the reactor, the temperature is maintained at 120� C. until a constant pressure indicates the end of the reaction. Residual monomers are then removed under vacuum at 80� to 90� C.
After the reaction is completed, 50 ml of water are stirred into the product at 80� C. Subsequently, 30 g of a 30% phosphoric acid solution are added and the product is stirred for 0.25 hours and then adjusted to pH 7 with NaH2 PO4. The water is then distilled off at 80� to 90� C. in a vacuum of 10 torr and the product is filtered using 10 g of a silicate based filter aid.
The hydroxyl number of the product obtained is 58.4 which corresponds to a molecular weight of about 960.
To 960 g (approximately 1 mole) of the polyether obtained, which has been carefully dried once again, 24.2 g (approximately 1.05 moles) of sodium metal are added in small portions at 120� C. under stream of nitrogen. At the end of this addition, heating is continued for a further 2 hours. The product is then cooled to about 50� C. and 80.3 g (approximately 1.05 moles) of allyl chloride are added dropwise over a period of 1/2 hour. The temperature is then raised once again to 120� C. The precipitated salt is filtered off after addition of a filter aid.
From the iodine number, determined by the method of Hanus, the conversion of the condensation reaction is estimated to be 98.8% and the hydroxyl number is 1.4.
The ketal ring of the polyether is split by heating the polyether, mixed with 1N hydrochloric acid and ethanol in a weight ratio of 1:1:1, for 8 hours under reflux. At the end of the splitting reaction, the reaction mixture while still hot, is neutralized with 50% aqueous sodium hydroxide. All volatile components are subsequently distilled off at a temperature between 70� and 80� C. and a vacuum of 10 torr. Again, the salt produced is removed completely by filtering hot using a filter aid.
The hydroxyl number of the polyether obtained is 109.
The product obtained in (A) (960 g, approximately 1 mole) is dissolved in 1,000 ml of a mixture of 5 parts by weight of water and 1 part by weight of ethanol. A solution of 149 g (approximately 1.5 moles) of ammonium hydrogen sulfite in 300 ml of water, as well as 50 ml of a 25% aqueous solution of ammonia are added with vigorous stirring in the presence of air over a period of 2 hours. After allowing the reaction to continue for a further 2 hours, the water and ethanol are removed at a temperature of 60� to 80� C. and a vacuum of 10 torr and the precipitated excess ammonium hydrogen sulfite is filtered off with the help of a filter aid.
The reaction yield, calculated from the iodine number of the product obtained, is 89.5%. The reaction yield, calculated from the total sulfur value as determined by the Carius method is 91.5%.
The hydroxyl number obtained after the ammonium sulfonate was converted into the corresponding sodium sulfonate, is 101.
A polyurethane-based adhesive is prepared from a polyol component of the following composition:
23 parts by weight of sulfonated 1,3-polyetherdiol as prepared in Section B;
17 parts by weight of a hydroxy-functional polyacrylate;
2 parts by weight of a propoxylated bisphenol A.
The hydroxy-functional polyacrylate is obtained by copolymerizing 80 g (approximately 0.63 moles) of n-butyl acrylate, 15 g (approximately 0.17 moles) of vinyl acetate and 5 g (approximately 0.04 moles) of 2-hydroxyethyl acrylate in the presence of 2.2 g (approximately 0.03 moles) of 2-mercaptoethanol and 0.3 g of azobisisobutyronitrile, as described in German Offenlegungsschrift No. 30 47 926.
The propoxylated bisphenol A is obtained by alkoxylating 228 g (approximately 1 mole) of bisphenol A with 203 g (approximately 3.5 moles) of propylene oxide in the presence of 20 g of potassium methylate at 125� C. in an autoclave as described in German Offenlegungsschrift No. 31 23 059.
A mixture of 96 parts by weight of a conventional commercial aliphatic triisocyanate, having the approximate structure ##STR6## and an NCO content of 22 weight percent, and 2 parts by weight of γ-glycidylpropyltrimethoxysilane is used as polyisocyanate component.
The molar ratio of hydroxyl groups to isocyanate groups in the adhesive mixture is 1:1.
The combined tensile and shear strength and the floating roller peel strength are determined in accordance with DIN 53 455 and DIN 53 289, respectively. For this purpose, two 0.5 mm thick aluminum sheets of the Al Cu Mg 2 pl alloy which have been pretreated with chromic acid, are glued together. The following values are obtained: combined tensile and shear strength--2.8 [N/mm2 ]--and floating roller peel strength--3.2 [N/mm].
In a comparative test, the sulfonated 1,3-polyetherdiol is replaced by an α,ω-polyetherdiol and an unsulfonated 1,3-polyetherdiol having a corresponding composition and molecular weight, as well as by two mixtures of sulfonated 1,3-polyetherdiol and α,ω-polyetherdiol. The adhesive obtained is tested in the manner described above. The results of this test are given in the following table.
TABLE______________________________________ Combined Floating Ratio of the Tensile Roller Components and Shear PeelDiol α,ω-Polyetherdiol/ Strength StrengthComponent 1,3-Polyetherdiol [N/mm.sup.2 ] [N/mm]______________________________________α,ω-Polyetherdiol 100/0 1.8 1.31,3-Polyetherdiol 0/100 1.1 0.6Sulfonated 1,3- 0/100 2.8 3.2polyetherdiolMixture of α,ω- 66/34 1.9 2.0polyetherdiol/ 34/66 2.0 1.9sulfonated 1,3-polyetherdiol______________________________________
The increase in bond strength due to the sulfonate group of the sulfonated 1,3-polyetherdiol is clear. The combined tensile and shear strength and the floating roller peel strength are increased by factors of about 2.5 and 5.3, respectively, relative to the adhesive, which had been prepared with the unsulfonated 1,3-polyetherdiol. Moreover, the increase in the floating roller peel strength in comparison to the adhesive based on the α,ω-polyether diol is surprising. If anything, the opposite result should have been expected here, because of the lower molecular weight of the main chain of the macromolecule.
|Cited Patent
|Filing date
|Publication date
|26 Sep 1966
|8 Jun 1971
|Celanese Corp
|Linear polyester polymers containing alkali metal salts of sulfonated aliphatic compounds
|10 Mar 1969
|13 Jul 1971
|Celanese Corp
|Linear polyester polymers containing alkali metal salts of sulfonated aliphatic compounds
|18 May 1973
|22 Apr 1975
|Bayer Ag
|Salts of 3-hydroxy-2-hydroxymethyl-propane-sulfonic acid-1
|Citing Patent
|Filing date
|Publication date
|29 Sep 1989
|22 May 1990
|Th. Goldschmidt Ag
|Polyoxyalkylene ether having hydroxyl and sulfonate groups and their use in the preparation of dispersable polyurethanes
|19 Jan 1990
|19 Mar 1991
|Th. Goldschmidt Ag
|Polyoxyalkylene ethers having hydroxyl and sulfonate groups and their use in the preparation of dispersible polyurethanes
|11 Jul 1991
|27 Apr 1993
|Ppg Industries, Inc.
|Aqueous emulsion polymers prepared with crosslinkable non-ionic surfactants
|9 Nov 1992
|14 Sep 1993
|Ppg Industries, Inc.
|Thermosetting waterborne coating compositions prepared from aqueous emulsion polymers
|4 Dec 1992
|22 Mar 1994
|Ppg Industries, Inc.
|Ethylenically unsaturated poly(alkyleneoxy) surfactants
|17 Sep 1993
|16 May 1995
|The Procter & Gamble Company
|Sulfonated poly-ethoxy/propoxy end-capped ester oligomers suitable as soil release agents in detergent compositions
|18 Dec 2002
|3 Jul 2003
|Clariant Gmbh
|Olefinically unsaturated ether carboxylic acids and their use in emulsion polymerization
|19 Dec 2001
|12 Feb 2004
|Ulrike Hees
|Use of poly (meth) acrylate units containing suphonate groups in binding agents for magnetic storage media
|16 Jun 1989
|28 Dec 1989
|Ppg Industries, Inc.
|Polymerizable surfactant
|29 Nov 2002
|5 Jun 2003
|Perstorp Specialty Chemicals Ab
|Process for alkylation of an alkoxylated mono di, tri or polyhydric compound
|U.S. Classification
|562/110, 524/381
|International Classification
|Cooperative Classification
|European Classification
|1 Mar 1985
Owner name: TH. GOLDSCHMIDT AG, GOLDSCHMIDTSTRASSE 100, 4300 E
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:ESSELBORN, EBERHARD;FOCK, JUERGEN;REEL/FRAME:004378/0633
Effective date: 19850212
|13 Apr 1990
|Fee payment
Year of fee payment: 4
|7 Apr 1994
|Fee payment
Year of fee payment: 8
|12 May 1998
|Maintenance fee reminder mailed
|18 Oct 1998
|Lapse for failure to pay maintenance fees
|29 Dec 1998
|Expired due to failure to pay maintenance fee
Effective date: 19981021


text:
Michael Kors Designer iPad and iPhone Cases
Michael Kors iPad and iPhone Cases: A Bit Pricey But Beautiful
Take note gadget fashionistas: the Michael Kors collection for Apple ($80 - $130) is here, and it's beautiful. Coming with three designs each for your iPad and iPhone, all six clutches and cases come in soft leather with python, gold, or metallic accents to suit your high-end fashion palette. My favorite has to be the Python iPhone 4 Wallet Clutch ($80), which not only stores your cell in soft leather but even has room for credit cards and ID, so you can leave your big day-to-day tote at home for a sleek night out on the town.
Plus, there's room for your headphone jack and charging cables, so you'd almost never have to take it out of the case. Except to talk maybe? Holding up that big clutch to your face would be kinda awkward. Check out more pics of each case when you read more.

subset: commoncrawl


text:
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NFL Network's Reggie Bush believes that Buffalo Bills running back LeSean McCoy and Kansas City chiefs running back Kareem Hunt will have a big week this week.
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Kareem Hunt has fallen off after a hot start, but he can get back on track against Buffalo
The Buffalo Bills and the Kansas City Chiefs are both going in the wrong direction. The Bills have fallen to 5-5 and are in the midst of a three-game losing streak...
Buffalo Bills coach Sean McDermott could have stubbornly stuck to his guns and trotted out overwhelmed rookie quarterback Nathan Peterman.
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NFL Network's Brian Billick and Shaun O'Hara discuss the Week 12 matchup between the Buffalo Bills and Kansas City Chiefs.
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NFL Network Insider Ian Rapoport and NFL Network's Mike Garafolo discuss whether Buffalo Bills quarterback Tyrod Taylor will be the starter for the rest of the season.
Buffalo Bills running back LeSean McCoy comments on quarterback Nathan Peterman.
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Buffalo Bills receiver Kelvin Benjamin was carted off the field early in Sunday's game against the Los Angeles Chargers , but he appears to have avoided any ligament damage in his knee, according to Mike Rodak of ESPN...
If the definition of insanity is trying the same thing over and over again and expecting a different result (an oft-repeated aphorism of questionable provenance, one must add)—then consider the Buffalo Bills insane. By now pretty much the whole of the football-watching world will know that the Bills
NFL Network's Deion Sanders and LaDainian Tomlinson reenact the conversation between Buffalo Bills head coach Sean McDermont and quarterback Tyrod Taylor.
Chargers quarterback Philip Rivers has a big bounce-back game against the Buffalo Bills after clearing concussion protocol earlier in the week. "It was the prudent thing to do," the veteran said of telling the Chargers of his concussion symptoms.
Los Angeles Rams cornerback Casey Hayward felt ''a little disrespected'' that the Buffalo Bills decided to let rookie quarterback Nathan Peterman make his first career start against their defense. The Chargers gave Peterman a forgettable introduction to the NFL, intercepting him five
Nathan Peterman struggled on his first NFL start, but he may get another chance for the Buffalo Bills.
The Buffalo Bills have one of the strangest quarterback controversies the NFL has had in a while.After Nathan Peterman threw five interceptions in the first half of his first career start and was replaced by Tyrod Taylor, Bills coach Sean McDermott said the two quarterbacks will both be evaluated this
Nathan Peterman's first NFL start for the Buffalo Bills was going just fine until his third pass deflected off his receiver's hands. It was snatched by the Chargers' Korey Toomer, who took it back for a touchdown.
The Buffalo Bills have been trying to survive without established receivers all season long, and the latest injury to Kelvin Benjamin only makes things more difficult for this offense...
Watch the best plays from the Week 11 match up between the Buffalo Bills and the Los Angeles Chargers.
Buffalo Bills head coach Sean McDermott had his eyes on the future when he elected to start rookie Nathan Peterman at quarterback for Sunday's 54-24 loss to the Los Angeles Chargers , but the future may apparently be over after one contest...
Buffalo rookie Nathan Peterman throws five interceptions -- in the first half -- and is replaced by the man he replaced, Tyrod Taylor, in the free-falling Bills' 54-24 loss to the Chargers.
Buffalo Bills quarterback Tyrod Taylor takes it in himself for a 2-yard rushing touchdown.
Yahoo Sports Fantasy Football expert Liz Loza offers some words of encouragement to owners of Bills players, despite Buffalo's five-INT debacle against the Chargers.
Buffalo benched rookie quarterback Nathan Peterman coming out of halftime after the Bills fell behind 37-7, thanks to a quintet of first-half turnovers.
Buffalo Bills quarterback Nathan Peterman threw more interceptions in the first half of Sunday's game against the Los Angeles Chargers than Tyrod Taylor did in Buffalo's first nine contests of the season...
In his first career start, Buffalo Bills rookie quarterback Nathan Peterman struggled mightily against the Los Angeles Chargers.
Buffalo Bills wide receiver Kelvin Benjamin was carted off the field in the first quarter of Sunday's game against the Los Angeles Chargers. The team announced that he would not return for the rest of the game due to a knee injury.Benjamin went down after completing a 20-yard catch from quarterback
Buffalo Bills wide receiver Kelvin Benjamin was ruled out for the remainder of Sunday's game against the Los Angeles Chargers with a right knee injury suffered on the opening drive. Benjamin was carted off to the locker room.
Buffalo Bills wide receiver Kelvin Benjamin suffered a knee injury early in Sunday's game against the Los Angeles Chargers and will not return...
The Buffalo Bills may have benched quarterback Tyrod Taylor , but don't expect them to move on this offseason without compensation...
NFL Network Insider Ian Rapoport has the latest on the Buffalo Bills decision to bench quarterback Tyrod Taylor, and the Minnesota Vikings plans for quarterback Teddy Bridgewater.
NFL Network's Marshall Faulk breaks down how the Minnesota Vikings offense has been able to adjust as the season has progressed, and how Buffalo Bills running back LeSean McCoy can bounce back.
1. The Buffalo Bills have changed quarterbacks. I have thoughts about that, and I have transferred those thoughts to the printed word. But first, because it all ties in, a quick look at the AFC playoff race.It is technically true that Buffalo is in a playoff race. If Jerry Jones decided the regular season
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Leighton Meester in Diane von Furstenberg Coat, Milly Skirt
Celeb Style: Leighton Meester
Queen B, Leighton Meester, waved to adoring fans while shooting an episode of Gossip Girl in NYC. The stylish socialite shielded herself from the Winter chill in a colorful layered ensemble — green Diane von Furstenberg coat, hot pink Autumn Cashmere scarf, and green suede gloves. We paired her plaid Milly skirt with a sequin Alice and Olivia sweater and calf-hair Alexander McQueen tote. Thick black tights and multitextured Casadei pumps completed Leighton's luxe look. Snag her coat, skirt, and other similar items now.
Image Source: Bauer-Griffin Online


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It's Friday! So I express this particular post from a philosophical angle as well as technical. And there will be plenty more of these in the future coming from me. It's an opinion from my personal experience as a developer from assembly to C#, nothing more, not from Microsoft or any other source. As developers we gain experiences that transcend trends and changes from other aspects such as programming languages which will continue to change and evolve for the better, for the most part. These aspects we can potentially carry into any programming environment as is currently understood and has been over the past few decades.
So in my 25 years as a software developer, I had a lot of experience with commenting and not commenting source code.
The good thing about comments is they explain the code, in ways that code cannot. However...
The bad thing about comments is often, we can use variable names, method names, class names, namespaces, filenames, folder names etc., that reflect what the code does instead. This enables us that drilldown experience. Furthermore, if you are putting comments in your code and change the code, you may also have to change the comments if applicable, that's extra work. Worst still, change the code and not the comment when it should, we are now out of sync with the code, now we have a problem for future developers who may take over on the code base that you are working on. If you spend time to think about the organization of the code and the flow upfront or refactor as you go along, fewer comments are actually required. After all as developers we prefer to write code, not comments. As developers we prefer to read code, not comments, if the code is well written.
In today's era, if you marry this notion with work items or change requests, then these are often contextual through a bug or task which can change without having an affect on the code. As I see it, if we can see a ChangeSet in TFS, for example, in which the change and the work item (bug, task, operational issue etc.) that was resolved within context to the code change, the requirement for comments in code is reduced even more so. Annotations in TFS help here, but that's another topic, I'll sometime cover soon.
I see comments as a last resort, only needed if it can't already be expressed by the code or through a change request which accompanies the check-in along with something along the lines of a work item.
In my experience, as I moved on in my career as a developer, I focused more on folks being able to understand my code and less on the comments. I spent more time thinking about meaningful names for variables etc and the design of the code.
Some of the best code I've seen, is where there were very few comments, the code was elegantly written, highly maintainable and self-explanatory to someone else looking at it with minimal comments. The most understandable code I saw over 25 years had very few comments. And even then, that was going back to the 1980's and 1990's without work items and Change Sets. Organize the project structure, files, namespaces, classes, methods and variables upfront, means less comments. No more comments on this topic from me. Apologies for the large comment in this blog.


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Bemidji's Josefson a leader on St. Cloud State women's hockey team
Bemidji native Courtney Josefson was recognized in the starting lineup at last Friday's hockey game between St. Cloud State and Bemidji State at the Bemidji Regional Event Center.
The St. Cloud State senior is an alternate captain for the Huskies and took some time after the game to reflect on her time at college and playing at Bemidji's newest hockey rink - just a few blocks from where she skated as a standout for the Lumberjacks.
"This place is amazing," Josefson said. "It's great to be able to come home and walk into our local rink and take it all in. It's such a different world than (Nymore Arena). It's just so new and nice."
Josefson is a 2007 graduate of Bemidji High School and was the Lumberjacks captain that season. She was a three-sport athlete for BHS and hockey was her strong suit. She scored 110 points during her high school career.
Her role has grown each year on St. Cloud State's team.
"It's been a pretty positive experience," Josephson said. "I'm a defensive forward here and I'm more of a role player on this team. It's been rewarding and I've been able to grow as a person."
Josefson's first collegiate goal came as a freshman against Minnesota during a season where she played in eight games.
As a sophomore, she played in all 37 games for the Huskies during a season where she was named a WCHA Scholar Athlete and a WCHA All-Academic player.
She played in 33 games last season during another WCHA Scholar Athlete and All-Academic season.
The points may not be coming as easy as they did during high school, but Josefson is an integral part of the team. She was named one of the captains in a process decided by a team vote.
"She's one of the hardest working players we have on our team," SCSU coach Jeff Giesen said. "She's done everything we could ever ask of her. She'll probably be the first to admit she's not the most skilled player on our team, but her heart is as big as anyone on the team."
Josefson is a physical education and health major and is currently in her student teaching track in Sartell.
"They call me Mrs. Josefson now," she joked. "I'm not quite used to that yet."


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Apple v. Samsung Appeal Ruling Huge Win For Design Patents
The Federal Circuit issued its opinion in Apple v. Samsung today—it is a win for Apple and a HUGE win for design patents. The Court affirmed the design patent damage award, and confirmed that in design patent cases, an award of total profits is proper. The Court explicitly rejected Samsung's argument that damages should have been limited to the profit attributable to the infringement because of "basic causation principles," and also explicitly rejected Samsung's call for damages based only on some smaller "article of manufacture," rather than the entire product. This is a huge win for industrial design and design patent IP!
Special Thanks to all who worked with us on, or signed the briefs. They obviously had a major impact. Sometimes the system works.
Article describing the ruling in detail: http://patentlyo.com/patent/2015/05/samsung-design-patents.html
Transcript of the ruling: http://patentlyo.com/media/2015/05/Apple-v-Samsung.pdf
Articles of Interest by Charles L Mauro
A List of All Amicus Briefs Filed
Apple v. Samsung: Impact and Implications for Product Design, User Interface Design (UX), Software Development and the Future of High-Technology Consumer Products
An Open Letter in Response to CNET's Larry Downes' Deceptive Article "Fighting over scraps in Apple's withering patent war with Samsung" Related to the Recent Filing of Amicus Briefs in Affirmance


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Hey, I'm going to Oahu during the summer and looking to do some surfing. I'm a begginer- intermidate. I understand the basic surfing ettiquette (don't drop in on others, etc.) I'm looking to shortboard. Is there any spots i can go where it's not super crowded and where i can get some good rides. Im staying on the south shore, and the west shore.
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Diana Containerships Inc., a global shipping company specializing in owning and operating containerships, has announced that yesterday it signed, through a separate wholly-owned subsidiary, a Memorandum of Agreement to sell to an unaffiliated third party the 1990-built vessel Maersk Malacca (renamed "Malacca") for demolition, with delivery due to the buyers by early June 2013, for a sale price of approximately US$10.3 million before commissions.
Upon completion of the sale of m/v Maersk Malacca and m/v Maersk Madrid as previously announced, Diana Containerships Inc.'s fleet will consist of 9 Panamax container vessels. A table describing the current Diana Containerships Inc. fleet can be found on the Company's website, www.dcontainerships.com. Information included on the Company's website does not constitute a part of this press release.(Reuters)


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23.3-mile aqueduct the key to Front Range development
By Bob Berwyn
SUMMIT COUNTY — As much as we here in the high country like to grumble about "our" water going to the Front Range, the diversions are one of those facts of life that isn't going to change anytime soon.
And while Dillon Reservoir is the visible symbol of that reality, that water wouldn't be going anywhere without the Harold D. Roberts Tunnel, a 23.3-mile aqueduct that carries the water under the Continental Divide, as deep as 4,500 feet below the spine of the continent.
In Park County, the water empties into the South Platte River, feeding the Front Range Reservoirs that have enabled Denver to grow into a thriving metropolis at the cusp of the Great Plains and Rocky Mountains. Water diverted from the Blue River Basin in Summit County provides nearly 40 percent of Denver Water's supply.
The tunnel turns 50 this year, and Denver Water is commemorating the birthday with an invitation-only two-hour ceremony at the Roberts Tunnel headquarters near Grants. Denver Water employees, retirees who worked at the tunnel and Park County commissioners will take a journey through the history of the Roberts Tunnel, with presentations and discussions highlighting the past 50 years.
At the time the tunnel was built, it was the third-longest water supply tunnel in the world, behind the 96-mile Thirlmere Aqueduct (completed in 1925) that supplies water to Manchester, and the 85-mile Delaware aqueduct that brings more than 500 million gallons of water per day from upstate reservoirs to New York City.
Denver Water engineer Erik Holck said the Roberts Tunnel is still in great shape on its golden anniversary. Major infrastucture projects are often built to last 100 to 200 years, but with good maintenance, Denver Water expects the Roberts Tunnel to last indefinitely.
Holck said Denver Water spent several years studying different alignments for the tunnel, which cost $40.4 million in 1956 dollars, the equivalent of $340 million in 2012.
The Roberts Tunnel was built without the massive drill machines commonly used in tunneling today. Some of the biggest challenges included keeping water out of the work area while tunneling was in progress. The complex faults and joints in the Rockies allowed a lot of water to flow into the tunnel, Holck said.
Learn more about the history of Denver Water at this website.


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Martini Gold
75cl / 18%
Dolce & Gabbana
Not Available
This product is currently out of stock
Enter your email address below, you will be notified when this product is available.
Martini Gold is an exciting blend of botanicals sourced from around the world to create a unique flavour, in packaging designed by fashion house Dolce & Gabbana. The taste of Martini Gold is described by the producers as naturally distinctive, with fragant lemon, deep, zesty orange and rich exotic spices such as saffron, ginger and myrrh.
Allergen InformationThis product may contain the following:
- sulphur dioxide and sulphites at concentrations of more than 10mg/kg or 10mg/l
Martini Gold Reviews
3 Customer Reviews
I think it is one of the best drinks I''ve ever had. I have many high priced bottles, but I love it so much I got two...
I drink it evey day, fantastic drink. I'll buy it again.
Truthfully i bought this drink for its bottle as i think it looks lovely, however it the taste is somewhat amazing!


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We hope we're not too late with this and that you still have a few baggies of Thanksgiving leftovers in the fridge, because our mailbag has a few letters regarding the use of white bread in making leftover turkey sandwiches.
Belmont Shore queenpin Dede Rossi wrote in with a plea to "Please don't eat the white bread. Try Pandor Bakery in the Shore. You will love the bread."
And reader James Mitchell wants to know if it's "possible to substitute a good rye bread? It has a lower glycemic index and better for my Type II diabetes."
Well, obviously you can use anything you want. Pumpernickel, slabs of fried chicken breasts, lettuce leaves. But for leftover turkey sandwiches, there is no substitute for white bread. The whitest, least nutritional white bread you can find. Shouldn't be more than a buck and a half for the whole loaf, the balance of which, after you make your sandwich, you should throw out and go back to tastier, more healthful bread.
Lots of confusion issues in the mailbag this week. We got a call from a man who didn't leave his number, regarding our mention of a Best Buy Christmas commercial that was filmed at a house on Country Club Drive in the Los Cerritos neighborhood in Long Beach.
"You know, somebody's a little confused. Country Club Drive is not in Long Beach. It happens to be in the city of Lakewood. I live on Country Club Drive. I didn't know if that was a typo; just thought I'd point it out."
Yes, there is a Country Club Drive in Lakewood. This country is littered with Country Club drives. Our guy should stay away from the one in Long Beach unless he wants to be crippled with buyer's remorse.
Our column about our youthful, third-grade confusion over our conservative parents' sadness over the assassination of President Kennedy confused reader Ron Moore (we think) who came away from our column with the impression that our parents were "not that sad" about the killing. It was only we who weren't that sad and it was because we were young and had grown up listening to how horribly wrong Kennedy was for the country, but, naturally, our parents were sad about his killing. Moore wrote about the memories of older writers in the paper that day and that he felt those feelings "were more of a reflection of the majority of people in the country."
Well, yes, of course, if they weren't crazy mixed-up children at the time. Reader Steve Grzesik writes, "Unlike you, I grew up in a house where my Irish Catholic mother idolized JFK. My biggest confusion at the time was why the assassination coverage and the various on-air tributes and funeral services that came on the following days had to pre-empt 'Heckle & Jeckle.' I remember getting in trouble for stating that Caroline and John-John were really showing their grief over missing the magpie cartoons as I was."
Finally, our column about our beloved Grandma Bet and her Thanksgiving feast she made for us one year managed to slide through with no howls of protest. Even our buddy Dimwit, who calls in constantly to urge us to read about the evils of liberalism, called in on Thanksgiving with, "Hey, I just read your column. It really touched me. What a nice column. Have a Happy Thanksgiving."
Thanks, Dimwit. We did.
Contact Tim Grobaty at 562-714-2116, firstname.lastname@example.com, @grobaty on Twitter.


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After thrilling audiences in its debut season, the hit CBS drama Under The Dome returns for a second season tonight at 10pm with even more twists and suspense than the first. Joining us on the phone to talk about the new season is actor Mike Vogel, who plays Dale "Barbie" Barbara on the show.
"Tonight's the big night. We're hoping we can hold everyone's attention again and we get into some really cool stuff here," Mike teased. "Taking off in the first episode, Stephen King wrote it, and has a little cameo in it himself. This season, stuff just keeps getting bigger and more chaotic for everyone in the town."
What kind of twists can we expect on the show? Well, right off the bat, Under The Dome says goodbye to two of its recurring characters.
"We kill off two very beloved characters. We gain two more and then a lot of other fun people join us throughout the year," Mike said.
On tonight's season premiere, "Heads Will Roll," Barbie's fate lies in Big Jim's hands, and the Dome presents a new threat when it becomes magnetized. Meanwhile, Julia seeks out the help of a stranger to save the life of a mysterious girl who may hold clues to origin of the Dome.
For those just getting into the show this season, Mike gave a quick run down of what happen in the first season to get you up to speed.
"A town in Chester's Mill, a dome comes down over top the town unexpectedly and the whole town is kinda of thrown into this chaos and panic on 'why is it here, how do we get out,'" he explained. "I like to say, the dome is just a device to see how people are going to react to a situation like that."
With so many people both inside and outside of the dome trying to figure out why it's there, Mike tells us that this season answers "a lot of those questions" that have left us wondering and hanging in suspense.
Plus, viewers will get to see a cameo from the creator of the Dome itself, Mr. Stephen King. Mike told us what it was like meeting the iconic horror novelist in person.
"He's as normal of a guy you'll ever meet, which is what scares me even more because a guy that is that normal and yet we see the stuff that comes out in his writing – I don't even want to know what's going on upstairs in his head, it's gotta be pretty dark," he joked.
Tune in to find out what happens next on Under The Dome tonight at 10 on CBS. Listen to our complete talk with Mike Vogel in the clip below.


text: Hi! My name is Krystal (26) and I have been lurking the DIS boards for a long time. I am a closet Disney freak and like to live through others on this board. I've been to Disney World several times and Tokyo Disneyland as a kid. I have also visited Disneyland in 2009, 2011, and 2012. My DH (29) has only gone once while he was in AF tech school and didn't really get to enjoy the parks. My daughter (5) is showing her Disney obsession lately since she pretends to fly to Disneyland and questions any money spent, asking if we are still saving for Disney. My son (3) is a huge Toy Story fanatic and likes to pretend with his sister. Anyways, the boards have been a great resource and is my way of escaping by planning our trip


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Saturday, January 30, 1999 Published at 07:26 GMT
World: Europe
England manager in row over disabled comments
Disabled groups in Britain have called for the resignation of the England football manager, Glenn Hoddle, after controversial comments he's reported to have made about disabled people.
Hoddle is quoted by The Times newspaper as saying that people born with disabilities may be paying for sins committed in a previous life.
He's accused the Times of a scandalous and disgraceful interpretation of his comments.
The English Football Association gave him its backing, saying he was an excellent supporter of disabled sportspeople.
It's not the first time the England manager's spiritual beliefs have provoked controversy.
Last year he was criticised over his use of a faith healer for the England team in the run-up to the World Cup.
From the newsroom of the BBC World Service


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Your donations keep RPGWatch running!
Risen 2 - Air Temple DLC Released
by Dhruin, 2012-05-27 01:33:35
Nikus points out the Air Temple DLC for Risen 2 is now available on Steam for $9.99 - here's the blurb:
Gargoyles have infested the world of Risen 2: Dark Waters. Explore the mysterious Air Temple to uncover the mystery that surrounds it as you embark on an extensive new quest. Explore and discover an additional island with new characters, quests and enemies with up to 8 hours of additional playtime.
Newsbit options: Add / View Comments (22) | Forward this newsbit | Link to this Newsbit
Information aboutRisen 2
SP/MP: Single-player
Setting: Fantasy
Genre: Action-RPG
Platform: PC, Xbox 360, PS3
Release: Released


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Gas-Trak Online (GTO)
With GTO managing your F-Gas refrigerant usage has never been easier. Complete with handy features, GTO is a fast and simple cylinder management F-Gas reporting solution which can be used on the move. GTO comes complete with two interconnecting elements: The Desktop Web Portal and The Mobile App.
Web Portal: Acting as the central control point, the Desktop Web Portal enables users to manage their accounts, customers, jobs and cylinder fleet and view all data in one place, producing useful analysis and cylinder tracking functionality.
App: Available in Android and iOS, the GTO App is a great tool for engineers to enter data whilst on the move. The App automatically syncs with the Web Portal, ensuring real-time data is available to the office at any point.
GTO Marketing
GTO Customers
GTO Jobs
GTO Reporting


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South Plains voters have just learned what the electorate in the Panhandle found out a couple of months ago.
Wherever there are contested legislative races mega donors from out of the area insert themselves into those races.
For those who missed the stories in the Avalanche-Journal, as of Tuesday Houston homebuilder Bob Perry, the most generous donor in Texas in more than a decade, had given a combined $70,000 to the campaigns of all four Republican candidates in the two legislative races in the South Plains.
Perry had given $20,000 to the campaign of Lubbock businessman John Frullo, who is running for the open seat in District 84, and $15,000 to former Texas Tech regent Mark Griffin, Frullo's opponent.
Perry also gave a $20,000 check to Charles Perry (no relation), who is challenging longtime state Rep. Delwin Jones in District 83, and $15,000 to Jones, too.
For Bob Perry, this is the second time this year he inserts himself in West Texas legislative races.
In February he gave $65,000 to Amarillo restaurant owner Victor Leal, who ran unsuccessfully in the March 2 Republican primary for the open seat in District 87.
And the way it looks, Perry may get involved in a West Texas race again.
For people not keeping track of all legislative races in the region, in the fall the South Plains is likely to have another heated race, in District 85.
Plainview Republican Jim Landtroop is running against incumbent Joe Heflin, D-Crosbyton, just like he did in 2006 when both men were vying for what was then an open seat.
Republican operatives, with the help of donors such as Perry, who give mostly to GOP candidates, have promised to help Landtroop, just like they did four years ago.
Heflin is one of about half-dozen Democratic incumbents the Republican Party has long targeted for defeat because they represent GOP-majority districts.
The only question now is whether Perry will be the only mega donor giving money to area candidates.
This is the $64,000 question because he is the only wealthy donor in recent years still giving millions of dollars to Texas Legislature incumbents as well as to statewide office holders and to some challengers and candidates for open seats.
All others are not giving as much as they used to, or, have recently died.
James Leininger of San Antonio, for example, who in 2006 virtually bankrolled some candidacies, including more than half million dollars to Van Wilson of Lubbock, one of two challengers Jones faced in that year's Republican primary, has been pretty much missing in action.
As of Tuesday, Leininger had given only $5,000 for the year. And last year he gave only $50,000 to Gov. Rick Perry and $1,000 to a candidate in another race.
And then there is Charles Butt, the San Antonio supermarket mogul who in the past has also given millions of dollars to other state office holders and open seat candidates.
As of Tuesday, Butt had given a total of $83,500 for the year, including $5,000 to Griffin and $2,500 to Jones.
Like Perry, most of Leininger's money has gone to Republicans. Butt, on the other hand, gives to Democrats and Republicans.
Fred Baron of Dallas and John O'Quinn of Houston, who used to give generously to Democrats died, in 2008 and last year respectively.
In all, even if Perry is the only mega donor in West Texas races, big money is going to be part of the story, just like it is in other contested races in the state.
ENRIQUE RANGEL is A-J Austin bureau chief. Address comments to email@example.com or P.O. Box 12457, Austin, TX 78711-2457.
© 2017. All Rights Reserved. | Contact Us


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Gerald Shulman, MD, PhD, FACP, FACE received the Frontiers In Science Award at the AACE 21st Annual Scientific & Clinical Congress in Philadelphia, on May 27, 2012.
Gerald Shulman, MD, PhD, FACP, FACE received the Frontiers In Science Award at the AACE 21st Annual Scientific & Clinical Congress in Philadelphia, on May 27, 2012.
The Frontiers In Science Award is given to an individual who has demonstrated exemplary contributions to their individual profession or area of expertise.
"I am delighted and honored to be selected as this year's recipient of the Frontier of Science Award from the American Association of Clinical Endocrinologists," Dr. Shulman said.
Dr. Shulman completed his undergraduate studies in biophysics at the University of Michigan with high honors and distinction, and he received his M.D. and Ph.D. degrees from Wayne State University School of Medicine. Following internship and residency at Duke University Medical Center, Dr. Shulman did an endocrinology fellowship at the Massachusetts General Hospital/Harvard Medical School and additional postdoctoral work in molecular biophysics and biochemistry at Yale University before joining the faculty at Harvard Medical School. He was subsequently recruited back to Yale and has remained there ever since. Dr. Shulman has pioneered the use of magnetic resonance spectroscopy to non-invasively examine intracellular glucose and fat metabolism in humans and using this approach he has conducted ground breaking basic and clinical investigative studies on the cellular mechanisms of insulin resistance in humans that have led to several paradigm shifts in our understanding of type 2 diabetes. Dr. Shulman has authored and co-authored over 340 peer-reviewed publications, and he has also trained more than 60 postdoctoral fellows and graduate students, many of whom now direct their own independent laboratories around the world. Dr. Shulman has been elected to the Association of American Physicians, the Institute of Medicine and the National Academy of Sciences.
Dr. Shulman's biography and high resolution photo are available here.
About the American Association of Clinical Endocrinologists (AACE)
AACE is a professional medical organization with more than 6,500 members in the United States and 91 other countries. AACE members are physicians who specialize in endocrinology, diabetes and metabolism. For more information about AACE, visit our Web site at www.aace.com, become a fan on Facebook at www.facebook.com/theaace or follow us on Twitter at www.twitter.com/theaace.


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OTTAWA (Reuters) - New home prices in Canada climbed 0.3 percent in June following a 0.4 percent advance in May, an increase which matched analysts' expectations, Statistics Canada data indicated on Thursday.
Prices rose in eight metropolitan regions, fell in three and were flat in 10.
The Toronto and Oshawa region contributed the most to the June increase with prices jumping by 0.8 percent on good market conditions. Winnipeg was just behind with a 0.7 percent advance prompted by higher costs for materials.
The most significant price decline was in Calgary, where prices dropped by 0.3 percent as some builders offered promotional pricing to generate sales.
Year on year, prices were 2.1 percent higher in June, the 18th consecutive rise.
Reporting by David Ljunggren, Editing by Chizu Nomiyama


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I am quite please with the intricate detail, clean cuts and delicate appearance of this piece. It is not fragile but thin enough to not bulk up a scrapbook page. I will happily buy any of these Kaisercraft laser cut pieces.
I am very excited to use this die cut on a journal cover I purchased from you also. I don't know exactly how i will do it, but I have faith in the creative process. With quality scrapbook supplies, I cant go wrong! :-) thanks again for your excellent service!
beautiful addition to a garden layout......perfect size (not too small, not to large).......beautiful design details.....absolutely love the color...material seem very fragile just be careful when handling/using it.
You just gotta love Kaiser Crafts chipboard/wood embellishments, they are all just so strong and sturdy!!!!! A must have for your chipboard/wood collection!!!!!!
beautiful.. want to get more of them. Way to go Kaisercraft.


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|Publication number
|Publication type
|Publication date
|19 Mar 1974
|Filing date
|7 Dec 1971
|Priority date
|7 Dec 1971
|Publication number
|Kaminstein B
|Original Assignee
|Olivetti & Co Spa
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (11), Referenced by (12), Classifications (11)
|External Links: USPTO, USPTO Assignment, Espacenet
United States Patent [191 Kaminstein 3,797,388 1 Mar. 19, 1974 APPARATUS FOR PRINTING BY REVERSE LITHOGRAPHY [75] Inventor:
[73] Assignee: Ing. C. Olivetti & C0., p.A., Ivrea,
Italy 22 Filed: Dec. 7, 1971 21 Appl. No.: 205,522
Bernard Kaminstein, Paramus, NJ.
[52] US. Cl. ..101/141,101/148,101/367, 101/451 [51] Int. CI B4lf 7/36 [58] Field of Search ..101/147,148, 367
[56] References Cited UNITED STATES PATENTS 1.201.599 10/1916 Lutz ..101/451 3.690.252 9/1972 Sokolov 101/147 3.513.000 5/1970 Vrancken et al. 101/450 X 2.965.911 12/1960 Hempel et a1. 101/367 X 37.727 2/1863 Reynolds 101/367 X 168.511 MacDonald et a1. 101/367 X 2.588.470 3/1952 Bassist 101/142 3,002,449 10/1961 Sherman 441.660 12/1890 Harrison et all. 101/367 X FOREIGN PATENTS OR APPLICATIONS 903,724 8/1962 Great Britain 101/450 957.533 5/1964 Great Britain 101/148 Primary Examiner-Clyde I. Coughenour Attorney, Agent, or FirmLindenberg, Freilich &
Wasserman [57] ABSTRACT A reverse lithographic printing apparatus incorporating a combined inking and fountain roller is disclosed. A water-miscible ink is applied to the surface of an oil loaded, porous inking roller A mixture of ink and oil is formed which is applied to the printing master. The oil selectively deposits on the oleophilic background portion of the master while the water-miscible ink selectively deposits on the image areas.
13 Claims, 10 Drawing Figures PATENTEDK'ARIQ 19w 3.797.388
same or 4 ROTATION OF 20 FIG. 4
INVENTORI BERNARD KAMINSTEI N PATENIEDIIARIB m4 3.797.388
SHEU a or 4 INVENTOR. BERNARD KAMlNS TEIN PAIENTEUIARIQ 1914 37971388 SHEET h 0F 4 20s ZIO/ZO4 INVENTOR.
BERNARD KAMINSTUN APPARATUS FOR PRINTING BY REVERSE LITHOGRAPHY BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates-to an inking system for a lithographic-type of printing master and, more particularly, to improvements in application of ink and fountain solutions to a printing master for reverse lithography.
2. Description of the Prior Art:
Lithographic printing is based on the mutual immiscibility of aqueous liquids and non-polar organic liquids. In conventional lithographic printing, a printing plate is employed in which an aqueous fountain solution is attracted and retained by the non-image areas and the oil or greasy ink covers the image areas from which it is subsequently transferred either directly to the stock being printed or as in off-set printing to a rubber blanket from which it is then transferred to the stock to be printed. The oil-based inks have objectionable odors which render conventional lithographic printing unsuitable for many purposes, particularly in the food packing industry.
In reverse lithography, the printing plate or duplicating master has non-image areas which preferentially attract a water-soluble or miscible ink repelling liquid. A water-miscible ink is defined according to the invention as an ink formulated with water or a liquid miscible with water such as a glycol. The water-iniscible ink is preferentially retained by the image areas and issubsequently transferred to the stock to be printed. In copending application, Ser. No. 711,519, filed Mar. 8, 1968, now abandoned, entitled Method of Printing and Ser. No. 807,325, filed Mar. 14, 1969, now patent number 3,608,483, entitled Inking System for Printing," printing processes employing reverse lithographic printing plates are disclosed.
These printing processes employ a printing plate or master formed on a smooth, support sheet suitably a clear, thermoplastic resin, such as polystyrene or polyethylene which is selectively wettable by oily liquids. The image pattern is supported on the sheet and is composed of a roughened, coarse, and porous pattern of material selectively attractive to aqueous, miscible printing inks. The non-image areas of the sheet are rendered repellent to the inks by applying a film of an aqueous immiscible liquid such as a nonpolar, hydro,- phobic hydrocarbon liquid to the sheet. It has been found in practice that the liquid must be frequently reapplied to the printing plate usually after several copies have been reproduced or the nonprinting areas take up some ink with result that the background areas of the prints become dirty.
The oily background liquid has been applied to the printing plate from a separate applicator employing a reservoir of oily fountain solution and rollers to apply the oil directly to the plate or to a train of rollers proceeding the inking rollers so that the oil is milled into the ink before the ink reaches the final inking or form rollers which ink the printing master.
In the printing processes employed to date, the metering and control of the background fountain solution must be fairly strictly controlled in order to assure that high quality prints are produced. This has required the complex mechanisms for applying the liquid such as oil drop control mechanisms and separate reservoirs and application rollers.
OBJECTS AND SUMMARY OF THE INVENTION An object of this invention is to provide a simpler arrangement than heretofore employed for applying oily fountain solution to planographic printing plates for reverse lithography.
A further object of this invention is to provide an improved reverse lithographic process in which the printing master is simultaneously inked and wetted with fountain solution and thereafter produces excellent prints.
Still another object of this invention is to improve the retention of ink in the image areas and the rejection of ink in the non-image areas of a reverse lithographic resinous printing plate.
Another object of the invention is to decrease the sensitivity of application of background liquid in a reverse lithographic duplicating process.
A still further object of the present invention is the provision of a novel and unique method and means for inking and wetting a printing master with hydrophilic ink and an oleophilic background fountain solution.
These and many other objects and attendant advantages of the invention will become apparent as the description proceeds.
An improved painting system for reverse lithography is provided in accordance with the invention by applying an aqueous-miscible ink to the surface of a porous inking roller impregnated with an oily fountain solution. The mixture of ink and oil is applied from the inking roller to the printing master and the oil selectively deposits on the oleophilic background portions of the master while the water-miscible ink selectively deposits on the image areas.
The compressible and absorbent surface of the roller when contacted with the master is found to deform around the slightly raised, porous, roughened image characters and to selectively apply ink to the image characters and to maintain a thin film of oil on the smoother surrounding background areas. Excellent prints are produced on a continuous basis.
The single printing and oil application roller may contain an internal reservoir of oil which is automatically metered onto the printing master by controlling the relative pressure between the master and the roller and the amount of oil necessary has been found to be less critical than in previously practiced systemsln a further preferred feature in accordance with the invention, the top surface of the inking roller is grooved and the oil is selectively applied from the sides of the grooves while the ink is selectively applied from the top surface of the adjoining ridges. A pair of the grooved rollers with the ridges of the rollers off-set to overlap the grooves of the other roller may be utilized to assure total inking of the master.
The invention will now become better understood by reference to the following detailed description when considered in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic illustration of rollers in a reverse lithographic printing system according to the invention;
FIG. 2 is a front elevation view partially in section of the combined inking and fountain roller of the invention;
FIG. 3 is a front elevational view of a grooved inkingfountain roller;
FIG. 4 is an enlarged schematic illustration of the application of ink and oil to the master from one raised ridge of a stationary grooved inking roller;
FIG. 5 is a schematic illustration of a printing system incorporating a pair of grooved inking-fountain rollers;
FIG. 6 is a view taken along the line 6-6 of FIG. 5;
FIG. 7 is a schematic illustration of a further embodiment of a printing system in accordance with the invention;
.FIG. 8 is an end view partly in section of the inking rollers of the system of FIG. 7;
FIG. 9 is a schematic view of a further embodiment of a printing system; and
FIG. 10 is a view taken along the line 10-10 of FIG. 9.
DESCRIPTION OF THE PREFERRED EMBODIMENTS Referring now to FIGS. 1 and 2, the printing master 10 is secured to a plate cylinder 20. An aqueous miscible ink is applied from an ink fountain 12 to a fountain roller 14. A doctor blade 16 controls the amount of ink applied by fountain roller 14 to the porous inking roller 18. The inking roller 18 includes a porous, absorbent sleeve 22 saturated with an oleophilic background liquid. Suitably, the mandrel 24 for the roller 18 contains perforations 26 and forms a reservoir 28 for the oleophilic background liquid 30.
As the rollers rotate, the oleophilic liquid 30 saturates the sleeve 22 and the ink applied to the surface 32 of the inking roller 18 mixes with the oil and the mixture is applied to the surface of the printing master 10. The ink will be selectively absorbed by the image areas and the oleophilic liquid will be selectively applied to'the smooth background areas and the latter areas will reject the ink. The inked image pattern is transferred to a sheet 34 of paper or other material to be printed or decorated being fed between impression cylinder 36, and the master cylinder 20. Alternatively, the inked image can be transferred to a blanket cylinder, not shown, and printed on the paper by an off-set process.
The printing master 10 is suitably formed of a base sheet material which is preferentially wettable by a liquid immiscible with water or with water miscible liquids. The base sheet is preferably formed of synthetic organic resins such as polystyrene.
The surface of the smooth base sheet may be evenly coarsened or roughened as disclosed in copending application, Ser. No. 3,160, filed Jan. 15, 1970, now abandoned entitled Printing Master for Reverse Lithography, the disclosure of which is incorporated herein by reference. This treatment forms a matte, grained surface having increased ability to retain the ink repelling liquid within the channels, irregularities or pockets formed by the roughening treatment.
The image pattern or areas are suitably formed of an organic resin having good tolerance to aqueous miscible liquids such as glycols and having very poor tolerance to glycol repelling liquids such as hydrocarbon oils. Suitable resins are polystyrene or copolymer of vinylacetate and ethylene and polyester resins such as Vitel 222 (Goodyear Rubber Co.). The image areas may contain pigment particles such as carbon black or zinc oxide dispersed in the resin binder film which can provide a rough surface for holding ink within the interstitial spaces between the pigment particles.
The image areas are preferably formed from an electrophotoconductive pigment such as zinc oxide dispersed in an organic binder resin but may also be formed of other photoconductive materials such as selenium, cadmium sulfide or cadmium selenid'e. The printing master may be prepared according to the procedure disclosed in application, Ser. No. 30,753, filed Apr. 22, 1970, now US. Pat. No. 3,648,608, for Method and Means for Making a Duplicating Master, the disclosure of which is incorporated herein by reference.
An ink composition suitable for use in the reverse lithographic process of the invention comprises an aqueous or polyhydric alcohol thinner, a film forming binder resin dispersed in the thinner and suitable dyes or pigments as coloring agents. Ink compositions for practicing the process of the invention are disclosed in co-pending applications, Ser. No. 3,096, filed Jan. 15, 1970, entitled, Ink for Reverse Lithography, and Ser. No. 533, filed Jan. 5, 1970, entitled, Ink Composition for Reverse Lithography, the disclosure of which are incorporated herein by reference.
The oleophilic background liquid is generally a hydrocarbon oil, a silicone oil or other hydrophilic ink repelling liquid having preferential adsorptivity for the smooth background areas of the printing master. Superior performance is obtained with high boiling aliphatic hydrocarbons such as kerosene oil fractions distilling between 520 to 560 F and other product, Deodorized 400 oil, distills between about 390 to 450 F. lsopar G is a mineral oil fraction distilling between about310 to 350 F. More copies per plate and better performance are obtained when the non-polar liquid is also a nonsolvent for the material forming the base sheet of the printing master. For this reason, when polystyrene is utilized in the printing master, liquids having a high percentage of aromatic hydrocarbons are preferably avoided to alleviate swelling and dissolution of the printing master.
In accordance with another aspect of the invention, it has surprisingly been discovered that better print quality and less criticality in the rate of metering the oleophilic liquid to the printing master are achieved when the ink is premixed with up to 15 percent by weight, suitably about 10-12 percent by weight of the oleophilic repelling liquid, such as Deodorized 400 oil. The hydrophilic ink and the oil are premixed and the mixture is added to the ink fountain 12. The ink will be blended with additional amounts of oil as'it passes over the porous inking roller 18 and the oil and ink will be redistributed between background and image when they contact the printing master l0.
The porous, absorbent outer sleeve 18 contains an interconnected network of open cellular pores. The matrix is formed of a tough, abrasion resistant, resilient synthetic elastomer having good wetting properties for the oleophilic fountain solution. The sleeve should be dimensionally stable and should dispense fountain solution on light pressure contact with the printing master. The void percentage can vary over wide limits. At a void volume of percent sufficient matrix elastomer remains to provide the desired compression and resiliency properties. The void volume should be atleast 20 percent to provide sufficient retention of liquid for quickly dispensing a controlled amount of liquid at working pressure. Pore size should be uniform and fairly small, typically below 100 microns suitable about -20 microns. Tensile and tear strength must be high. Hardness as measured by Shore A durometer can range from about -35, preferably about -30.
The porous elastomer sleeve can be fabricated from many different polymer systems such as natural or synthetic diene latices, polyolefms such as polyethylene, polypropylene or polyvinyl chloride, polyamides such as Nylon or polyurethanes. The open pore structure can be provided by the controlled sintering of particles of the resin or by the use of chemical or glass blowing agents.
A suitable material known as Micro-well (Elastolabs Corp.) is an abrasion-resistant, polyurethane material having a 70 percent void density containing an interconnected network of 13-14 micron open pores, and having a Shore A hardness of about 27 and a specific gravity of 1.30 to 1.35. Light finger pressure readily dispenses the oleophilic liquid at the depressed location in controlled amounts without excessive flooding of the surface. The small diameter pores act as capillaries to pump the liquid from the internal part of the sleeve to near the surface. The near surface capillaries act as a dispensing valve to controllably meter the liquid onto the surface of the printing master.
The sleeve can be initially charged with oleophilic fountain solution and can supply the solution to the master for a finite amount of copies before recharging is necessary on a batch or continuous basis. A preferred manner of recharging the sleeve is to continuously sup ply fountain solution to the sleeve from a reservoir. As illustrated in FIG. 2, the reservoir 2% can be located in the interior of the mandrel 2d for roller 18. The hollow mandrel is closed by end plates 40, 42 and contains a series of perforations 26 communicating the reservoir 28 of liquid 30 with the interior portion of thesleeve. The liquid movesoutwardly through the interconnecting capillaries to near the surface 32 of the roll. The reservoir 28 can be refilled through plug 50 in end plate 42. It was further discovered that when the printing system was operated with plug 50 removed, more liquid was dispensed.
The outer surface pores of the sleeve exhibits some tendency to close on application of pressure from the print master. Referring now to FIG. 3, this problem is obviated by forming a plurality of spaced, parallel, vertical grooves 60 in the face of the sleeve, such that the grooves 60 alternate with ridges 62. Thus, when the grooved sleeve 64 contacts the printing master it), the oil will be dispensed from the side walls 66 of the ridges 62. The ink is only received on the top surface 68 of the ridges 64 and the ridges 64 selectively transfer the ink to the image areas of the master.
Since incomplete inking of the master may occur, it is preferred to utilize a set of grooved inking rollers 70, 72 as illustrated in FIGS. 5 and 6. The inking rollers are in contact with a roller 73. The fountain roller T4 is transported back and forth between the ink fountain l2 and the roller 75 of the inking train in order to control the amount of ink applied to the porous inking rollers 70, 72. The grooves 76 are slightly narrower than the ridges 78 and one of the rolls is off-set the width of a groove 76 such that the opposing ridges 78 from each roll overlap the opposite grooves 76 of the other roll. Thus, complete inking of the plate 10 is assured and high quality prints are obtained on sheet 34 passing between the master cylinder 20and impression roller 36. In an illustrative embodiment, the sleeve has a 2 inch outer diameter and a 1 inch inner diameter. The grooves are Vi inch deep and inch long while the ridges have a top face length of V2 inch. A fresh printing master should be conditioned before use by rubbing the sleeve against the plate to apply an initial film of oil on the background areas, and deposit some ink in the image areas. The plate will then be ready to deliver high quality prints on start-up of the printing press.
in the preferred printing process using the porous roller, according to the invention, there are two distinct phases: preoiling and printing. During the preoiling stage, the porous rollers 18 are held stationary, while the master cylinder 20 carrying the printing master 10 is rotated with the master in contact with the rollers. Referring now to FIG. 4, the imprint of one of the high portions or ridges 68 of the porous inking roller on the master it) is shown. The ink on the surface of the porous roller tends to seal the pores therein. This is especially true since, with a pigmented ink, the pigment particles tend to clog the pores of the porous roller. The oil, however, escapes from the side walls of the groove which side walls are compressed by the contact with the master. Thus, as shown in FIG. '4, the oil 80 tends to surround the portion of the roller in contact with the printing master. Therefore, as the master cylinder 20 rotates, causing the master to rub against the stationary porous rollers, the portion of the oil 82 squeezed out in front of the roller 70, 72, wets the background area 84 of the master and coats it. In the image area 86 most of the oil deposited thereon is immediately squeezed off by the porous roller immediately therebehind, and what little bit is left is absorbed into the porous character 86. The porous roller in contact. with the image also coats theimage with ink preventing any further deposition of oil. In this way, at the end of the preoiling, the background areas 84 of the master are coated with oil, while the image areas 86 are relatively free of oil and have some ink coated thereon.
The second phase of the operation of the system is the printing phase. During printing, the porous rollers 70, 72 rotate in synchronism with the master cylinder 20 so that there is rolling contact between them rather than the sliding contact which occurred during the preoiling phase. The ink deposited on the surface of the porous rollers then inks the image portions 86 of the master while the oil from the interior of the porous roller replenishes the supply of oil on the background 84. The amount of force exerted by the master on the porous inking roller is fairly substantial and may be on the order of about 50 pounds. Rather strong pressure is needed in order to squeeze out a sufficient amount of oil from the side walls of the grooves of the porous rollers.
A further and most preferred embodiment of a printing system is illustrated in FIGS. 7 and 8. This system incorporates means to regulate the rate of ink and oil delivery to the printing master. Even though the ink is much more viscous than the oil, it has been found that the ink tends to spray from the fountain roller and other rollers in the inking train. Referring now to FIG. 7, a much improved ink delivery train is provided by means of an ink delivery roller 90 in contact with both of the grooved inking rollers 70, 72:.
The inking roller 90 includes a central hollow, perforated mandrel 92 covered with a sleeve 9d of a soft, re-
silient compressible cellular material such as an open cell foamed organic resin such as polystyrene or polyurethane. The pores of the sleeve are fairly large to permit dispensing the pigmented, viscous ink. The resin may be modified to increase its hydrophilic properties to insure good wick action to dispense the ink from the ink reservoir 96 within the hollow mandrel 92.
The outer surface of the porous sleeve 94 may optionally be covered with a tubular band 98 of an open mesh fabric such as Nylon. This band 98 serves to retain the sleeve 94 on the mandrel and to decrease the abrasion of the sleeve 94 during rolling contact with the inking rollers 70, 72. The ink delivery roller assembly 90 may be provided as a disposable, batch cartridge which is thrown away after the ink supply is exhausted. The ink contained in the reservoir within the hollow mandrel may be a glycol based carbon black, acid dye, shellac binder ink as disclosed in application Ser. No. 533 and need not be premixed with oil.
As the rotating ink delivery roller 90 contacts each inking roller 70, 72 the sleeve 94 is compressed and ink is dispensed onto theportion of the top surface 68 of the ridges 62 of the sleeve 64 in contact with the sleeve 94. As the roller 90 passes out of contact with the inking roller 70, 72, the sleeve expands to its original shape and absorbs the excess ink back into the sleeve 94. The sleeve 94 is much softer than the sleeve 64 of the inking roller and is therefore preferentially compressed when in pressure contact with the roller 70, 72. Therefore, little oil is dispensed from the inking roller 70, 72 during inking. The oil is dispensed from the side walls 66 of the ridges when the inking rollers 70, 72 contact the printing master 10.
Referring now to FIG. 8, the oil delivery from inking rollers 70, 72 is regulated by installing a rotating seal 100 atone end of each of the rollers 70, 72. The seal includes an O-ring 102 installed between the hollow stub shaft 104 of each roller and the housing 106. A line 108 containing a valve 110 is connected to the housing 106 and to a closed cannister 112 which, however, is open to ambient pressure. During rotation of the rollers 70, 72 a slight vacuum is formed as the oil is dispensed through the hollow mandrel 24 into the porous sleeve 22. The seal 100 maintains the decreased pressure and prevents equalization of pressure with the ambient at the rotating seal. The pressure within the reservoir 28 is equalized with the closed cannister 112 by means of the valve 110 which opens in the presence of the vacuum, and thus serves to regulate the rate of oil delivery through the slotted porous sleeve.
A further embodiment of a printing system is illustrated in FIGS. 9 and 10. Oil and ink are applied to the master 202 on the master cylinder 200 by means of an oil charged porous roller 204. The roller 204 is formed of a perforated mandrel 206 forming a reservoir for the oil supply. A porous, absorbent, sleeve 208 which may be formed of the materials previously described is mounted on the mandrel 206. In order to assure an adequate oil supply at the surface of the sleeve 208, a series of spaced vertical slits 210 are cut into the roller, for example, the sleeve can be about V1 inch thick and the slits are Va inch apart and about inch deep.
The ink reservoir for the system is contained within a screen roller 212. The roller 212 includes an axial rotatable rod 214 supporting end plates 216. A cylindrical screen 218, suitably a 100 mesh metal screen is mounted on the end plates 216.
The ink is transferred from the surface of screen 218 to the roller 204 by means of a soft, porous transfer r01 ler 220 which rotates in pressure contact with the screen roller 212 and the oil charged roller 204. The roller 220 includes a central core 222 supporting a soft sleeve 224 of compressible foam. The transfer roller 220 rotating in pressure contact with the roller 204 causes the ink and oil to mix within the pores of the foam sleeve 224 and aids in insuring the application of a smooth, uniform layer of ink and oil to the surface of the oil-charged roller 204 and to regulate the thickness of the ink coating. The sleeve 224 of the porous transfer roller 220 can be made of any plastic foam which is not attacked by the ink or oil and is preferably more resilient than the sleeve 208 of the oil loaded roller 204.
The printing system of the invention provides a much simplified apparatus for printing by reverse lithography and eliminates many rollers previously thought necessary while not being as sensitive to replenishing background fountain solution.
It is to be understood that only preferred embodiments of the invention have been described and that numerous substitutions, modifications and alterations, are all permissible without departing from the spirit and scope of the invention as described in the following claims.
What is claimed is:
1. A system for inking a printing master having shaped image regions which preferentially absorb water-miscible inks and background regions which do not absorb water-miscible inks, comprising:
roller means including a rigid mandrel having an outer sleeve of a porous, liquid absorbent, compressible material;
said sleeve outer surface containing a plurality of grooves alternating with ridges, said ridges and grooves being disposed transverse to the axis of said mandrel;
means for applying water-miscible ink directly to the surface of said outer sleeve;
means for applying hydrophobic liquid to said surface of said outer sleeve from the interior of said roller means; and
means for rolling said roller means to roll the surface of said sleeve over the surface of said master, whereby said ink is selectively deposited on said image regions and said liquid coats said background regions.
2. A system according to claim 1 in which said sleeve is formed of a tough, abrasion-resistant, resilient synthetic elastomer containing an interconnected network of open cellular pores.
3. A system according'to claim 2 in which said elastomer is a polyurethane having a void volume between 20 and percent.
4. A system according to claim 1 in which said mandrel is hollow forming a reservoir for said hydrophobic liquid and said mandrel is perforated for applying said liquid to the surrounding porous, absorbent sleeve.
5. A system according to claim 4 further including hydrophobic liquid regulating means connected between said mandrel and said reservoir, said hydrophobic liquid regulating means including valve means operable responsive to a pressure drop caused by loss of liquid from said mandrel for enabling replenishment of said liquid from said reservoir.
6. A system according to claim in which said regulating means includes a rotary seal connected to an end member of said mandrel, a housing surrounding said seal, a closed member and conduit means connecting said housing to said closed member.
7. A system according to claim 4 in which said ink applying means includes an ink delivery roller having a soft, porous, ink loaded outer sleeve in contact with the absorbent sleeve of said roller means.
8. A system according to claim 7 in which said ink delivery roller includes a hollow, perforated mandrel forming a reservoir for said ink and said soft, porous sleeve is received on said mandrel.
9. A system according to claim 7 in which said ink applying means includes a hollow roller having a perforated outer cover enclosing a reservoir for said ink and said soft porous sleeve is in pressure contact with said cover and the outer sleeve of said roller means.
10. A system according to claim 1 in which said means for applying ink includes a fountain roller for applying ink to the outer surfaces of said ridges.
1 l. A system according to claim 1 in which said roller means includes a plurality of rollers having said grooved sleeves for contacting said master; the ridges of a sleeve of at least one roller overlapping the path of travel of the grooves of another sleeve over said master. 12. A system for inking a printing master having shaped image regions which preferentially absorb water-miscible inks and background regions which do not absorb water-miscible inks, comprising:
roller means including a rigid mandrel containing an outer sleeve of porous, liquid absorbent, compressible material; said sleeve outer surface containing a plurality of spaced slits, means for applying water-miscible ink directly to the surface of said outer sleeve; means for applying hydrophobic liquid to said surface of said outer sleeve from the interior of said roller means; and means for rolling said roller means to roll the surface of said sleeve over the surface of said master, whereby said ink is selectively deposited on said image regions and said liquid coats said background regions. 13. A system according to claim 12 in which said slits are disposed perpendicular to the axis of said mandrel.
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|U.S. Classification
|101/141, 101/451, 101/367, 101/148
|International Classification
|Cooperative Classification
|European Classification