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- Publisher: NovaLogic
- Release Date: Jun 15, 2004
User Score
Universal acclaim- based on 46 Ratings
User score distribution:
Positive: 43 out of 46
Mixed: 1 out of 46
Negative: 2 out of 46
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Mar 26, 2011This game is great! Servers are still well populated and the game is still fun! Even for today's standards (2011) this game could beat any other. Good graphics, gameplay ,etc. Worth the buy!
Aug 26, 2010This game is old, but a classic. Huge maps, many drivable vehicle, and great online play modes. Advance and Secure is in my opinion the best mode ever created. I would have given it a ten if it wasn't for the fact that the anti-cheat engine is no longer updated and most servers are plagued with hackers. Other than that Joint Ops, is still one of my all time favorites.
Jun 3, 2011Much agree with JohnHorkman. Picked this game up recently and is some of the best gameplay I've seen! Games to need to be made more often like this. I even showed it to a few friends (which were COD fanboys) and they thought it was the coolest game they've EVER seen! They felt jealus because they didn't have a PC good enough to run it. They are Xbox 360 nerds btw lol. ;) Look no further gamers! This is the way to go. Also, check out the Escalation expansion if you are getting this. Pure epicness and nothing more!… Expand
May 2, 2011Till this day this is one of the best multiplayer shooters out there, no question. The huge sprawling battlefields and really exciting game play makes this a fun experience. Strategy is key to this game, not a run n gun like COD etc. What I love most is that many of the servers have battles that have an almost unlimited time limit so you can technically play this game for hours on end with the battle still raging when you finally log off, unless of course one team captures all the checkpoints. I remember playing one battle that raged for 15 hours once, HA. The graphics are dated, but what do you expect from a game 10 years old? WELL worth buying, even today, the expansions are fun too, and their are TONS of mods for this. Also, check out the taunts.... they are hilarious. HOOO RAAAAA!!!!… Expand
Apr 21, 2012Even with the age of this game, it still out plays all the latest/modern games. With the ability to make custom maps, and the amount of people you can fill a server with(150+) it is still a great game. Can't stop playing it! This game even has a tournament that has been in existence since 2004, www.icjo.info
Apr 22, 2012I have bought most FPS game to come out in Recent years All the COD and BF series, But within a couple of days, Im back with JO, It is by far the best FPS out there. The things you can do with this game is awesome, Moding is easy, Map building easy. We even have a tournament which is great. Anyone out there who rads this and doesn't have Joint operations should try it.
Oct 4, 2013I love this game still. Good online multiplaye, lan, Radio Team Speak e.g I need back up, Good missions, Good stages.
Get this game it's very good.
Dam 148 words :D
What it does have, though, is rock-solid netcode and the most exquisite balancing and map design I've ever seen. [Aug 2004, p.104]
It is much more suited towards the serious cyber solider rather than the ex-quake junky with its heavy dependency on tactics and planned strategies, and whilst it is far from perfect itself, the detail and depth offered in Joint Operations is quite exceptional to say the least.
When it works it works well and offers a very challenging online experience. The fun is hampered by both horrendous load times and the fact that you need a high-end system to coax performance from the engine. There are also some issues with unbalanced units, rampant camping, and the lack of any "functional" vehicles other than transportation.


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This product is amazing! It drys out the pimples and leaves your face without shine which is great. You just put this on a cotton ball after you wash your face, or put it in a spray bottle and spritz throughout the day and before applying make up! This stuff is unbelievable and for the price? It doesn't get any better. Not to mention it's 100% natural which I love. Guys please try this you don't understand how great it is.
was is this really supposed to do? i apply after my cleanser, and before moisturizer and/or benzoyl peroxide treatment. yes ill admit i do feel a tad bit cleaner afterwards, but it hasnt cleared up any acne or reduce surface redness. it has a weird smell, difficult to describe. i have a big bottle from cosco and i dont think ill repurchase.
This works great to reduce redness in the face and cleanse the skin. I put this in a spray bottle and mist other areas of my body that can sometimes break out. It has helped with minor breakouts tremendously and also helps to heal the occasional hormonal cystic acne I get on my jawline and chin.
I also find it works great after shaving, misted on the skin regularly, it prevents ingrown hairs and bumps.
This is an actual lifesaver. Ever since I started using it my skin has cleared up so much, its unbelievable. I used to break out quite often, now I just don't. Since its summer my skin is oily and this helps control that too, if you're contemplating getting this, do it.
1 out of 1 people found this review helpful. Did you? Yes No
Okay firstly this may do a good job.. But it STINKS and it feels so rough on delicate face skin yuk
This is a great product. I have very very oily skin and recently had a nasty breakout due to hormonal issues [but I have mild acne to begin with] and after just a couple of uses this is clearing up my breakout and making my skin so soft and feels refreshed and clean. I highly recommend this product if you have acne, and want a nice natural way to clear it FAST. Go buy this!!!!!
Out of all the toners I've tried this one has giving me great results without overly drying, or irritating my eczema prone skin. I tend to get occasional acne around my jawline and chin. Just swabbing a squirt of this on those area's solves the problem in a day or two. Many of times I don't even have to apply any other form of acne medication. I have even used this in the morning to cleanse my face without soap. It's super refreshing and has a slight cooling sensation when applied. It comes in such a large bottle that it has literally lasted me over a year, and for around $2-$3 for a natural product, it's a steal. I really don't have anything negative to say about it. It's just that great!
1 out of 1 people found this review helpful. Did you? Yes No
I mix this with water, lemon juice, and a small amount of grapeseed or sunflower oil to use as a toner. It works great! I have had issues with acne for years and most recently a LOT of redness. It has been so bad that it looked like I had a sunburn all winter. I used to use so many products with chemicals to try and get rid of acne that I'm pretty sure I ruined my skin and now it has to heal. I use Burt's bees intense hydration or sensitive cleanser, this toner, and a natural based moisturizer such as desert essence that is oil and plant based. If I wear a full face of makeup I will even precleanse with OCM and then continue with my cleanser. I see improvement in my skin everyday, it is finally healing and the redness is fading. I can use this full strength as well and haven't had any problems. Any zits that do pop up with this routine go away in a day or two. I recommend this!
More reviews by kitkatkate1013
I really wanted to like this product but was disappointed. I have combination/dryish skin and I'm always looking for natural products and was excited to give it a try. The first week I used it, my skin was pretty good (a bit drying but with moisturizer I had no complaints) But on the second week I BROKE OUT. Badly. I usually have one or two small pimples but I broke out in small bumps on my forehead, all over my chin going up onto my cheeks, and around my nose and upper lip. They were mostly clogged pores. I think the reason I got them was because the alcohol dried out my skin, making it produce more oil, and clogging my pores! I really wish this had worked after all the good reviews but i guess it's just not for me :(
I love this product! About a month or so ago I decided to bring a toner into my skin care routine and now I can't believe I hadn't used one until recently! This one is especially great because it's natural (I hate putting harsh chemicals on my face). It's amazing at reducing redness/irritation in the skin, whether it be pimples or even redness in the cheeks, which I have personally always struggled with. The thing I like most about this product is that it helps with clearing away pimples and fading scarring from previous ones, and I've also found that my skin has been super clear since I've been using this. It does everything it says on the bottle, it was such a great purchase and I'm so happy with it! It has a really strong smell but I don't find it unpleasant, I'm not super sensitive to that sort of thing. I will definitley repurchase, I can't imagine my skin care routine without it :)

subset: commoncrawl


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Originally written on Fox Sports Arizona | Last updated 11/20/14
PHOENIX -- Alvin Gentrys lineup purge appears to be the shift that keeps on giving. But the new-and-improved Suns starting lineup may have settled for a one-night honeymoon. Thanks to some uninspired play against the Hornets on Black Friday night, the new-and-improved (for now, at least) second unit was required to step in and lead a crucial rally. In what became a 111-108 overtime triumph, the Suns second unit lifted Phoenix from four points down going into the fourth quarter and into a six-point advantage by the time starting center Marcin Gortat returned with 4:53 left in regulation. It should be noted the second unit finished at plus-10 in Wednesdays trial-run victory over the Trail Blazers. So even though the bench five offers less overall speed than youll witness in a relay of garbage trucks, its group success may not be a fluke. The biggest star turn in the triumph over New Orleans was taken by 17-year veteran center Jermaine ONeal. One game after Gortat made 11 of 14 sho...
Original Story: http://www.foxsportsarizona.com/11/24...
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Mariah Yeater: Yearbook Photo Found!by Hilton Hater at . Comments
Easy, Beliebers. Do not throw anything at your computer screen.
But a high school yearbook of Mariah Yeater has allegedly surfaced, giving the public its first view of the woman who claims to be the mother of Justin Bieber's three-month old son. Here it is:
To recap:
Yeater is featured in this week's issue of Star Magazine. She has sued Bieber for child support, alleging that he took her into a bathroom on October 25, 2010 after a concert in Los Angeles and, in her words, said he wanted to "f-ck the sh-it" out of her." They proceeded to have 30 seconds of unprotected intercourse.
Bieber addressed the charge directly this morning and said he's never met Mariah Yeater.
[Photo: Pacific Coast News]
30 seconds ONLY!!!!! Is he that much of a mediocre lover...!!!
I really dont believe this, but if its true Justin had to be extremely drunk to even look at something like that. Come on!
man i feels sorry for this bitch she is lier and she need too look for her real baby daddy
WOWWWWWWWW this is such bull . She looks like crap......
Can he bring charges on her she was 19 he was under age --- child rape
that was imposible thing.she's not beautiful.I think justin never interested with her.
This is so fckn sad tbh if u dont noe who ya baby daddy is search dont try and make false acusations on a inocent man n its sad how now the bby mite not noe who his daddy cuz (mommy was whoren around befor she had em) smfh so sad.......
Its not possiable that a 30 sec intercourse would lead to a pregnancy and shes not sure because she didnt tel justin first instead she told her ex.


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Jessica, the mastermind behind Goddess Rising Fitness, began her fitness journey after losing her job of 11 years and deciding to try something new. She started Goddess Rising Fitness in 2010, when she rented studio space for an hour a week to teach a sexy chair-dancing class. Today, Jessica and her team of dance-trained instructors lead more than 15 weekly classes, which include high-energy Zumba classes, relaxing yoga, and strength-building ?bombshell ballers? classes using stability balls. She offers Zumbatomic classes that get kids ages 4?12 dancing to age-appropriate tunes and working on age-appropriate long division problems. She also leads six-week boot-camp sessions that aim to help guests lose weight and build strength with functional exercises, weekly weigh-ins, and food journals.
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Limbs are jiving, feet are stomping, and hips are swaying. That's dancing. It's also a great way to stay fit. At Dance Trance Deltona, instructors lead high-energy, exciting, upbeat dance fitness classes designed to be fun while burning calories. Classes feature fast-paced, high-cardio, and nonstop dancing. If it sounds intimidating, it's not. To make it accessible to all fitness levels, they offer a Dance Trance Breakdown class. That session slows the pace so that routines and dance moves are broken down and easy to learn.
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... of the kids and a few adults also had a bit of a water-ski.
These long Norwegian nights are amazing and we all sat around for hours until about midnight before they drifted off, some by boat, some by car, some on foot.
It was a sea-food day, so there were prawns aplenty, crabs, marron-like things, and Anika cooked some fresh-caught (like off the quay right here) local mackerel.
But it was a great day and I have to ...
Short and Sweet-Sweden, Into Norway
... were reasonably busy with holiday traffic. This was the only downside of the Swedish portion of the route-a fair portion of our riding was on busy roads rather than designated cycling routes as we'd been accustomed to. We gained the impression too from the very old North Sea cycle route signs-often completely faded away, that cycling isn't a huge pastime in Sweden. Nonetheless the route was still pretty spectacular, although a little unnerving at times!
Again ...
Norway - and a little Sweden (24 July - 5 August)
... with a hot chocolate/tea/coffee/soup before taking the scenic rout back to Stina's mum's place for yummy reindeer stew and potatoes (thanks Stina). On Wednesday Camilla and I had originally planned to drive west to the fjords and coast, however, the weather was still miserable and therefore we wouldn't have been able to see much. So instead we drove inland down the E16 past Lillehammer and Hamar down towards Oslo, stopping at a couple of churches, lakes, cheesery ...
Brevik, , Stavern
... color: rgba(26, 26, 26, 0.296875); -webkit-composition-fill-color: rgba(175, 192, 227, 0.230469); -webkit-composition-frame-color: rgba(77, 128, 180, 0.230469); -webkit-text-size-adjust: auto; ">The town had 10 dry-docks, although these have reduced over the years to the current 5, but the massive timber buildings and magazine remain, and it is a major tourist attraction, with many people making day-trips there by car or boat.
... by the truck-load. And then attached, he has his men's shed where he has every wood-working machine imaginable. What a set-up! Love it!
Then we came home again for lunch and K and I ...


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- 100% off Waterproof Furniture Cover expires: 12/02/2014Get deal & saveUsed 5 times
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US shuttle, the most complex flying machine ever built
The US space shuttle is the most complex and costly flying machine ever built. It helped build a pioneering space outpost but also kept Americans confined to low Earth orbit for 30 years.
The US space shuttle is the most complex and costly flying machine ever built. It helped build a pioneering space outpost but also kept Americans confined to low Earth orbit for 30 years.
(AP) -- How America gets people and stuff into orbit is about to be outsourced in an out-of-this-world way.
The space shuttle passed into history Thursday, the words "wheels stop" crackling over the cockpit radio for the very last time.
This month is the 40th anniversary of the Apollo 15 launch. This mission was the eighth manned mission in the Apollo program and the fourth to the Moon. The Apollo 15 mission is important because it was another ...
The US space agency is offering schools and universities a special deal on astronaut cuisine and heat tiles from the now extinct space shuttles, just over 20 dollars a pack, NASA said Monday.
Dr. William Schonberg says academia is cool because you usually get to research what you're really curious about. As chair of civil, architectural and environmental engineering at Missouri University of Science and Technology, ...
Boeing is taking over one of NASA's old space shuttle hangars to build a new capsule that the company hopes will lift astronauts to orbit in four or five years.
A NASA astronaut who spent more hours walking in space than any other American and also set a record for the longest spaceflight mission has retired to join the private sector, the US space agency said Monday.
The unmanned Dragon cargo vessel operated by US company SpaceX on Thursday completed its deorbit burn, one of the final steps in its return to Earth for an ocean landing, NASA said.
Kennedy Space Center is getting a new neighbor: XCOR Aerospace announced they intend to establish an operational base in Florida, and also hope to build a manufacturing and assembly center for the XCOR Lynx ...
A test launch of an unmanned rocket that would eventually help carry supplies to the International Space Station has been rescheduled.
Kansas State University researchers are improving astronauts' outerwear for outer space.
US astronaut Mark Kelly, who is commanding the shuttle Endeavour's final space flight, said Tuesday he is concerned about a drain of NASA talent once the US shuttle program ends later this year.
As a teenager in Costa Rica, Franklin Chang-Diaz had an improbable goal: becoming an American astronaut. Ultimately, he would fly a record seven shuttle missions and today wants to fly to Mars.
If you think of the shuttle as a kind of big space bus, the future for US astronauts will be a lot like squeezing into a three-seat compact car, made by Russia, for a very long road trip.


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Custom Photo
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The Walking Dead: Season Two – Episode 4 Trailer: (Pen)Ultimate Suspense
Now that The Wolf Among Us has finished, we can all shift our focus back to the world of The Walking Dead with Episode Four of Season Two, 'Amid the Ruins.'
Now that The Wolf Among Us has finished, we can all shift our focus back to the world of The Walking Dead with Episode Four of Season Two, 'Amid the Ruins.'
Clem has both melee and ranged weapons covered in these latest screenshots of Episode Four of The Walking Dead: Season Two, 'Amid the Ruins.'
The Blazblue franchise is taking a page from the Hearthstone manual with Blazblue Battle Cards, coming to iOS devices very soon.
Cyanide and Focus Home Entertainment have announced that they are bringing their 2009 game, Blood Bowl, to tablets.
Square Enix Montreal has announced that Agent 47's mobile puzzle antics are getting some additional features in a new update for Hitman Go.
This free-to-play MOBA takes what you love about The Witcher series and puts it in the palm of your hand.
The man who created the Final Fantasy series has announced his newest RPG.
This Android-operated microconsole has gotten its entire library of hundreds of games opened up for a very low price.
These leaked photos of an alleged Android TV controller remind us of some other peripherals we are very accustomed to using.
Indie studio, Versus Evil, has announced Kyn, the mobile version of The Banner Saga and a new title based on Afro Samurai are all on the way.
A recent survey indicates that the number of female developers in the gaming industry are on the rise, but unpaid overtime is still too frequent.
The official sequel to Sid Meier's Civilization Revolution has been announced for mobile devices.


text:
Evers Implements Victory
Edwin Evers scrapes, poles and trims out win on St. Johns River.
On the Water: Edwin Evers
See the images of Edwin Evers catching his winning fish on the St. Johns River.
Jones' Stealthy Measures
Alton Jones pulled out all the stops to conceal himself from bedding fish.
Power-Pole Citrus Slam Final Weigh-in
The final day weigh-in photo gallery from the Power-Pole Citrus Slam on the St. Johns River.


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Strenuous Hikes at Island in the Sky
The longer hiking trails at the Island generally begin on the mesa top and descend via switchbacks to the White Rim bench. A few trails continue down to one of the rivers. All are considered strenuous, with an elevation change of 1,000-2,000 feet, and require negotiating steep slopes of loose rock as well as sections of deep sand. Water is scarce in most areas. Trails are marked with cairns (small rock piles).
Gooseberry Canyon
Lathrop Canyon
Murphy Loop
Syncline Loop
Taylor Canyon
Wilhite Canyon


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A jet electrostatic printing process is described which uses a unique ink formulation suitable for use on certain dark colored surfaces. This process provides rapid, automatic, non-contact printing with high contrast on dark-colored surfaces. It is particularly suitable for marking cable with dark sheathing such as carbon-doped polyethylene.
1. A process for jet video printing on a surface with diluted ink using a jet video printer in which printing takes place by forming a stream of ink droplets, some of which are charged electrically and electrostatically deflected onto the surface being printed, and the diluted ink is cured with radiation after printing CHARACTERIZED IN THAT the diluted ink comprises:
a. polar organic solvent in sufficient quantity so that the viscosity of the diluted ink is less than 20 cps in which said polar organic solvent accepts electric charge when ionizing agent is dissolved in said polar organic solvent, said polar organic solvent comprising at least one substance selected from the group consisting of methanol and ethanol,
b. radiation-curable prepolymer which on curing yields a polymer with elastic modulus between 2000 and 500,000 psi and elongation at least 10 percent, said prepolymer having a solubility in said polar organic solvent of at least 10 weight percent,
c. pigment in which 90 percent by weight of said pigment has agglomerate size less than 40 microns, said pigment present in amounts between 5 and 50 weight percent of the prepolymer,
d. ionizing agent which permits the diluted ink to accept electric charge present in amounts up to the weight of prepolymer.
2. The process of claim 1 in which the polar organic solvent is methanol.
3. The process of claim 1 in which the pigment is titanium dioxide.
4. The process of claim 3 in which the amount of pigment is between 10 and 30 weight percent of prepolymer.
5. The process of claim 1 in which the prepolymer is the reaction product of at least one epoxy compound and substance containing at least one photopolymerizable group.
6. The process of claim 5 in which the substance containing at least one photopolymerizable group is acrylic acid or methacrylic acid or a mixture of both.
7. The process of claim 5 in which the epoxy compound comprises a mixture of aromatic and aliphatic diglycidyl ethers.
8. The process of claim 7 in which the epoxy compounds comprise a mixture of 1,4-butanediol diglycidyl ether and the diglycidyl ether of monobromo bisphenol A.
9. The process of claim 8 in which the prepolymer is made by carrying out a reaction between 40-41 weight percent monobromo bisphenol A, 33-34 weight percent 1,4-butanediol diglycidyl ether and 26-27 weight percent acrylic acid.
10. The process of claim 9 in which the mixture contains 0.1 to 0.3 phr diethylaminoethanol and 0.1 to 0.3 phr hydroquinone, and the reaction is carried out at temperatures between 100-150 degrees C. until the acid value is less than 1.0.
11. The process of claim 1 in which the prepolymer is a urethane-acrylate.
12. The process of claim 11 in which the urethane is prepared from a mixture of aromatic and aliphatic diisocyanates.
13. The process of claim 12 in which the acrylate is hydroxyethylmethacrylate or hydroxypropylmethacrylate or a mixture of both.
14. The process of claim 1 in which the diluted ink comprises in addition
a. nonpolar solvent which leads to a small amount of dissolution of the surface being printed so as to promote greater adherence of the ink to surface being printed,
b. antisettling agent,
c. silane coupling agent, and
d. titanium coupling agent.
15. The process of claim 1 in which
a. the nonpolar solvent is toluene,
b. the antisettling agent is titanium di(octylphosphate)oxyacetate,
c. the silane coupling agent has the structural formula ##STR2## and d. the titanium coupling agent is tetra(2,2 diallyloxymethyl-1-buteneoxy) titanium di(di-tridecyl)phosphite.
16. The process of claim 1 in which an undiluted ink consists essentially of
a. 100 phr prepolymer,
b. 10-30 phr pigment,
c. 0-20 phr nonpolar solvent,
d. 0-20 phr polar solvent,
e. 0-1 phr antisettling agent,
f. 0.01-1 phr silane coupling agent, and
g. 0-1 phr titanium coupling agent, and said undiluted ink is diluted with polar organic solvent until the viscosity of the diluted ink is less than 20 cps.
17. The process of claim 1 in which the ionizing agent is ammonia.
18. The process of claim 1 in which the diluted ink contains photosensitizer.
19. The process of claim 18 in which the photosensitizer is either benzoin isobutyl ether or diethoxyacetophenone.
20. The process of claim 1 in which the surface is dark in color.
21. The process of claim 1 in which the surface is cable sheathing.
22. The process of claim 1 in which the radiation is ultraviolet radiation.
23. The process of claim 1 in which the radiation-curable prepolymer on curing yields a polymer with elastic modulus between 2000 and 50,000 psi and elongation at least 20 percent.
24. The process of claim 7 in which the epoxy compounds comprise a mixture of 1,4-butanediol diglycidyl ether, diglycidyl ether of bisphenol A and glycidyl ether of dibromophenol.
25. The process of claim 24 in which the prepolymer is made by carrying out a reaction between 28-29 weight percent diglycidyl ether of bisphenol A, 12-13 weight percent glycidyl ether of dibromophenol, 33-34 weight percent 1,4 - butanediol diglycidyl ether and 26-27 weight percent acrylic acid.
26. The process of claim 24 in which the prepolymer is made by carrying out a reaction between 10.5 to 12.5 weight percent of glycidyl ether of dibromophenol, 24-28 weight percent of diglycidyl ether of bisphenol A, 31-37 weight percent 1,4-butanediol diglycidyl ether and 26-29 weight percent acrylic acid.
27. The process of claim 24 in which the prepolymer is made by carrying out a reaction between 20-30 weight percent of diglycidyl ether of bisphenol A, 40-50 weight percent of 1,4-butanediol diglycidyl ether and 28-35 weight percent acrylic acid.
28. The process of claim 1 in which 90 percent of the pigment has agglomerate size less than five microns.
29. The process of claim 1 in which 60 percent of the pigment has agglomerate size less than 2.5 microns.
30. The process of claim 1 in which 60 percent of the pigment has agglomerate size less than one micron.
This application is a continuation-in-part of my copending application, Ser. No. 965,777, filed Dec. 4, 1978 now abandoned, a continuation of Ser. No. 793,861, 05/04/77, now abandoned.
1. Field of the Invention
The invention is a video jet printing process employing a unique ink composition.
2. Description of the Prior Art
Various printing processes are extensively used in commerce both for communication purposes and for marking goods. With increased sophistication and speed in manufacturing various articles, more sophisticated, flexible and rapid printing processes are needed. In addition, advances in computer technology and speed have increased the need for higher-speed printing processes to handle large data output at computer terminals.
One of the problems involved in the adoption of more sophisticated and rapid printing processes is the development of inks which are compatible with the printing process and have sufficient contrast with the surface being printed to be useful. Indeed, even adherence to surfaces is a major problem, particularly where various plastics and polymers are involved. A typical example is marking cable sheathing made of carbon-filled polyethylene.
The video jet printing process is an advantageous procedure for marking and printing on certain articles. This procedure exhibits high speeds, is automatic and does not require contact with the surface being marked. It has no moving parts and requires a minimum of printed attention. Printing may be carried out on irregular surfaces with good results.
In summary, the video jet printing process is well suited to many printing applications including, for example, marking sheathing on wire cable.
An understanding of the invention is facilitated by a description of the video jet printing system. An ink stream is developed under pressure at a nozzle assembly. This stream is modulated at ultrasonic frequencies so as to produce droplets of more or less uniform size. The droplets are directed toward the substrate to be printed. The electric charge is transferred to some of the drops in a predetermined way so that they are deflected appropriately during subsequent passage between high voltage plates. This deflection controls the vertical axis landing pattern since the deflection is proportional to the charge on ink drops. Horizontal axis spacing is controlled by frequency of strokes and the speed of the substrate. Uncharged drops are returned to the ink reservoir.
Inks usually consist of dyes dissolved in a suitable solvent such as methanol. Such an ink system is satisfactory where the background is light in color or transparent, but for dark backgrounds the contrast is insufficient. In addition, other restrictions of the characteristics of the ink system are imposed by the nature of the video jet printing system and the nature of the surface being printed. For example, each droplet of the ink produced by the print system should be approximately the same weight to be compatible with the deflection system. Some mechanism should be provided so the ink will adhere to the surface being printed. The color should be light (white or yellow) so as to produce contrast with the dark background. The viscosity should be low (preferably less than 10 cps) so as to be compatible with the printing system. The ink should be soluble in polar solvents like methanol.
The invention is a jet electrostatic printing process in which an ink of unique formulation is used. The ink is particularly suitable for jet printing and printing on dark-colored or black surfaces. The ink is a solution of radiation-curable prepolymer with pigment suspended in the solution. Various pigments may be used including BaSO4 and ZnO, but TiO2 is preferred because of greater hiding power (high refractive index). Composition of the prepolymer is adjusted so that on curing, its properties will be compatible with the surface being printed. For example, elastic modulus is preferably within a factor of two of that exhibited by the surface being printed (10,000-50,000 psi for many polymer surfaces). The cured polymer is flexible and has an elongation of at least 10 percent. Other components may also be contained in the ink, such as antisettling agents, titanium and silane coupling agents, diluting agents (generally methanol and toluene), small amounts of ionizing agent (generally ammonia), and a sensitizing agent. The jet electrostatic printing process practiced in accordance with the invention produces rapid printing with good contrast even on dark or black surfaces.
FIG. 1 shows a diagramatic sketch of a jet electrostatic printer;
FIG. 2 shows a black, polyethylene-sheathed cable with printed numbers produced in accordance with the invention.
In its broadest aspects, the invention is a video jet prnting process with a unique type of ink. The ink comprises radiation-curable prepolymer, pigment, certain additives such as coupling agents, surface modifiers, antisettling agents, solvents and conductivity-enhancing material (ionizing agent). Also, other agents may be included such as a stabilizer and photosensitizer.
In general, the prepolymer may be any compound or mixture of compounds which can be radiation cured with physical and chemical properties suitable for attachment to the surface being printed and which, together with the other ingredients of the ink, is compatible with the video jet printing system. The prepolymer system should have preferably some polar groups so that it will have reasonable solubility in the polar organic solvents (e.g., methanol, ethanol) used in the printing process. Polar organic solvent includes liquids with one to four carbon atoms and polar groups such as hydroxyl, nitro, amino, halogen, carboxylic and ketone groups. The solvent may be a mixture of various polar organic liquids although a single liquid (e.g., methanol, ethanol, etc.) is generally preferred. Also, the prepolyer molecule contains groups which polymerize on exposure to radiation (generally ultraviolet light). These photopolymerizable groups are generally double bonds (often carbon-carbon double bonds).
Particular prepolymers are made by chemically reacting epoxy compounds and preurethane compounds with various compounds containing photopolymerizable groups such as double bonds.
Two exemplary prepolymer systems are the epoxy-acrylate system and the urethane-acrylate system (either single components or mixtures). These systems can be tailored so as to result in radiation-cured polymers with certain desirable mechanical properties. These mechanical properties are elastic modulus between 2000 and 50,000 psi for relatively low modulus substrates and 2000-500,000 for relatively tough substrates and elongation of at least 10 percent. Elastic modulus and elongation are preferably matched to the surface being printed and in most instances should be between 5000 and 15,000 psi for elastic modulus and at least 20 percent for elongation. Generally, the prepolymer should be polar to permit significant solubility in polar solvents such as methanol for use in the jet electrostatic printer. A polar solvent is used in the jet electrostatic printer because droplets used in the printing process are electrically charged. Also, the polar solvent preferably should be fairly volatile to insure rapid evaporation after printing on the surface to be printed. These mechanical properties are obtained with a single epoxy-acrylate or urethane-acrylate system, but it is usually more convenient to use a multicomponent epoxy-acrylate or multicomponent urethane-acrylate system.
For example, with the epoxy-acrylate system, aromatic glycidyl ethers, when reacted with acrylic acid systems and radiation cured tend to form hard, brittle, high elastic modulus polymers whereas aliphatic glycidyl ethers form soft, rubbery, high elongation-low elastic modulus polymers. Excellent prepolymers for the practice of the invention are made by mixing suitable amounts of aromatic and aliphatic glycidyl ethers together to achieve the desired mechanical properties. Many aromatic and aliphatic glycidyl ethers are well known and described in the polymer literature. Some are described by Henry Lee and Kris Neville in Handbook of Epoxy Resins, McGraw-Hill, New York, especially Chapter 2. Diglycidyl ethers of aromatic or aliphatic compounds (or both) are preferred for two reasons. First, the cured polymer has more desirable properties. The greater polarity of the prepolymer permits greater solubility in the polar solvent and greater compatibility with the jet electrostatic printing system.
Excellent results are obtained with 1,4-butanediol diglycidyl ether and a diglycidyl ether of an aromatic compound such as bisphenol A, substituted bisphenol A and particularly chlorinated or brominated bisphenol A. Monobromo bisphenol A gives excellent results in terms of properties of the radiation-cured prepolymer compatibility with the printing system and solubility of the prepolymer in polar solvents.
In its more general form, the prepolymer is formed by reacting the epoxy compound with a double-bond compound which will yield a photopolymerizable prepolymer. This may be achieved by reacting the epoxy compound with an acrylic acid derivative (including acrylic acid itself) to form the epoxy-acrylate prepolymer. Various acrylic acid derivatives may be used but usually acrylic acid and/or methacrylic acid is preferred because of easy availability and good results.
The epoxy-acrylate system may contain two other ingredients useful in making the prepolymer. These components, although not necessary to the practice of the invention, make it easier to carry out the reaction between glycidyl groups and carboxylic acid groups and minimized unwanted polymerization of the double bond. First, a catalyst may be used to enhance reaction of the glycidyl ether group on the epoxy and the carboxylic acid group of the acrylic acid. Various catalysts are described in the above-mentioned reference by Lee and Neville, especially in Chapter 8, 9, 10, 11 and 12. Diethylaminoethanol and dimethylaminoethanol are particular examples.
A stabilizer is also used to prevent polymerization of the double bond during the formation of the prepolymer. Various stabilizers may be used such as the methyl ether of hydroquinone, tertiary butyl catechol, etc. Hydroquinone is preferred because of low cost, easy availability and excellent results obtained.
The epoxy compound or compounds are mixed with the acrylic acid compound together with catalyst and stabilizer if used and the mixture stirred and heated if necessary to promote reaction. Generally, the reaction is carried out until the acid value [mg KOH needed to neutralize 1 gm reactants ] is less than one.
A particular example serves to illustrate the use of this type of prepolymer. The following ingredients are mixed together: 40-41 weight percent monobromo bisphenol A, 33-34 weight percent 1,4-butanediol diglycidyl ether and 26-27 weight percent acrylic acid. Added to this mixture is 0.1 to 0.3 parts per hundred (phr) diethylaminoethanol and 0.1 to 0.3 phr hydroquinone. This entire mixture is heated in a flask at from 100-150 degrees C. until the reaction has proceeded to where the acid value is less than 1.0.
In another example, the 40-41 weight percent monobromo bisphenol A is substituted with 28-29 weight percent diglycidyl ether of bisphenol A and 12-13 weight percent of glycidyl ether of dibromophenol.The remainder of the process is carried out as above. Because the epoxy equivalent weight varies from batch to batch, the above compositions may vary accordingly. Such a composition is 10.5 to 12.5 weight percent of glycidyl ether of dibromophenol, 24-28 weight percent of diglycidyl ether of bisphenol A, 31-37 weight percent 1,4-butanediol diglycidyl ether and 26-29 weight percent acrylic acid. The remainder of the experiment is carried out as above.
Another example is as follows. 20-30 weight percent of diglycidyl ether of bisphenol A, 40-50 weight percent of 1,4 butanediol diglycidyl ether and 28-35 weight percent acrylic acid. The remainder of the example is carried out as above.
Another prepolymer system which is useful in the practice of the invention is the urethane-acrylate prepolymer system. Again, composition is adjusted so that the radiation-cured polymer has the mechanical properties outlined above the system and is compatible with the jet electrostatic printing system. Single urethane-acrylate systems may be used to achieve these requirements. More frequently, these properties are more conveniently obtained from mixtures of urethane-acrylate systems. Often, the systems contain prepolymers that cure into rubbery polymers such as aliphatic isocyanate-acrylates and prepolymers which cure into hard polymers such as aromatic isocyanate-acrylates. Typical aliphatic and aromatic isocyanates are given in various parts of the scientific literature such as Advances in Urethane Science and Technology, Vol. 1 and 2 by K. C. Frisch and S. L. Reegen, Technomic Publishing, Stamford, Conn.
Particularly advantageous are diisocyanate compounds because the resulting prepolymer is more soluble in polar solvents. Examples are given in the above references.
The isocyanates are reacted with a hydroxyl containing acrylate compound to form the prepolymer. Various hydroxy acrylates may be used provided the compound contains at least one hydroxy group, has no more than 15 carbon atoms and no more than 4 hydroxy groups. Particular examples are hydroxyethylmethacrylate and hydroxypropyl-methacrylate.
The mechanical properties of the cured polymer may be altered by the addition of organic hydroxyl compounds. The addition of long chain (4-15 carbon atoms) monohydroxyl compounds makes the cured polymer softer, more rubbery, with lower elastic modulus and greater elongation. The addition of short-chain (6 carbons or less) dihydroxyl the organic compounds or trihydroxy organic compounds makes the cured polymer harder, with higher elastic modulus.
The ingredients, isocyanate, hydroxy acrylate and optionally organic hydroxy compound are reacted together with a catalyst to form the prepolymer. Various catalysts and mixed catalysts are discussed in Chapter 1, volume 1, of the above reference. Stannous octoate catalyst yields particularly good results. Generally, the reaction is carried out until at least 90 percent of the isocyanate groups are reacted. Often, essentially complete reaction is preferred because of the excellent mechanical and chemical properties obtained.
A number of examples might serve to illustrate the prepolymer system.
A quantity of 168 gms of 1,6-hexamethylene diisocyanate (HDI) is reacted with 273 gms of hydroxyethylmethacrylate in the presence of stannous octoate catalyst until nearly all (at least 90 percent by weight) the isocyanate is reacted. Moderate amounts of heat as well as mixing may be used to promote the reaction.
The same as example 1 except that 302 gms of hydroxypropylmethacrylate is used in place of the hydroxyethylmethacrylate.
A quantity of 174 gms of toluene diisocyanate (TDI) are reacted with 102 gms of hexanol until essentially all the hexanol is reacted. Then, 143 gms of hydroxyethylmethacrylate are added and reaction carried out until nearly all (at least 90 percent by weight) the isocyanate is reacted. Moderate heat and mixing may be used to promote the reaction.
Various pigments well known in the art may be used including zinc oxide, barium sulfate, and titanium oxide. Titanium oxide is preferred because of its greater hiding power, easy availability and suitable particle characteristics. Quite wide variations in amount of pigment are permitted (say from 5-50 weight percent of prepolymer) but best results in terms of cured polymer properties and hiding power are obtained with 10-30 weight percent. Because of the nature of the jet electrostatic printing or video jet printing system the pigment should be used in a particular physical form especially regarding particle size. Small particle size is preferred; generally, it is advantageous if 90 percent by weight of the pigment have an agglomerate size less than 40 microns.
Pigments obtained commercially should be processed in such a way as to reduce their particle size to some small value preferably less than 40 microns. For example, titanium dioxide obtained commercially (as for example from American Cyanamid Company with oil absorption less than 40) is processed usually by grounding (ball milling, sand milling, etc.,) usually for times between one hour and 100 hours or more so as to achieve small particle size.
Pigment particle size less than five microns is generally preferred because it is relatively easily achieved and ensures uniform droplet weight. Generally, it is sufficient that 90 percent of the pigment have particle or agglomerate size less than five microns.
A particularly convenient way of both achieving small particle size for the pigment and insuring good uniform mixing of the ink is to add together the ingredients of the ink and then mixing preferably by grinding and/or ball milling the components together. The pigment, prepolymer and polar solvent are mixed together. The polar solvent should be suitable for dissolving the prepolymer and be compatible with the jet electrostatic printer. Typically, methanol is used. Optionally, a nonpolar solvent such as toluene may be added. Since methanol is particularly suitable for use in the printer, its use at this stage is also convenient. The nonpolar solvent is added to promote a small amount of dissolution of the surface being printed. Such dissolution of the surface being printed is believed to lead to greater adherence of the ink to the surface.
For smaller character size and/or clearer printing (greater separation of individual drops), drop size should be reduced to 50 microns or even 20 microns for especially small print character size. Droplet weight should be uniform to ensure that each droplet can be accurately deflected to a given predetermined point. To ensure uniform weight distribution, the size of the pigment particles should be small compared to droplet size. Generally, this requires that pigment particle size is less than approximately 1/20th of the droplet size. For a droplet size of 50 microns, this requires pigment particle size to be less than approximately 2.5 microns. For a droplet size of 20 microns, pigment particle size should be less than about one micron. Since considerable error can be tolerated in the printing process, only about 60 percent of the pigment particles must meet this requirement although 90 percent yields clearer and more efficient printing.
In addition to the above, it is preferred that small amounts of antisettling agent, silane coupling agent and titanium coupling agent be added to the mixture. Aromatic solvent may also be added to give solvent balance and keep the pigment in the diluted ink from settling or agglomerating. Suitable antisettling agents are disclosed in the literature. A typical example is titanium di(octylphosphate)oxyacetate. Various silane coupling agents are also well known in the literature. The chemical formula of a typical silane coupling agent is given below. ##STR1## Various titanium coupling agents are also well known from the literature. A typical example is tetra(2,2 diallyloxymethyl-1-buteneoxy) titanium di(di-tridecyl)phosphite. Concentrations of the various components making up the ink may vary over wide limits.
Excellent results are obtained using for every 100 phr prepolymer, 10-30 phr pigment, 0-20 phr nonpolar solvent, 0-20 phr polar solvent, 0-1 phr antisettling agent, 0.01-1 phr silane coupling agent and 0-1 phr titanium coupling agent. The mixture is then ground (e.g., by ball milling or sand milling) to achieve uniform mixing and small particle size.
Prior to use in the jet electrostatic printer, the ink is preferably diluted down with polar solvent and ionizing substance added. Ionizing substance is added to make the ink more conductive and to permit the ink to accept electric charge more readily. Ammonia is a preferred ionizing substance. More preferably, the polar solvent should be mixed with some aromatic solvent, generally up to 20 volume percent aromatic solvent. The aromatic solvent is generally toluene. Dilution should continue until the viscosity is preferably less than 10 cps. A dilution between 100 and 200 volume percent often gives a good compromise between suitability for the jet electrostatic printer and density of the printing on the surface to be printed. A photosensitizer is also added to promote photopolymerization of the prepolymer. Generally, a photosensitizer active in the ultraviolet region is preferred since it allows exposure of the ink-diluent mixture to ordinary (visible) light without adverse effects. Photosensitizers like benzoin isobutyl ether and diethoxyacetophenone give excellent results. Typical concentrations are 0.1 to 5 weight percent based on diluted ink.
Various photosensitizers may be used, many of which are described in the literature. (See, for example, "Aromatic Keto Compounds as Initiators in Photopolymerizations" by H. G. Heine et al, Angew Chemical International Edition, Volume 11, No. 11, page 974 (1972). Particularly convenient are various aromatic keto compounds including benzoin and some of its derivatives (methyl and isobutyl ethers) as well as benzil and derivatives.
Typical compositions which yield excellent printing results with the jet electrostatic printer were 30-60 weight percent ink, 40-70 weight percent polar solvent. The polar solvent preferred is methanol with 0.01 to 1.0 weight percent ammonia and 0.01 to 5 weight percent photosensitizer.
Before use in the jet electrostatic printer, the diluted ink is preferably filtered (sometimes internally in the jet electrostatic printer) to remove particles (including pigment) larger than 20-40 microns. Where smaller particle size is desired, a correspondingly smaller filter size (five microns or one micron, for example) may be used. After printing, the ink is cured by exposure to radiation. Where photosensitizer is used, it is preferred that much of the radiation be in the spectral range (frequency or wavelength range) where the photosensitizer is highly sensitive. An medium pressure ultraviolet lamp is generally used, typically with a power output of 200-300 watts per linear inch and a length of up to six feet. With cable marking, the cable may be run along the length of the lamp after printing.
An understanding of the invention is facilitated by a description of the operation of a jet electrostatic printer. A block diagram of a typical electrostatic printer is shown in FIG. 1. The printer 10 has a nozzle 11 into which ink is injected under pressure through the tube 12. The ink is broken up into droplets 13 by an ultrasonic vibrator (usually a piezoelectric crystal) with an applied ultrasonic signal from a signal source 14. The droplets of ink pass through a charging tunnel 15 which has applied to it a charging signal on conductor 16. The charged ink droplets pass through deflection plates 17 which either deflect the charge droplets to a particular place on the printing surface 18 or into a return tube 19 if no ink is to fall on a particular spot. The return tube returns ink to the ink reservoir.
FIG. 2 shows a particular surface 20 (in this case a cable sheathing) with numbers imprinted 21 in accordance with the inventive process.
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Students kicked off part of Litchfield playground after engandered birds lay eggs.
These two killdeer eggs have been laid in the center of the active playground at Griffin Memorial School in Litchfield.
The area around the eggs has been roped off to protect the nest. LEFT AND ABOVE: kimberly Houghton
bark mulch Two eggs are well camouflaged within the bark mulch at Griffin Memorial School's playground in Litchfield. Kimberly Houghton
Kindergarten students and a paraprofessional noticed the two birds hovering in the area on Monday and spotted the two speckled eggs. As a precaution against disturbing the eggs, Principal Scott Thompson kept students inside during recess on Monday. The school also contacted the state Fish and Game Department and the Audubon Society of New Hampshire.
Killdeer typically lay their eggs in depressions in open areas, often ringed by stones or mulch.wikipedia
According to Becky Suomala, a biologist with the Audubon Society, killdeer are very common in New Hampshire, and they are not endangered or threatened. Even so, Suomala stressed, they are protected under the Migratory Bird Treaty Act of 1918, meaning the law prevents their nests from being disturbed.
"They like to nest on open, flat ground such as construction sites, farm fields and roofs," she said. "They seem to be fairly tolerant of disturbance, but you cannot move the nest to a different location."
"Hopefully the birds will adapt to the activity there. If they don't, they could abandon the eggs if it isn't adaptable," she said.
If the nesting is successful, there is a chance the two adult birds will return next year to lay their eggs in the same location or nearby, Suomala said.
"We have warned the students to be respectful and careful. We realize it is difficult though, as these eggs are right out there in the open," Thompson said.
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