Dye bleach chemistry

Discussion in 'Color: Film, Paper, and Chemistry' started by Photo Engineer, Nov 14, 2007.

  1. Photo Engineer

    Photo Engineer Subscriber

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    I read how it is getting more and more difficult to buy Ilfochrome chemistry or more and more difficult to have it shipped.

    It is interesting to note that the chemistry contains nothing that cannot be shipped. That puzzles me.

    In any event, the developer is an ordinary B&W developer like Dektol or D-19. I know that is a broad range, but it is due to the contrast needs of the paper and I have not played with any for years, so I have to give you a range.

    The dye bleach solution is just sulfamic or sulfuric acid + a catalyst such as phenazine at about 10 - 100 mg/liter. There are dozens of catalysts in the literature that I can list if interested and dozens of formulas for this.

    The fix is a sodium hypo fix.

    Thats about it.

    I have been getting back up to speed on this and will post some dye bleach formulas for people. In the mean-time, someone like Dave Travis might be able to suggest alternate developers.

    Eventually, enthusiasts could be in a position to mix their own from common items. The sulfuric acid for example, can be gotten at an automobile store. Battery acid is 35% and certainly strong enough for dye bleach.

    PE
     
  2. Wayne

    Wayne Subscriber

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    I'm all ears. I already make (or made) my own developer and fix when I was doing Ilfochromes before, and will hopefully be starting again this year.

    How hard is the paper to make though? When chemicals become impossible to find that will mean the paper is dead. On the other hand if people could make their own bleach maybe it would increase demand for the paper. I somehow doubt it would make a difference but I can dream.


    Wayne
     
  3. Photo Engineer

    Photo Engineer Subscriber

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    Wayne;

    Dye bleach chemistry is doable. I have some chemicals on order right now that I will test and if it works, I will post the results.

    Dye bleach paper is coatable, provided you have the dyes and support. I have almost everything I need right now to make a 2 layer demonstration.

    So, when the time is ripe, when I have everything together, I will do it. It does not need to die.

    PE
     
  4. Bob Carnie

    Bob Carnie Subscriber

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    I purchase all my chemicals for Cibachrome from Wynit , who is the distributer for Ilford.
    Part of the problem is Cibachrome product line was hit tremendously with the advant of inkjet,
    Also the companies that were involved with managing this product over the last few years have gone through some very strange times.
    It seems to be easier now for me to get my product into Canada, basically it takes about a two month planning of what amounts will be reguired, placing the order with Wynit, the product is then shipped and if all goes well all the product lands at my door.

    Some things to consider.

    Wynit does not warehouse significant amounts of Cibachrome due to a small demand.* I do not blame them*
    Your local camera store may/maynot be in a good fiscal situation with Wynit. Or may not want to tie inventory in a slow product.
    Ilford Switzerland for some unknow reason does not want to market this excellent product.
    As all here well know the product is very expensive.
    Custom making chemicals for this product is ok, but I do not do this, for example there is an agent in the developer and fix that is there for a purpose. *this is a sticky point with any techrep/factory and when I tried to do this 10 years ago I was basically told that they would not support my quality/stability claims if I did so.. now this could of been a slick one pulled over my head, I did purchase the Brooklyn Bridge a few years back.
    Just be aware that there are these issues to look into.

    Some solutions.

    Someone decides to round up all the ciba users that are purchasing in small bulk packages and sets up a good arrangement with Wynit and drop ship orders to each client at the middlemans request.
    I would do this but right now my fingers are into so many pies that it would not make a lot of sense unless there were enought people willing to jump on board.
    One main purchaser, would be of interest to Wynit and I could make the introductions for anyone interested.
    I am sure that this person will be obligated to purchase the kits complete, and I know that if I was that person I would do so.
    One year down the line it would be painful to find all the spare Dev, Fix kits lying at Wynit not being ordered with nobody to purchase them.
     
  5. Wayne

    Wayne Subscriber

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    Wynit will not sell directly to end users in the US. They probably only do it for you because you are in Canada. In the US they recommend lab-ciba.com as the source for end users, it will then get drop-shipped from Wynit. I've spoken with them several times about this, most recently yesterday. However it may be cheaper to order from Calumet unless you are interested in very large quantities.

    You are absolutely right that Ilford is not marketing the product, and that does not bode well for its future. In fact Wynit doesnt even list it in their catalog or website so stores that they distribute to dont even know it exists. There definitely is a system firmly in place to prevent or deter its widespread use, whether by design or accident.

    Wayne
     
  6. boyooso

    boyooso Member

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    I can't remember in the past 12 years that ilford or any of its parent companies ever have promoted ilfochrome, it IS still around and a unique product in its industry. Obviously OJI in Japan and Ilford in Switzerland still think it is profitable and/or believe in it. So why the negative thoughts (don't produce a self fulfilling prophesy). FWIW, my lab has had little troubles getting our hands on materials since Ilford Imaging USA is out of the picture. Thanks for their demise!!!

    I can 'drop ship' P3 or P3X chemistry from 'wynit' if you like...

    Corey
     
  7. David A. Goldfarb

    David A. Goldfarb Moderator Staff Member Moderator

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    So if the developer is an ordinary B&W developer, someone must have tried other developers to control the contrast over all these years, but it must not have worked for some reason, or everyone would be doing it rather than contrast masking, which is much more labor intensive. Any ideas why not? I'd assume it's a color balance issue, but I'd be interested to hear if anyone has any real information on this topic.
     
  8. Wayne

    Wayne Subscriber

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    It used to work. There is somebody here who claims it still does, but I tried it extensively 6-7 years ago, and it just doesnt work in my experience. That was also the experience of others who used to do it previously, came back to it, and found it doesnt work anymore. Conclusion: There was an emulsion change sometime in the 90s, and afterwards it just didnt work like it used to, if at all. I never used the old emulsion, but I found the difference in contrast with assorted low contrast developers (including divided development) minimal to non-existent. I used the same formulas that previously worked for others in my inital tests, then tried a bunch of others. I also found that hydroquinone was needed or weird and undesirable things happened, so low contrast developers devoid of HQ were out of the question. My testing was not terribly scientific (science is my day job, my photography is by the gut), but it was fairly extensive. And I did write a lot of it down, somewhere...


    Wayne
     
  9. David A. Goldfarb

    David A. Goldfarb Moderator Staff Member Moderator

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    Thanks. When I did a lot of Cibachrome printing in the 1980s and early 1990s, I used to shoot a lot of Agfachrome 100, which was a relatively low contrast film, so it worked perfectly with Cibachrome without much need for masking. A little dodging and burning was sufficient.
     
  10. Wayne

    Wayne Subscriber

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    So how much do you charge for drop-shipped P3 bleach starter? PM me if you want. I have never used the P3 (only the old P30) and would like to because it can be bought separately, but I am wary because of its ill-defined need for replenishment. Do you have any current literature on P3? I have old literature on it but all I can find currently is the mixing instructions. Pretty useless if you dont know what you can do with it after mixing it.

    My understanding is that the P3 replenisher is the same as the starter, only a different dilution, but its far more expensive. But again, no literature.

    Wayne
     
  11. Ian Grant

    Ian Grant Subscriber

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    Not long after Cibachrome became popular in the 70's there were a number of alternative B&W developers published for contrast reduction, these worked well and caused no problems with colour balance. Masking can give much greater contrast reduction.

    Alternative developer suggestions for contrast reduction were regularly published in various US/Canadian photo magazines, and very occasionally in UK magazines. They can be found in back issues of Photo Techniques.

    One article suggested using De Beers variable contrast developer, I think a halide solvent like thiosulphate needed to be added after the new version of Cibachrome(Ilfochrome) was introduces.

    Ian
     
  12. Wayne

    Wayne Subscriber

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    But they wont anymore...


    Wayne
     
  13. Photo Engineer

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    Minor modifications could probably make it possible to use common developers.

    The problem is the cost of Cibachrome. That makes it prohibitively expensive. I used to do these types of experiments.

    PE
     
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  15. John Meyer

    John Meyer Member

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    I got an account with Ilford back in 1996 so i could get Ilfochrome chemicals/paper delivered to my door.All they wanted was a minimum order of $750 .. A yr ago i called in a order and Wynit answered the phone,
    they approved my application but said i would need a state of Texas resale number..I explained that im a photographer who finishes his own work for resale ..Well that was not a problem but they still need a resale number.
    Since then i have been traveling to Chicago Calumet to pick up orders,its 2400 mile round trip. Ive written to the guy in charge of color sales at Ilford Switzerland Jean-Noel.Gex@ilford.com. ,and sent a letter through the post all with no answer. If i lived close to Switzerland i would for sure knock on their door and find out what the problem is..For now unless i can find a for sure supply of the product ill just finish the materials that i have and be done with Ilfochrome.
    John
     
  16. Wayne

    Wayne Subscriber

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    Its usually easy enough to get the resale number but can be a PIA when you have to report to the state every year, and if you arent reselling they may take it away.

    But not to worry. There are at least 3 places to get the chemicals from, all mentioned in this thread. Lab-ciba.com, Calumet, and now boyooso too. BTW, Calumet told me they would ship with a $25 hazmat fee. I'm not sure if thats per kit or per order.

    I have never gotten a single word in response to questions sent to Ilford since the Disorganization a couple years ago. They used to have great technical support, now they effectively have none. I try to just be happy that their products are available-sort of, anyway.

    Wayne
     
  17. Wayne

    Wayne Subscriber

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    I was scouring old Usent posts and found this about recipes:

    " > Cibachrome (Ilfochrome) Bleach (I'm not interested in this one).

    Have you tried Wall's Enc. of Photog? Think the Ciba bleach is in there.
    Or in Heist's book. "



    I suspect the poster was wrong but I don't have the books to confirm it. Perhaps it was some other dye bleach recipe. Thought I would point it out though, in case it's helpful. We've solved the availability crisis for now; it'd be nice to solve the expense crisis too.


    Wayne
     
  18. Photo Engineer

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    Haist has no mention of the process that I could find, just a one liner. Wall, AFAIK, says nothing, not sure because I'm only really familiar with his books on emulsion making. The original name for dye bleach was Gasparcolor and is treated in a full chapter in Friedman's "History of Color Photography". There are at least a half dozen or more formulas for the bleach alone. In addition, I have many patent references here in addition to my own work at EK to rely on.

    PE
     
  19. Wayne

    Wayne Subscriber

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    Excellent. Let me know if I can help when you find time to work on it. I might be able to donate some paper to the cause. I know I've got some in a friend's freezer but I dont know how much. I've also got some old P30 bleach concentrate, but I dont know if its good anymore. Its probably 6 years old and its not getting any younger. Would you be attempting to make something similar to P3 or P30? The latter would probably be most useful for the home user.

    Wayne
     
  20. Roscoe

    Roscoe Member

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    See this thread:
    http://www.apug.org/forums/forum40/43590-ilfochrome-freestyle.html
     
  21. Wayne

    Wayne Subscriber

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    You may want to double check the accuracy of that thread. When I talked with Freestyle recently they said they were not selling Ilfochrome chemicals anymore. BUt there is so much confusion about what is and isnt available that its worth double and triple and quadruple checking. I was told recently by a Calumet salesman that P3 was being discontinued, but it is not. He even said he had checked with Wynit, their distributor, but I find that hard to believe because Wynit knows it isnt being discontinued. The SKU number changed, thats all. This is the kind of utter confusion and misinformation you will encounter trying to obtain Ilfochrome chemicals.

    Another mistake in that thread is the P3X is not the replacement for P30. P3.5, 5 liter kits was the replacement, and it looks like now that is being replaced by 2 liter kits again (just like the old P30 was a 2 liter kit) which will be called P3.2 just to ensure there is total confusion and chaos all around. This is for the US anyway. It may be different elsewhere.


    Wayne
     
  22. Photo Engineer

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    Wayne;

    I am so tied up with the book and DVD on emulsion making plus some other projects, that I cannot do work on this right now. And, when I do get into it, I will be testing it on my own dye bleach hand coatings aimed at generating some sort of home made dye bleach print material. IDK. It is still in the rough stages.

    I can give you the formulas though if you wish to experiment.

    PE
     
  23. boyooso

    boyooso Member

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    It is my understanding that the new Kit 30.2 IS NOT the same as the P30.

    The P30 had a safer bleach for home use. 'sulfonic' (?) acid instead of sulfuric acid.

    Again, it is my understaing (hopefully accurate) that the Kit 30.2 is P3 Chemicals...

    Corey
     
  24. Photo Engineer

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    Most formulas of the bleach used sulfamic acid. IDK what else they can use as the reaction does not take place easily much above about pH 2. Let me know what the MSDS says. Or what it says on the box of the new stuff. Maybe I can shed light on it.

    Most all solutions rely on an acid solution with pH of about 1.0 and a catalyst such as phenazine. Sulfuric acid was first used because it aids in the bleach reaction. In any event, the acid breaks the azo bond -N=N- into two -NH2 groups on the rings in the dyes and the dyes become colorless while silver is oxidized and partially dissolved.

    Dye is destroyed everywhere there is a negative silver image leaving behind a positive dye image. This way you get a positive dye image from a negative silver image directly. This works with most azo dyes or ones with -N=N- groups in them.

    PE
     
  25. Wayne

    Wayne Subscriber

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    Hi Corey,

    I emailed you a spreadsheet that I got from Wynit, which is what I'm basing my statement on. Its confusing, if you think I'm mistaken after seeing the spreadsheet please let me know. I couldnt figure out how to post it here.


    Wayne
     
  26. Wayne

    Wayne Subscriber

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    Absolutely, if you are primarily going to do it for a homemade print material I would be willing to test your bleach formula(s) on Ilfochrome. I dont know when I can get to it either; I may have time for some preliminary tests in the next month though, if I can get all the chemicals in time. After that I might be pretty busy too, until later this year.


    Wayne