Dye bleach chemistry

[Wayne]

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.

This is from P30, 6-7 years old, the 2 liter home use kit


PartA
p-toluene sulfonic acid
a quinoxaline adduct (CAS confidential) and
sodium m-nitrobenzenesulfonate

Part B
Potassium carbonate
potassium iodide
trialkylphosphine sulfonate (CAS confidential)

Part C
sulfamic acid

I posted this last year when this topic came up
(there was a url link here which no longer exists)

One poster said that it could be expensive, so I'll qualify my volunteering to test a recipe to say "if its not too difficult or expensive".


Wayne

 

[Photo Engineer]

The quinoxaline adduct is like the phenazine. It is the catalyst.

The two acids are there to get the right pH. The Iodide helps bleaching by supplying a halide. The trialkylphosphine sulfonate is some sort of sequestrant IIRC and may be in the Dequest class of sequestrants which can be found by googling.

I have a whole list of quinoxalines that work. These are expensive and tend to be carcinogens. You can see from my post there in your other thread, one of the formulas that I looked up for you.

PE

 

[Wayne]

The quinoxaline adduct is like the phenazine. It is the catalyst.

The two acids are there to get the right pH. The Iodide helps bleaching by supplying a halide. The trialkylphosphine sulfonate is some sort of sequestrant IIRC and may be in the Dequest class of sequestrants which can be found by googling.

I have a whole list of quinoxalines that work. These are expensive and tend to be carcinogens. You can see from my post there in your other thread, one of the formulas that I looked up for you.

PE

I didnt reread that whole thread, I just went back because I recalled posting the ingredients. If I had remembered everything that other fella said, I would probably have been smart enough not to volunteer myself for the job.
I think this is probably best left to someone skilled than I am. I can certainly mix and test a formula, but it sounds like it may be a lot more involved than that.

Wayne

 

[Photo Engineer]

Wayne;

If/when I get there, I will publish the entire formula for a dye bleach material. If I can, I'll try to find notes on work done with Haist on this.

PE

 

[Roscoe]

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

Hmmm. Check the accuracy. Well, I just looked in the darkroom and the Ilfochrome paper (CLM1K) and chem (P30.2) the Freestyle had drop shipped from Oji/Ilford in November isn't a hallucination, so I guess that's accurate.

Wot?

Also, the replacement for P30 is P30.2, still 2L, but now all liquid. The fact that the bleach is now liquid seems to be the cause for the shipping problems.

Confusion? The Ilford/Oji site lists the products, and more info is available via phone. All I had to do is ask about availability at Freestyle and they looked into a special order. The CLM1K was backordered so it took 3 weeks to arrive. CPS would have been shipped right away.

I'd like to thank Ron, here, for his insights and attention to the dye bleach process and materials. There is nothing that looks as lovely as an Ilfochrome Deluxe Glossy print and I hope to continue using it or something like it despite the vagaries of the marketplace.

 

[Photo Engineer]

Since this started anew, I have found another bottleneck. We discussed this at our engineers lunch last Wed.

Ilford color dye bleach material is coated on a white plastic material which is a polymer mixed with titanium dioxide. This is becoming less and less available. One US source seems to have dropped it from their product list. I have about 50 feet of a 42" roll here for coating experiments, but that is it.

The reason this plastic like material must be used is that the acid bleach attacks most paper supports and they dissolve in the bleach. It even goes after RC by means of edge penetration.

So, IDK what the situation wrt support is out there, but it is restricted to this one type - or else!

PE

 

[PHOTOTONE]

Since this started anew, I have found another bottleneck. We discussed this at our engineers lunch last Wed.

Ilford color dye bleach material is coated on a white plastic material which is a polymer mixed with titanium dioxide. This is becoming less and less available. One US source seems to have dropped it from their product list. I have about 50 feet of a 42" roll here for coating experiments, but that is it.

The reason this plastic like material must be used is that the acid bleach attacks most paper supports and they dissolve in the bleach. It even goes after RC by means of edge penetration.

So, IDK what the situation wrt support is out there, but it is restricted to this one type - or else!

PE

While that I'm sure is true, Ilford DID make (if they don't still) a RC variant of Ilfochrome, which was advertised as having slightly lower contrast. I wonder how they got around the bleach penetration issue?

 

[Photo Engineer]

If it had lower contrast and if it took a different process, it was probably achieved by raising the pH of the bleach and changing the formulation of the bleach and the paper to avoid the problem. Another way, which is very expensive, is to crimp and heat seal the edges of the RC paper as it is slit and chopped. Very difficult and expensive.

The final way is to just accept the defect of swollen edges that absorb chemicals and become ragged.

So, OTOMH, there are several suggestions, but the final analysis is that the paper was lower in contrast and therefore saturation, so they paid a price. It was not identical to the other products.

PE

 

[PHOTOTONE]

I don't think it (the RC version) took a different process. Rather the lower contrast could have been the difference in the reflectivity of the base between a RC style paper base, and Titanium oxide coated plastic.

 

[Photo Engineer]

The reflectivity is pretty much the same. Kodak made a support for Kodachrome prints and a dye bleach material and internally the support was called Azochrome support. I have a small sample here, and have coated on it and seen Kotavachrome prints. Not much difference if the same level of titanox is kept. Reflectivity = reflectivity after all. But, if you skimp on TiO2, then you have problems.

I've done dye bleach on RC suppor and on paper support both. You can do it but the resultant prints are not as pretty as those on the real polymer + TiO2.

PE

 

[Wayne]

Hmmm. Check the accuracy. Well, I just looked in the darkroom and the Ilfochrome paper (CLM1K) and chem (P30.2) the Freestyle had drop shipped from Oji/Ilford in November isn't a hallucination, so I guess that's accurate.

Wot?

Also, the replacement for P30 is P30.2, still 2L, but now all liquid. The fact that the bleach is now liquid seems to be the cause for the shipping problems.

Confusion? The Ilford/Oji site lists the products, and more info is available via phone. All I had to do is ask about availability at Freestyle and they looked into a special order. The CLM1K was backordered so it took 3 weeks to arrive. CPS would have been shipped right away.

I'd like to thank Ron, here, for his insights and attention to the dye bleach process and materials. There is nothing that looks as lovely as an Ilfochrome Deluxe Glossy print and I hope to continue using it or something like it despite the vagaries of the marketplace.

Hmm...in October you spoke with Freestyle and they said they would ship Ifochrome chemicals, and last week I spoke to them and they said they cant or wont. I call that confusion.

Last week I called Calumet and the salesman told me P3 was discontinued and gone forever, and I confirmed with the distributor that what changed was the SKU number and product code and concentrate sizes, but it is still available. I, the customer, had to call Calumet back and tell them, the seller, that it was indeed still available. (actually I didnt have to call them back, I did it so yet more misinformation wouldn't be spread by one of the largest photo retailers in the country). I call that confusion.

P3.5 replaced the P30 which was not available for some time after the initial disorganization of Ilford, P3.5 is now being replaced by P3.2, like I already said above. I have the old/new product cross reference spreadsheet from Wynit that I can email you if you would like.


Wayne

 

[Wayne]

I don't think it (the RC version) took a different process.

I recall it using the same process too-I only used it a few times but I used P30 chemicals.

 

[boyooso]

Yes, the RC material was processed using the same P3, or P3X chemistry. And it was discontinued 3-4 years ago, though even 1.5 years ago Ilford Imaging USA hadn't liquidated it all yet. But by now is is gone or gone bad.

Wayne, just to clarify the new process kit is called "Kit 30.2"

Confusion, yes. In my experience Ilford Imaging USA was a great believer in NOT TALKING about what was going on. Now Wynit is in the picture, and they may be more willing to talk about it all, but they do not have the knowledge, they are a distributer trying to distribute a product, that is it.

I am happy that Wayne is getting some feedback from them, it is encouraging.

FWIW, Oji Ilford has an office in USA. As a lab / dealer I have had just a little luck getting a response from them. I would be curious to know of your luck?

Here is their info

OJI ILFORD USA
1350 Main St
Springfield, MA 01103
Toll Free : 888.453.6731
Main : 413.732.8269
Fax : 413-732-8033

Good Luck,

Corey

 

[Wayne]

Wayne, just to clarify the new process kit is called "Kit 30.2"

Corey

Yes, you're right Corey. My bad.

 

[Bob Carnie]

I have used both versions , and they did indeed go through the same chems.

If it had lower contrast and if it took a different process, it was probably achieved by raising the pH of the bleach and changing the formulation of the bleach and the paper to avoid the problem. Another way, which is very expensive, is to crimp and heat seal the edges of the RC paper as it is slit and chopped. Very difficult and expensive.

The final way is to just accept the defect of swollen edges that absorb chemicals and become ragged.

So, OTOMH, there are several suggestions, but the final analysis is that the paper was lower in contrast and therefore saturation, so they paid a price. It was not identical to the other products.

PE

 

[John Meyer]

Yes im allso happy that Wayne is getting feedback from Wynit and others ..
It made me think of a company called Dye Chrome Research in Florida,back in the 90's that had their own mix of Ciba chems .. Something like K1 & K2,
different temps. Ctein mentions it in his book Post Exposure. I only wish we could convince Wynit to sell to us through some kind of co-op large or small orders..Im afraid that if something dont happen soon we wont be seeing Illfochrome any more. I wonder if they still make a 20l kit.. I called Freestyle this week and they seem like they dont even want to talk about it. I will be calling OJI Ilford USA nexk week. John

 

[narigas2006]

Catalyser for cibachrome bleach

Hi PE,

I am having some difficulties in finding the quinline for the bleach, would you have other candidates for substitution? Many thanks!

 

[Photo Engineer]

No, it is a phenazine or similar quinoline derivatives. I have a whole patent full of them. All I have to do is find the patent, but to date, no luck.

The basic reactant has a molecular formula of C4N2H4. Other derivatives put an additional C4 ring on this and some have -OH added to the ring. This venue is not good for organic chemistry structures.

PE