Modern Rodinal Substitutes Part II

[Photo Engineer]

I have found no reference in my notes about sulfonic acids as antioxidants, but I have found notes about sulfinic acids being used as antioxidants. I have no mention in those notes what types of sulfinic acids. I have only conducted a very simple google search so far. So, I have no more to add.

PE

 

[Kirk Keyes]

Sulfonic acids, as a class, are often used as detergents/wetting agents. Benzene sulfonic acid is probably not used for that much as it's rather reactive, I thought. But longer chained sulfonic acids are, as you can have an alkane or aromatic on an alkane chain and the sulfonic acid group on the other end, and that's good for detergents.

 

[Photo Engineer]

The classic detergent or surfactant of that class is di-nonyl-napthalene sulfonic acid sodium salt. Yes, I agree Kirk, they seem to be detergents, but then Sorbitol is a sugar but can act as an oxygen barrier by eating up free radical oxygen, so I don't rule this possible use out.

PE

 

[Ian Grant]

It appears that I had the Orwo R09 formula sat on my laptop from 2 years ago, and misplaced it but couldn't translate "Benzosulifinian sodowy" from the Polish.

So the question is are Sodium benzenesulfonate and Benzosulifinian sodowy the same. The compound is in Patent's for a medical thermal imaging films as an anti oxidant, one made by a Rochester based company (not Kodak).

In general anti-oxidants are rare in B&W developers - except Champlin's formulae, the high sulphite level rules out many that are used in Colour developers.

Ian

 

[Photo Engineer]

Grant;

AFAIK, Benzenesulfinian is Benzene sulfinic not sulfonic which would be -sulfonian or somehing like tht. Polish speakers please verify my very rusty translating efforts of organic chemistry.

An afterthought: We might ask pavel if he can verify that his Russian translation is benzene sulfonic..... That might also be questioned in view of my notes on Sulfinic acids.

PE

 

[Ian Grant]

Look at USP 4095982. Fuji are using Sodium benzenesulfonate (Benzenesulfonic acid sodium salt) as an anti-oxidant. As it's use as an anti-oxidant is referenced in a number of other Photographic Patents I think we can be 100% certain that Pavel's got it right. It's used as an anti-oxidant in many other field too and made & sold in bulk quantities.

I have another Polish source calling it "Benzosulifinian sodow" in Orwo RO9. But I suspect this is a Typo or translation in a publication as the sulphonic group translates as Sulfonian as Ron says.

Ian

 

[Photo Engineer]

Maybe David Goldfarb could step in here and give us a definitive reading on the Polish translation.

PE

 

[Ray Rogers]

Look at USP 4095982. Fuji are using Sodium benzenesulfonate (Benzenesulfonic acid sodium salt) as an anti-oxidant.

Ian, are you quite sure about that?

That sulfonate is a soap as well as a biocide and is mentioned as a coating aid, not as an antioxidant, (as far as I was willing to read anyway)...

Did they tuck that info somewhere I did not look,
or did you give us the wrong number?

In anycase, I think the comment that it acts to "decrease" the diffusion of oxygen is much more interesting however. I gather this can be done by forming at least 2 phases of different oxygen solubilty... from my lack of knoweledge of how soaps work, I can only say that it sounds like it might at least be plausable.

Ray

 

[Ian Grant]

Maybe David Goldfarb could step in here and give us a definitive reading on the Polish translation.
PE

Not needed as it's almost certainly an error probably of translation into Polish originally, I've now confirmed the Agfa link to Sodium Benzenesulfonate use in developers in the 1930, which fits the time frame for these additives in Rodinal.

About 7 or 8 years ago I was given a list of Eastern European formulae in Polish but with translations of every chemical name except "Benzosulifinian sodow" which was why I'd put the formula to one side.

However it turns out that Kodak reference Benezesulfonates specifically in USP 2,618,558 and the cited references link Sodium benzenesulfonate directly to a 1930's Agfa Ansco Patent USP 2,000,353 (German 506,838), others cite different German Patents. Some of the other German pre-WWII Patents may be more specific and useful.

Ian, are you quite sure about that?

That sulfonate is a soap as well as a biocide and is mentioned as a coating aid, not as an antioxidant, (as far as I was willing to read anyway)...

Did they tuck that info somewhere I did not look, or did you give us the wrong number?

Ray

It's in a few Fuji Patents, perhaps this one is better USP 2618558 where Sodium Benzenesulfonate is specifically mentioned as an anti-foggant, see attachment.

What's important is that the Patents show Agfa, Kodak and Fuji using Benzenesulfonates as anti-foggants, Agfa as far back as the 1930's.

Ian

 

[Ray Rogers]

Ian, are you quite sure about that?

That sulfonate is a soap as well as a biocide and is mentioned as a coating aid, not as an antioxidant, (as far as I was willing to read anyway)...

Did they tuck that info somewhere I did not look, or did you give us the wrong number?

Ray

It's in a few Fuji Patents, perhaps this one is better USP 2618558 where Sodium Benzenesulfonate is specifically mentioned as an anti-foggant, see attachment.

What's important is that the Patents show Agfa, Kodak and Fuji using Benzenesulfonates as anti-foggants, Agfa as far back as the 1930's.

Ian

Ian,

Please slow down and take another lookat those patents.

This is twice you have stated a certain patent claims sulphonates as antioxidants yet in both cases that does not seem to be the case.

Here, you also have provided an attachment that says Benzene sulfonate is an anti-oxidant, and by sentence structure, you imply it is from the named patent, but that does not seem to be the case either.

What is the correct source of the attachment?
(It actually looks familiar to me...)

I have been aware of the use of both sulfonates and sulfinates and I am not inspired by any of these examples; they are known technologies.

I am a little worried about your claim that those patents say something that they appearently do not. (I SURE hope I did not overlook it -if I did I do apologize, but...) Perhaps we all might fare better if we slow down a bit.

For me at least,
it would be better to get solid information at a snails pace,
than flimsy info faster than a speeding bullet.

I lost a few hours today as a result of those speeding bullets.

Ray

 

[Ian Grant]

You need to read things , but I could have given all the Patent No's use the search feature in Adobe Acrobat: Try another US 3765892 this is the one I cut & pasted from. I'm skipping between Patents rather fast looking at it's uses, and the Fuji Patents are interlinked through citations etc.

2nd line states . . . . . . sodium benzenene-sulfonate, ascorbic acid, diethylhydroxylamine, etc are used as antioxidants. Page 3 of the Patent bottom of Column 3.

The fact that Fuji refer to it in at least 4 Patents, and that many other companies/patents refer to it as an antioxidant is rather conclusive that it can be used as such.
:

Sulfonic acids, as a class, are often used as detergents/wetting agents. Benzene sulfonic acid is probably not used for that much as it's rather reactive, I thought. But longer chained sulfonic acids are, as you can have an alkane or aromatic on an alkane chain and the sulfonic acid group on the other end, and that's good for detergents.

Sodium Benzenesulfonate may well fall somewhere between what Mason (& Levenson) cal anti-oxidants and wetting agents - which include sodium alkyl sulphonates.

I was more interested in finding a link to it's use by Agfa, I've save some of the other Patents for later reading but didn't think they were of that much interest.

Ian

 

[Photo Engineer]

Well, with the help of a friend, and after an exhaustive search of my Kodak literature and his German literature, we find only references to Benzenesulfinic acid as an antioxidant and generic sulfonates as wetting agents.

This is quite perplexing to find the sulfinic acids in both places as antioxidants and the sulfonic acids as wetting agents, and neither agreeing with what has gone on above. The above posts indicate that the sulfonic acids have both functions.

Either this is a "new" discovery on the part of researchers into the properties of sulfonates, or it is a very serious misprint/typo in the published literature. The materials we have come from our notes and actual usage.

PE

 

[Ian Grant]

Well the wealth of Patents that I've uncovered using Sodium Benzenesulfonate as an antioxidant in developers and thermal imaging emulsions plus what you say, and Mason (Levenson) seems to indicate it may have potential duel uses.

The early 30's Agfa Patent is using a wetting agent sodium dibutyl-napthalene-a(alpha)sulphonate in a p-Aminophenol developer to overcome uneven development. This compound is the only link to the Kodak & Fuji patent(s) that cite it, and they all use Sodium Benzesulphonate or other derivatives as well in some..

So what else did the Germans discover about using a sulphonate with a p-Aminophenol developer? Something that Fuji understood (much later), and Kodak (in the 40's). They are being used in ppd colour developers by Kodak at too high a level to be a wetting agent in USP 2618558 other cross citations go to other compounds used as antioxidants like Salicylic acid, andother sulphonic acids etc, USP 2444803 which is about anti-oxidants.

There's to many cross links to just be a coincidence:

Agfa/Bayer manufacture Sodium Benzenesulphonate
A related derivative is in an Agfa Patent, alongside p-Aminophenol.
Then Sodium Benzenesulphonate and derivatives are in Kodak Patent(s) not as wetting agents, there's only a trace of sulphite 0.5g to 5g PPD but 100g of the Sulphonate so it's the preservative. .
More recently they appear again as anti-oxidants in Fuji Patents for developers and thermal imaging products, and also as an anti-oxidant in thermal imaging materials in the US

Finally it's in the RO9 Formula that Pavel postedn and there must be some logic. There so many cross linked Patents Citations in two directions and often just hidden away but important

Ian

 

[Ray Rogers]

You need to read things , : Try another [...]
US 3765892
this is the one I cut & pasted from. I'm skipping between Patents rather fast... Ian

Well Ian yes you need to read things.

I don't understand why you are not more sensitive regarding your release of misinformation /misdirection but well, OK. whatever. You did finally get it right on your third try!

I thought that text looked famaliar... I still have notes notes from Dr. Iwano's lectures - He is a very cheerful person. The last time I spoke to him was when the director of IPI was here, some months ago. (Photographer Eiko Hosoe was there as well - if you are one of those who like his work/ideas)

Anyway I was quite happy to be reminded of Dr. Iwano.
I think I gave him a really hard time!

 

[Photo Engineer]

I tried a search of USP 3765892 and find no reference to benzene sulfonates. The "find" utility in the PDF file does not find it, but it is found in the search of the text version. It becomes clear though that there are errors such as the claim of an antioxidant called potassium fulfite!

Errors do happen. The point is that we do not know for sure in spite of that patent.

I might add, in support of my comments, that diethy hydroxyl amine, which is claimed as an antioxidant, would be a very poor one for B&W developing agents, especially at that pH.

PE

 

[Ian Grant]

I don't understand why you are not more sensitive regarding your release of misinformation /misdirection but well, OK. whatever. You did finally get it right on your third try!

I thought that text looked famaliar... I still have notes notes from Dr. Iwano's lectures - He is a very cheerful person. The last time I spoke to him was when the director of IPI was here, some months ago. (Photographer Eiko Hosoe was there as well - if you are one of those who like his work/ideas)

Anyway I was quite happy to be reminded of Dr. Iwano.
I think I gave him a really hard time!

Aplogies I actually thought I'd given the right Fuji Patent No, when you speed read 20/30 in a row saving the relevant for later reading it's easy to grab the wrong number

Yes I know Eikoh Hosoe's work some is very interesting but I've not seen a book or exhibition yet.

Ian

 

[Alan Johnson]

You will be happy to find out that the experiment failed when I tried to bring the concentrations of p-aminophenol and ascorbic acid up to the level we're looking for in a concentrated stock. The only real difference is the substitution of about 29 grams of potassium ascorbate for 192 grams of potassium sulphite in 500 ml. What am I missing?

Ascorbate may not regenerate p-aminophenol.
I made some PaRodinal,added sulfite to make it solvent,then reduced the pH to about 8.5 by adding either ascorbic acid or boric acid.The ascorbic acid did not seem to give any extra activity compared to boric acid.I found no benefit in modifying PaRodinal in this way,it merely produces a developer that takes twice as long as D-76 to produce a rather similar result.IDK if the p-aminophenol version is more resistant to oxidation than D-76.
However,this was only one experiment but IIRC many have found adding sodium ascorbate to Rodinal to have some benefit,I don't know the cause of that.

 

[Ian Grant]

I tried a search of USP 3765892 and find no reference to benzene sulfonates. The "find" utility in the PDF file does not find it, but it is found in the search of the text version. It becomes clear though that there are errors such as the claim of an antioxidant called potassium fulfite!

Errors do happen. The point is that we do not know for sure in spite of that patent.

I might add, in support of my comments, that diethy hydroxyl amine, which is claimed as an antioxidant, would be a very poor one for B&W developing agents, especially at that pH.

PE

The Text part is OCRed which is why Text usually not there for old poor quality photocopied Patents.

Patents are waffle full of irrelevances hiding facts, ascorbic acid won't work at that high pH (examples) as an antioxidant either.

Kodak's ppd/Benzenesulphonate Patent is more interesting as the citation is to a an anti-oxidant Patent.

Ian

 

[Photo Engineer]

PDF files usually search well using the PDF find utility. I use it all the time. But the active word is "usually". I was just warning the readers.

I'm still not sure what role these two compounds play, nor am I sure that they are identified correctly.

PE

 

[Kirk Keyes]

Sodium Benzene sulphonate

Well, in the pesticide world, it's used as a soap (detergent).
http://www.pesticideinfo.org/Detail_Chemical.jsp?Rec_Id=PC34890

 

[Ian Grant]

Well, in the pesticide world, it's used as a soap (detergent).
http://www.pesticideinfo.org/Detail_Chemical.jsp?Rec_Id=PC34890

But is it ?

I think it's right on the borderline for classification, wetting agents are longer chains. A 2nd Kodak patent has quite similar although more complex organic compounds sulphonates/sulphonic acid salts as antioxidants but they aren't long chain.

In the Kodak PPD/Benzenesulfonate Patent they say it's used to help PPD dissolve, that's nonsense it's there for another reason.

There's some misinformtation in these early Patents, later Fuji hide it, although newer Patents are more open.

You can use a detergent as an Insecticide, or a soap, spray a solution of it on the insects and they drown, but if it's an antioxidant it'll be better

Ian

 

[Photo Engineer]

Ian;

It is well known that Benzene sulfonates help PPDs dissolve! In fact, a close analog, pTosyl (para Toluene Sulfonic Acid) is used for all CD3 developers and CD6 developers today.

PE

 

[Ray Rogers]

Ron

Both you and Ian have mentioned pH as one factor relating to usefulness of compounds clamed as antioxidant... Can you explain?

What other factors might be involved?

What could make one chemical a good AO in one case, but not in another?

Correct me if I am wrong, but isn't being an AO or not depandant upon the specific rxn being examined?

 

[Kirk Keyes]

But is it ?

I think it's right on the borderline for classification, wetting agents are longer chains.

Well, that's plain wrong. Follow the link I gave it is it clearly listed as a soap (i.e. a detergent).

In the Kodak PPD/Benzenesulfonate Patent they say it's used to help PPD dissolve, that's nonsense it's there for another reason.

Have you heard of co-solvents? A small amount of one compound is added to help another compound dissolve into the primary solvent (water in this case). The reason benzene sulfonate is going to be a good cosolvent is that it has both hydrophobic (water hating - the benzene part) and hydrophyllic (water loving - the sulfate part) functional groups in the molecule. That's pretty much how detergents work too.

You can use a detergent as an Insecticide, or a soap, spray a solution of it on the insects and they drown, but if it's an antioxidant it'll be better

Not sure why any possible antioxidant properties make a difference for pesticides...

But for use as a soap in pesticides, it is not going to be the major toxic component in those pesticide formulations!

 

[Kirk Keyes]

It is well known that Benzene sulfonates help PPDs dissolve! In fact, a close analog, pTosyl (para Toluene Sulfonic Acid) is used for all CD3 developers and CD6 developers today.

Didn't benzyl alcohol serve this porpose as well - as a cosolvent?