US2388816A - Photographic developer - Google Patents

Description

Patented Nov. 33, 1945 PHOTOGBAPMC DEVELOP Frederic R. Bean, Rochester. N. Y., asslgnor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application June 25, 1M2,

Serial No. 448,415 I is ens.

This invention relates to photographic developing solutions and more particularly to concentrated photographic developing solutions and dry mixtures of chemicals suitable for dissolving in water to form photographic developing solutions.

In making concentrated solutions of Photo graphic developing compounds, reagents such as polyhydric, alcohols, amino alcohols, and caustic alkalis have been used singly or in combinations to act as solubilizing agents for the developer in the presence of sodium sulflte. When caustic a1- kall is used the developing solutions tend to have poor keeping properties, when amino alcohols are used the solutions may give fog and thepolyhydric alcohols are not especially good solvents for sodium sulfite.

I have found a class of compounds useful in making developer solutions, especially composipreservatives and prevent formation of sludge during development.

Compounds useful in developing solutions according to my invention are the alkali metal salts of aminomethane sulfonates and of aminomethane sulilnates as, for example, the sodium salts 'of amine and the solution is warmed at about 50- 60 C. for about 30 minutes. If desired, one mole of solid sodium formaldehyde-bisulfite may be caused to react with the monoethanolamine in a similar manner. The resulting product may be isolated and added to a photographic developing solution, or if desired, the photographic ingredients may be added to the above solution and made up to the required volume by the addition of water.

In a similar manner di-(p-hydroxye'thyl) aminpmethane sulfonate may be prepared as follows: 420 grams of diethanolamine and 536 grams of sodium formaldehyde bisulfite are placed in 300- 400 cc. of water and the mixture is warmed at about 50-60 C. for 30 minutes and allowed to stand-overnight at room temperature. The reaction product may beisolated from the resulting syrupy reaction mixture by the addition of organfi-hydroxyethylaminomethane sulfonates, di-(,B

hydroxyethyl) aminomethane sulfonate, ethylenediamino-bis-methane sulionate, ,B-hydroxyethylaminodimethylmethane sulfonate, cyclohexylaminomethane sulfonate, morpholihomethane sulfonate, p-carboxyphenylaminomethane sulfonate and sulfinate, ethylenediamino-bis-methane sulfinate, ethylenediamino -bis-dimethylmethane sul- -finate, carboxymethylaminomethane sulionate,

lo solvents such as acetone, methyl alcohol, tertiary butyl alcohol, etc., which cause the reaction product to precipitate out as fine white crystals.

' Aminomethanesulfonates of ketones capable of reacting with sodium bisulfite may be prepared in a manner analagous to those above-described by the reaction of an amine with a ketone and sodium bisulflte or a ketone-bisulflte compound, by heating for a suitable length of time.

The aminomethanesulfinate compounds of the invention may, ior instance, be prepared by reaction of an amino compound with aldehyde sulfoxalates such as formaldehyde sulfoxalate. A typical aminomethanesuli'inate compound useful in my invention, that is, di-sodlum-p-carboxyphenylaminomethane sulflnate, may be prepared asi'ollows: 34.2 grams of p-aminobenzoic acid are added to 30-40 cc. of water containing 10 grams of sodium hydroxide. Thereafter, 38.5 grams of tones by reaction with sodium bisulflte and an A suitable method of preparation oi-the above compoundis as follows: '75 cc. of 40% formaldehyde are added to 150,-200 cc. of water and then 104 grams oi sodium bisulflte are then added. I To this solution are added 61 grams or monoethanolformaldehyde sulioxalate are added to the hot solution and the mixture heated at 70 C. for 1-2 hours. After cooling the reaction product is precipitated from the syrupy mixture by the addition of acetone.

Qther aminomethane sulilnates are prepared in a similar manner by reactionol other amino compounds with formaldehyde sulioxalate, or other suliox'alates as, for example, prepared by the reduction of aminomethane sulionates.

A method 01 preparing a mixture-of aminomethane sulionate and an aminomethane sulflnate compound is given as follows: molecular proportions of formaldehyde and sodium hydrosulflte are caused to react in aqueous solution, and thereafter, the product consisting of sodium formaldehyde sulioxalate and sodiumformaldehyde bi-' sulflte is reacted with an amine or amines to form The compounds of my invention may be used in developing solutions, especially concentrated developing solutions, as shown in the following examples which are intended only for illustration.

Example 1 Sodium-,8-hydroxyethylaminomethane sulfonate grams 81.5 p-Methylamino-phenol sulfate do 5.0 Potassium thiocyanate do 1.0 Potassium bromide do 0.5 Hydroquinone r do 1.0 Water I e 250 For use this solution is made to the required volume with water.

Example 2 Di-sodium ethylenediamino-bis-methane sulfonate grams '73 p-Methylamino-phenol sulfate do 5.0 Potassium thiocyanate do 1.0 Potassium bromide do 0.5 Water to 250 Example 3 Water 385 Sodium sulfite grams 18 Acetic acid (glacial) cc; 10 Sodium-p-hydroxyethylaminomethane sulfonate grams 531 p-Methylamino phenol sulfate do 25 Hydroquinone do 6 Potassium bromide do 10 Sodium thiocyanate do 6 Glycerin or 200 Water to liter 1 Example 4 Sodium-B-hydroxyethylaminomethane sulfinate grams 322 Hydroquinone d 90 Potassium bromide do 6.3 Water to liter 1 In a similar manner'a mixture of aminomethane sulfonate and sulfinate are incorporated into a developer formula in the amount required to make concentrated developers or dry mixtures of chemicals for dissolving in water.

Example 5 Di-(phydroxylethyl) aminomethane sulfonate grams; 110 p-Methylamino-phenol sulfate do 5 Potassium thiocyanate do 1 Potassium bromide do 0.5

advisable, especially from the standpoint of economy, to use as much sodium sulfite in the con-' centrated developing solutions, as is possible, and adding the compounds of the invention as solubilizers and to aid in the preservation of the so lutions.

One advantageous feature of the compounds when used in developing solutions, resides in their a mixture of 'sulfonate and sulfinate compounds.

solubility characteristics. The compounds, especially the hydroxy alkyl derivatives, are considerably more soluble than sodium sulfite and accordingly are especially suitable for use inconcentrated developing solutions. The anti-sludge properties of a developer containing compounds of my invention were demonstrated as follows: several rolls of amateur film were developed in a developing solution of the following composition:

IIJ'he same number of rolls of the same film were developed under the same conditions in a second developing solution of composition shown in Example 1 with the result that whereas a continuously heavier sludge formed in the first developer after development of a certain number of rolls of film, the second developer was nearly asclear as at first after developing the same amount of film.

Asshown in Example 3, the pH of the developing solutions may be regulated by the addition of acid compounds such as meta-bisulfites, bisulfites, acid sodium acetate, acetic acid, etc., or basic compound such as sodium metaborate and the like. Suitable solid acids and-bases may also be added to the dry mixtures of chemicals of my invention. Of course, the compounds of my invention also aid in the regulation of pH.

Other aminomethanesulfonates useful in developing solutions according to my invention may be prepared from aldehydes such as crotonic aldehyde, acrolein, etc., and ketones such as acetone, acetonyl-acetone, etc., by reaction with bisulfites and amines employing suitable conditons of time and temperature.

It is to be understood that the disclosure herein is by way of example and that I consider as included in my invention all modifications and equivalents falling within the scope of the appended claims.

What I claim is:

1. A photographic developing solution comprising a. developing agent and a compound selected from the group consisting of alkali salts of aminomethane sulfonates and aminomethane sulfinates.

2. A photographic developing solution comprising a developing agent and an alkali metal salt of an aminomethane sulfonate.

3. A photographic developing solution comprising a developing agent, an alkali metal salt of an aminomethane sulfonate. and sodium sulfite.

4. A photographic developing solution comprising a developing agent and ,d-hydroxyethylaminomethane sulfonate.

5. A photographic developing solution comprising a developing agent and a sodium salt of ethylenediamino-bis-methane sulfonate.

6. A photographic developing solution comprising a, developing agent and an alkali metal salt of an aminomethane sulfinate.

7. A photographic developing solution comprising a developing agent and an alkali metal salt of an aminomethane sulfinate and sodium sulfite.

8. A photographic developing solution comprising a developing agent and an alkali metal salt of ,B-hydroxyethylaminomethane sulfinate.

9. A solid mixture of chemicals suitable for forming a, photographic developing solution by dissolving in water comprising a developing agent and a compound selected from. the group consisting of alkali metal salts of aminomethane sulfonates and aminomethane sulilnates.

10. A solid mixture of chemicals suitable for forming a photographic developing solution "by dissolving in water comprising a developing agent and an alkali metal salt of an aminomethane sulfonate. I

11. A solid mixture of chemicals suitable for forming a photographic developing solution by dissolving in water comprising a developing agent and an alkali metal salt of an aminomethane sulflnate.

12. A solid mixture of chemicals suitable for forming a photographic developing solution by dissolving in water comprising a developing agent -metal salt of an aminomethane and an alkali metal salt of p-hydroxyethylaminomethane sulfonate.

13. A photographic developing solution comprising a developing agent, an alkali metal salt oi an aminomethane sulfonate, and an alkali sltioncomis A photographic developing prising a. developing agent, an alkali metal salt of an aminomethane w Sultanate, and an alkali metal salt of an aminomethane sulfinate, and so- 15. A solid mixture of chemicals suitable for forming a photographic developing solution by dissolving in water comprisinga developing agent and an alkali metal salt of, an aminomethane sulionate and an alkali metal salt of'an aminomethane sulflnate.