Patent GB-557178-A (GB)
Title: Improvements in and relating to photographic sensitive emulsions
IPC: B65B19/10
Filed: 1942-01-07
Abstract: 557,178. Surface active agents ; halogen substituted compounds. KODAK, Ltd. (Eastman Kodak Co., and Carroll, B. H.). Jan. 7, 1942, No. 272. [Classes 2 (iii) and 15 (ii)] [Also in Group XX] Photographic material comprises a lightsensitive silver salt emulsion sensitized with a sensitizing quantity of a cationic surface-active ammonium salt, the cation of which is free from carboxyl and sulphonic acid groups and the salt forms of such groups. The cation is preferably free from acidic and other salt-forming groups and salt forms of such groups. A quaternary ammonium salt, e.g. in which the quaternary ammonium nitrogen atom is attached to four separate alkyl groups may be used. The quaternary nitrogen atom may be one of the nuclear atoms of a heterocyclic ring devoid of fused-on aromatic rings. The nuclear atoms may consist only of carbon and nitrogen. The salt may be a pyridinium salt or a quaternary salt derived from dibenzylmethylamine or dibenzylethylamine. The ammonium cation may contain a lipophile organic group having a chain of 8 or more members selected from C, O, N and S atoms and benzene rings. The chain may have 9 to 12 members. A naphthalene ring can replace two atoms of the chain. The lipophilic group can be attached directly to the ammonium nitrogen atom or indirectly thereto by means of a group. Chains specified are octyl, nonyl, decyl, lauryl, cetyl, heptoxymethyl, undecoxymethyl, heptylthiomethyl, capro-oxyethyl, carbonoxymethyl, butoxyethoxyethyl, p-tertheptylphenoxyethoxyethyl, p-formylphenoxyethoxyethyl, p-phenylphenoxyethoxyethyl, p-methylphenoxypropoxypropyl, 3:7-dimethyloctanoxymethyl, citronelloxymethyl (alcohol radicals in commercial oil of sandalwood)-O-CH 2 , #-hydroxydecyl, #- naphthoxyethoxyethyl, and laurylcarbamylmethyl. Anions specified are chloride, bromide, iodide, p-toluenesulphonate, perchlorate, and alkylsulphate radicals. From 10-200 mgm of surface-active salt per gram-mole of silverhalide in the emulsion may be employed. More or less than the optimum quantity may be used. Spectral sensitizing dyes, when used in addition, are preferably used in optimum concentration, but more or less may be used. With fine grain emulsions, larger quantfties oi dye are preferably used. Non-acidic (i.e. neutral or basic) sensitizing dyes are used, e.g. cyanines, merocyanines, hemicyanines and hemioxonoles. The surface-active salt may be incorporated before, simultaneously with, or after the sensitizing dye. Both are preferably incorporated after washing and just prior to coating. The emulsion may be gelatine-silver bromide, chloride, or bromiodide emulsion, or the binder may be a resinous or cellulosic substance. The support may be glass, paper, cellulose acetate or polyvinyl acetal. The surface-active ammonium salts may be (1) tetra alkyl and analogous quaternary ammonium salts of the formula R R<SP>1</SP> R" R<SP>111</SP> N X, wherein at least one of the groups R, R<SP>1</SP> R<SP>11</SP> and R<SP>111</SP> is a lipophilic group containing a chain of at least 8 members chosen from C, O, N, and S atoms and aromatic rings, and the remaining R, R', R", and R<SP>111</SP> represents alkyl or analogous groups, e.g. methyl, ethyl, butyl, amyl, cyclohexyl or benzyl and X represents an acid radical; (2) pyridinium quaternary salts having a lipophilic group attached to the nitrogen atom ; (3) pyridinium quaternary salts of formula wherein R represents an alkyl or analogous group e.g. methyl, ethyl, butyl, or benzyl, one of the groups R<SP>1</SP> and R<SP>11</SP> represents a lipophilic organic group the other of the groups R<SP>1</SP> and R<SP>11</SP> represents hydrogen or a low molecular weight alkyl or analogous group (e.g. methyl, ethyl or butyl), and X represents an acid radical; (4) piperidinium salts of formula wherein one of the groups R and R<SP>1</SP> represents a lipophilic group, the other hydrogen or a low molecular weight alkyl or analogous group, and X is an acid radical; (5) pyrazolium quaternary salts of the formula wherein one of the groups R and R<SP>1</SP> represents a lipophilic group, the other hydrogen or a low molecular weight alkyl or analogous group, and X is an acid radical; and (6) imidazolium quaternary salts of the formula wherein one of the groups R and R<SP>1</SP> represents a lipophilic group, the other a low molecular weight alkyl or analogous group, and X is an acid radical. In an example, a methyl alcohol solution of 2, 2<SP>1</SP> - diethyl - 8 - methyl 3 : 4 - 3<SP>1</SP>: 4<SP>1</SP>-dibenzothiacarbocyanine chloride and an aqueous solution of lauryltriethylammonium perchlorate are successively added to a finished washed gelatino-silver bromoiodide. Sensitizing data are also given in respect of a gelatino - silver bromoiodide sensitized with (a) 2 : 2<SP>1</SP> - diethyl - 8 - methyl - 3 : 4 : 3<SP>1</SP> : 41 - dibenzothiacarbocyanine chloride ; (b) 2 : 21 - diethyl - 8 - methylthiacarbocyanine bromide ; (c)2:2<SP>1</SP>- diethyl - 8 - methyl - thiacarbocyanine bromide and lauryltriethylammonium perchlorate; (d) 3 - ethyl - 5 - (2 - ethylbenzoxazolylideneethylidene)-rhodanine ; (e) 3 - ethyl - 5 - (2 - ethylbenzoxazolidene - ethylidene) - rhodanine and lauryltriethylammonium perchlorate ; (f) 2 - diphenylamino - 5 - (2 - ethyl - 1 - benzothiazolylidene - ethylidene)- - 4 (5) - thiazolone ; (g) 2 - diphenylamino - 5 - (2 - ethyl - 1 - benzothiazolylidene - ethylidene) - 4 (5) - thiazolone and N - heptoxymethylpyridinium perchlorate ; (h) 2 - (4 - (1- piperidyl - butadienyl)) - # - naphthathiazole ethiodide ; (i) 2 - (4 - (1 - piperidyl - butadienyl)) -#- naphthathiazole ethiodide and N - heptoxymethylpyridinium perchlorate ; (j) 3 - ethyl - 5 - (y - (1 - piperidyl) - alkylidene) rhodanine ; (k) 3 - ethyl - 5 - (y - (1 - piperidyl) - allylidene) rhodanine and N - heptoxymethylpyridinium perchlorate ; (1) 2 : 2<SP>1</SP> - dimethyl - 8 - ethylthiacarbocyanine bromide ; (m) 2 : 21 - dimethyl - 8 - ethylthiacarbocyanine bromide and (i) nonyl pyridinium perchlorate, (ii) decylpyridinium perchlorate, (iii) N - nonyl : N - - methylpyridinium perchlorate, (iv) p - tert.- butylphenoxyethoxyethylpyridinium perchlorate, (v) N - nonylpiperidinium methyl - p - tolu-. enesulphonate, (vi) hexoxymethylpyridinium perchlorate, (vii), heptoxymethylpyridinium perchlorate, (viii) octoxymethylpyridinium perchlorate, (ix) nonoxymethylpyridinium perchlorate, (x) N - decyl - 1 : 3 : 5 - trimethylpyrazolium perchlorate, and (xi) N - carbononoxymethylpyridium perchlorate. The addition of a cationic surface-active ammonium salt according to the invention to a gelatinosilver bromiodide emulsion containing a mixture of thiocarbocyanine and 2<SP>1</SP> - cyanine dyes is referred to. Cationic surface-active quaternary ammonium perchlorates are obtained by treating surfaceactive quaternary ammonium salts other than perchlorates with an alkali metal perchlorate. N - (n - nonyl) pyridinium perchlorate is prepared by refluxing together n - nonyl - p - - toluenesulphonate and pyridine and adding to a methyl alcohol solution of the solidified cooled product an aqueous solution of sodium perchlorate. N - methylpiperidinium - - n - nonyl - p - toluenesulphonate is prepared by reacting N - methylpiperidine and n - nonyl - p - toluenesulphonate. N - (n - heptylthiomethyl) - pyridinium perchlorate is prepared by warming together n -  heptylthiomethyl chloride and pyridine, dissolving the syrup obtained in methyl alcohol, and adding aqueous sodium perchlorate. n - Heptylthiomethyl-dimethylbenzylammoniumperchlorate and n - dodecylthiomethyl - pyridinium perchlorate are similarly prepared. n- Heptylthiomethyl chloride is prepared by treating a mixture of n-heptyl mercaptan and formaldehyde with hydrogen chloride at 0-10‹C. N - (n - heptoxymethyl)- pyridinium perchlorate is prepared by mixing together n - heptoxymethyl chloride and pyridine, dissolving the product in methyl alcohol, and adding thereto an aqueous solution of sodium perchlorate. N - (n - hexoxymethyl) - pyridinium,N - (n - octoxymethyl) pyridinium, N - (n - nonoxymethyl)- pyridinium ; N - ( n - decoxymethyl) - pyridinium, N - (n undecoxymethyl) - pyridinium, N - (# - cyclohexylethoxymethyl) - pyridinium, N - (# - phenylethoxymethyl)-pyridinium, N - - citronelloxymethyl - pyridinium, N - geranioxymethyl - pyridinium, N - cinnamyloxymethyl - pyridinium, N - rhodinoxymethyl - pyridinium, ( 3 : 7 - dimethyloctanoxymethyl) - pyridinium, N -abietyl-oxymethyl-pyridinium, N - (γ - phenyl-n-propoxymethyl) - pyridinium, N - (# - n - amyl-oxyethoxymethyl) -pyridinium, and N - "Sandaloxy" - methyl - pyridinium perchlorates are similarly prepared. N - Heptoxymethyl chloride is prepared by treating a mixture of n - heptyl alcohol and formaldehyde with hydrogen chloride at 0 - 10‹C. n - hexoxymethyl, n - octoxymethyl, n - nonoxymethyl, n - decoxymethyl, n - undecoxymethyl, # - cyclohexylmethyl , # - phenylethoxymethyl, citronelloxymethyl, geranioxymethyl, cinnamyloxymethyl, rhodinoxymethyl, 3 : 7 - - dimethyloctanoxy - methyl, abietyloxymethyl, γ - phenyl - n - propoxymethyl, # - n - amyloxyethoxyethoxymethyl and "Sandaloxy"-methyl chlorides are similarly prepared, the alcohol involved in the preparation of the last mentioned compound being the mixture occurring in sandalwood oil. n-H eptoxymethyldimethylbenzylammonium perchlorate is prepared by reacting dimethylbenzylamine with n-heptoxymethyl chloride and adding to the warm methyl alcoholic solution of the product an aqueous solution of sodium perchlorate. NNonyldimethylbenzylammonium, n-heptoxymethyldiethylbenzyl - ammonium, n-nonyldiethylbenzylammonium and p-tertbutylphenoxyethoxyethyldiethylbenzyl - ammonium perchlorates are similarly prepared. N-carbo-n-nonoxymethylpyridinium perchlorate is prepared by refluxing together n-nonyl chloracetate and pyridine in dry benzene and adding aqu