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Publication numberUS3444138 A
Publication typeGrant
Publication dateMay 13, 1969
Filing dateAug 16, 1965
Priority dateAug 16, 1965
Also published asDE1295368B, DE1547716A1, DE1547716B2, DE1547724A1, US3425833, US3438779, US3455693
Publication numberUS 3444138 A, US 3444138A, US-A-3444138, US3444138 A, US3444138A
InventorsJack L R Williams
Original AssigneeEastman Kodak Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Mordants for bleachable filter layers
US 3444138 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent 3,444,138 MORDANTS FOR BLEACHABLE FILTER LAYERS Jack L. R. Williams, Rochester, N.Y.. assignor to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed Aug. 16, 1965, Ser. No. 480,111 lint. C]. G03c 7/32, 7/28; C09b 65/00 U.S. Cl. 260-65 7 Claims ABSTRACT OF THE DISCLOSURE This invention relates to certain bulky, i.e., relatively high molecular Weight, quaternary nitrogen heterocyclic compounds which function as mordants for use in photography, and to methods for the preparation of said compounds.

The use of organic dye containing light-filter and lightabsorbing layers in photographic elements is well known, as is the use of mordants which form substantially insoluble salts or otherwise react with water-soluble dyes, to render the dyes non-diffusing. Such dye-mordant lightscreening salt may be in a layer overlying a light-sensitive emulsion or overlying two or more light-sensitive emulsions; or it may be in a light-sensitive emulsion for the purpose of modifying a light record in such emulsion or for protecting an overlying light-sensitive emulsion or emulsions from the action of light of wavelengths absorbed by such light-screening substance, or it may be in a layer not containing a light-sensitive substance but arranged between two light-sensitive emulsions; or it may be in a layer serving as a backing on an element having one or more light-sensitive emulsions (for example, to reduce halation).

In particular, light-screening substances are often required (a) in overcoatings upon photographic elements to protect the light-sensitive emulsion or emulsions from the action of light which it is not desired to record, (-b) in layers arranged between differentially color sensitized emulsions, e.g., to protect redand green-sensitive emulsions from the action of blue light, and (c) in backings forming the so-called anti-halation layers on either side of a transparent support carrying the light-sensitive emulsion or emulsions.

In most cases and especially where the element contains a color sensitized emulsion or color sensitized emulsions, it is particularly desirable to employ light-screening substances which do not affect the general sensitivity or the color sensitivity of light-sensitive emulsions with which they may come into contact. It is also particularly desirable to employ light-screening substances which do not substantially diffuse from the layers or coatings in which they are incorporated, either during the manufacture of the element or on storing it or in photographically processing it. Finally it is generally necessary to employ light-screening substances which can readily be rendered inelfective, i.e., decolorized or destroyed and removed prior to or during or after photographic processing. For many purposes it is particularly convenient to employ 3,444,138 Patented May 13, 1969 light-screening substances which are rendered ineffective by one of the photographic baths employed in processing the element after exposure, such as a photographic developing bath or fixing bath.

Numerous substances have been proposed as mordants to prepare the dye-mordant salts used as light-screening and light-absorbing materials for the purposes indicated above. Among the proposed mordants are relatively high molecular weight compounds having ionic charges opposite to those of the particular light-absorbing dye. For example, the dye employed might be an acid dye, in which case the mordant would be a cationic compound. Typical of such proposed mordants are, for example, derived polymers such as the basic reaction products of polyvinylsulfonates and C-aminopyridines as described in D. D. Reynolds et al., US. Patents 2,701,243 and 2,768,078, granted Feb. 1, 1955, and Oct. 23, 1956, respectively. While polymeric mordants such as illustrated by the above-mentioned patents have the advantage of bulky molecules and do function to fix acid dyes in photographic layers, within their particular limitations, they have not been found entirely satisfactory in many applications primarily because these polymeric mordants on alkaline development do not tend to release the dye, i.e., they still retain their mordanting property and, accordingly, not only tend to retain some residual dye as evidenced by background stain or coloration, but more importantly retain, i.e., fix, an appreciable amount of thiosulfate ion in the subsequent hypo processing used to remove unexposed halide. This results in relatively poor quality and stability of the produced image. In view of this, it would be very desirable to have an effective mordant available that is free from such disadvantages.

I have now found that certain bulky or relatively high molecular weight quaternary nitrogen heterocyclic compounds are especially useful as precipitants and mordants for acid dyes in photographic layers, and that these compounds, moreover, satisfactorily overcome the abovementioned shortcomings of heretofore known mordants for this purpose. Thus, our new class of mordants do not retain any residual dye or deleterious amounts of thiosulfate ion in the layers after processing, and further the produced images are of very good quality and of outstanding keeping properties. These novel mordants are soluble in aqueous solutions, for example, in dilute aqueous solutions of acids such as acetice, butyric, lauric, etc., acids. Furthermore, they have good compatibility with various hydrophilic materials such as gelatin and readily form substantially non-dilfusible salts with water-soluble acid dyes. In general, they have a molecular weight of about at least 300, although polymeric materials having a molecular weight of 600 to 50,000, and higher, have been found to be particularly useful in my invention.

It is, accordingly, an object of the invention to provide a new class of polymeric quaternary nitrogen heterocyclic compounds, and salts thereof with water-soluble acid dyes. Another object is to provide an imbibition blank containing at least one of the above salts. Another object is to provide a process for preparing the new class of compounds and salts. Other objects will become apparent from consideration of the description and examples.

The new class of polymeric quaternary nitrogen heterocyclic compounds of the invention include those represented by the following general formula:

(I) o R; x 2.,

R,(o)m 1- i '3111 'r OR:

wherein m represents an integer of from 1 to 2, R, represents a linear polymeric structure, for example, an addition type polymer such as a polymer of a monoethylenically unsaturated polymerizable compound having periodically occurring groups of the structure:

attached to carbon atoms in the polymeric chain of a monoethylenically unsaturated polymer (e.g., a polyvinyl ester or alkyl ketone, a polyisopropenyl ester or alkyl ketone), the said chain may also include units of vinyl alcohol, unquaternized vinyl ester or vinyl alkyl ketone; R represents the hydrogen atom, a lower alkyl group (e.g., methyl, ethyl, etc.), or a phenyl group; R represents the hydrogen atom, an alkyl group (e.g., methyl, ethyl, propyl, isopropyl, butyl, hexyl, dodecyl, pentadecyl, benzyl, phenethyl, etc.), a hydroxyl, a halogen (e.g., chlorine or bromine), or an aryl group (e.g., phenyl, tolyl, biphenylyl, etc.); X represents an acid anion (e.g., chloride, bromide, iodide, thiocyanate, sulfamate, perchlorate, methyl sulfate, ethyl sulfate, p-toluenesulfonate, etc); and Z represents the non-metallic atoms required to complete a nucleus containing a to 6-membered heterocyclic ring having nitrogen, oxygen, sulfur and selenium as the hetero atoms, typically a thiazole nucleus (e.g., thiazole, 4-meth ylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4 (2 thienyl)thiazole, etc.)

a benzothiazole nucleus (e.g., benzothiazole,

4-chlorobenzothiazole, S-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, S-methylbenzothiazole, tS-methylbenzothiazole, S-bromobenzothiazole, 6-bromobenzothiazole, 4-phenylbenzothiazole, 5-phenylbenzothiazole, 4-methoxybenzothiazole, S-methoxybenzothiazole, 6-methoxybenzothiazole, 5-iodobenzothiazole, 6-iodobenzothiazole, 4-ethoxybenzothiazole, S-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-dioxymethylenebenzothiazole, S-hydroxybenzothiazole, fi-hydroxybenzothiazole, etc.)

a thianaphtheno- 7',6,4,5-thiazole nucleus, (e.g.,

4'-methoxythianaphtheno- 7',6',4,5-thiazole, etc.

an oxazole (e.g., S-methyloxazole, 4-phenyloxazole,

4,5-diphenyloxazole, 4-ethyloxazole, 4,5-dimethyloxazole, S-phenyloxazole, etc.),

a benzoxazole nucleus (e.g., benzoxazole,

Schlorobenzoxazole, S-methylbenzoxazole, S-phenylbenzoxazole, -methylbenzoxazole, 5,6-dirnethylbenzoxazole, 4,6-dimethylbenzoxazole, S-methoxybenzoxazole, S-ethoxybenzoxazole, 6-chlorobenzoxazole, S-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.)

a naphthoxazole nucleus (e.g., u-naphthoxazole, fl,,8-naphthoxazole, ,B-naphthoxazole, etc.),

a selenazole nucleus (e.g., 4-methylselenazole,

4-phenylselenazole, etc.),

a benzoselenazole nucleus (e.g., benzoselenazole,

S-chloroselenazole, S-methoxybenzoselenazole, S-hydroxybenzoselenazole, tetrahydrobenzoselenazole, etc.

a naphthoselenazole nucleus (e. g., u-naphthoselenazole, fiJi-naphthoselenazole, fl-naphthoselenazole, etc.

a thiazoline nucleus (e.g., thiazoline,

4-methylthiazoline, etc.)

a quinoline nucleus (e.g., quinoline,

3-methylquinoline, S-methylquinoline, 7-methylquinoline, 8-methylquinoline, 6-chloroquinoline, S-chloroquinoline, 6-methoxyquinoline, 6-ethoxyquinoline, 6-hydroxyquinoline, 8-hydroxyquinoline, etc.),

an isoquinoline nucelus (e.g., isoquinoline,

4 3-methylisoquinoline, S-methylisoquinoline, 6-chloroisoquinoline, 6-methoxyisoquinoline, 8-hydroxyisoquinoline, etc.

a 3,3-dialkylindolenine nucleus (e.g.,

3,3-dimethylindolenine, 3,3,S-trimethylindolenine, 3 ,3 ,7-trimethylindolenine, etc.

a pyridine nucleus (e.g., pyridine, Z-methylpyridine,

2-benzylpyridine, 3-chloropyridine, 3-hydroxypyridine, 2-rnethyl-5-ethylpyridine, 2,5-dibutylpyridine, 3-diphenylmethylpyridine, 4-diphenylmethylpyridine, hydroxydiphenylmethylpyridine, etc.

an imidazole nucleus (e.g., imidazole, l-alkyl imidazole,

1-alkyl-4-phenylimidazole, 1-alkyl-4,5-dimethylimidazole, etc.

a benzimidazole nucleus (e.g., benzimidazole,

l-alkylbenzimidazole, 1-aryl-5,6-dichlorobenzimidazole, etc.),

a naphthimidazole nucleus (e.g., 1-alkyl-a-naphthimidazole, l-aryl-fl-naphthimidazole, 1-alkyl-5-rnethoxy-u-naphthimidazole, etc.

a 1,2,4-thiadiazole nucleus,

a l or 4 alkyl-1,2,4-triazole nucleus (e.g.,

1-methyl-1,2,4-triazole, 1-butyl-1,2,4-triazole, 4-ethyl-1,2,4-triazole, etc.)

a tetrazole nucleus (e.g., tetrazole,

S-methyl-1,2,3,4-tetrazole,

S-phenyl-l ,2,3,4-tetraz0le, etc.

and the like nuclei.

More particularly the new class of quaternary nitrogen heterocyclic polymers of the invention include derived resinous copolymers consisting essentially of not less than 25% by weight of polymerized units of the general structure:

the remainder of the polymer molecule may be polymerized units of the structures:

and/ or when m is the integer 2.

In accordance with the invention, I prepare the derived resinous copolymer coming under above Formula II by reacting a resinous addition polymer of a monoethylenically unsaturated polymerizable compound having the general formula:

(IV) 0 R;

with a heterocyclic tertiary amine having the general formula:

N CR3 prepared, for example, by polymerizing monomeric vinyl chloromethyl ketone (Catch et al., J. Chem. Soc., 1948, p. 278) in a solvent such as dioxane at 60 C. in the presence of a polymerization catalyst, e.g., azo-bis-isobutyronitrile. The proportions of the heterocyclic tertiary amine of Formula V above can vary widely, but preferably it is employed in the reaction in excess of the stoichiometrically calculated quantity, for example, from about 1.2 to 5, or more equivalent moles. Advantageously, the reaction is carried out in an inert reaction medium which is a solvent for the starting polymer such as, for example, in acetone, dimethyl sulfoxide, N,N-dimethylformamide, 'y-butyrolactone etc. The reaction mixture is allowed to stand for several days or more at room temperatures or heated for several hours. The quaternary salt product which forms is isolated by precipitation into a nonsolvent for the salt product, or in the case where the salt product forms as a precipitate in the reaction mixture, the supernatant liquor can be simply decanted. The quaternary salt product can then be further purified by washing with a non-solvent and dried preferably under vacuum. The quaternary salt products consisting from about 25-100% by weight of quaternized units and from 75-0%, by weight of unquaternized residual units have been found to be especially efilcacious mordants in photographic layers and are preferred.

The photographic elements prepared with the abovedescribed polymeric and non-polymeric mordants of the invention comprise a support material having thereon at least one hydrophilic colloid layer containing a mordant of the invention, which layer may also contain a lightsensitive silver halide. However, the preferred light-sensitive photographic elements comprise a support having thereon at least one hydrophilic colloid layer containing a mordant of the invention and at least one light-sensitive silver halide emulsion layer. The mordant containing light-screening and antihalation layers are customarily prepared by coating on the sup ort or photographic element by methods well known in the art, a water solution comprising at least one mordant of the invention, an acid dye, a water permeable hydrophilic colloid binder and a coating aid such as saponin. For most purposes, it is also desirable to add agents to harden the colloidal binder material so that the light-screening layer will remain intact in the photographic element during and following the processing operations. The pH of the coating solution is adjusted when necessary to a level that is compatible with the light-sensitive emulsion layer by the usual methods. The proportions of mordant, dye, colloidal binder, hardener and coating aid may be varied over wide ranges and will depend upon the specific requirements of the photographic element being produced. The methods used to determine the optimum compositions are well known in the art and require no further elucidation here. Suitable support materials include any of those used in photography such as cellulose acetate, cellulose propionate, cellulose acetate-butyrate, cellulose nitrate, synthetic resins such as nylon, polyesters, polystyrene, polypropylene, etc., paper, and the like.

Suitable hydrophilic colloid materials that can be used in the mordant containing compositions and layers, and photographic elements, of the invention include gelatin, albumin, collodion, gum arabic, agar-agar, cellulose derivatives such as alkyl esters or carboxylated cellulose, hydroxy ethyl cellulose, carboxy methyl hydroxy ethyl cellulose, synthetic resins, such as the amphoteric copolymers described by Clavier et al. in U.S. Patent 2,949,442, issued Aug. 16, 1960, polyvinyl alcohol, polyvinyl pyrrolidone, and others Well known in the art. The above-mentioned amphoteric copolymers are made by polymerizing the monomer having the formula:

CH2=CR' COOH wherein R represents an atom of hydrogen or a methyl group, and a salt of a compound having the general formula:

wherein R has the above-mentioned meaning, such as an alkylamine salt. These monomers can further be polymerized with a third unsaturated monomer in an amount up to about 20 percent, and preferably from 5-15 percent, of the total weight of monomer used, such as an ethylene monomer that is copolymerizable with the two principal monomers. The third monomer may contain either a basic group or an acid group and may, for example, be vinyl acetate, vinyl chloride, acrylonitrile, methacrylonitrile, styrene, acrylates, methacrylates, acrylamide, methacrylamide, etc. Examples of these polymeric gelatin substitutes are copolymers of allylamine and methacrylic acid; copolymers of allylamine, acrylic acid and acrylamide; hydrolyzed copolymers of allylamine, methacrylic acid and vinyl acetate; the copolymers of allylamine, acrylic acid and styrene; the copolymers of allylamine, methacrylic acid and acrylonitrile; etc.

The dyes that can be effectively mordanted in accordance with my invention include any filter dye that has one or more acidic group substituents such as sulfo or carboxyl groups, for example, the oxonol dyes described and claimed in copending application of Joseph Bailey, Ser. No. 98,709, filed Mar. 27, 1961, having the formula:

and more particularly the dyes of the formula:

0 II C wherein Z represents the nonmetallic atoms necessary to complete a 1-carboxyalkyl-3-hydrocarbon substituted hexahydro-2,4,6,-trioxo*5pyrimidine nucleus, 12 in each case is an integer of from 1 to 3, each R represents a carboxyalkyl group in which the carboxy substituent is attached to an alkyl group having from 1 to 2 carbon atoms, R is an alkyl group of from 1 to 8 carbon atoms or an aryl group such as phenyl or an alkyl or alkoxy substituted phenyl group, and X is hydrogen or an alkyl group of from 1 to 4 carbon atoms, such that no more than one X is an alkyl group. Other suitable acid dyes include the benzoxazolepyrazolone merocyanine dyes described in copending application of Jones et al. U.S. Ser. No. 167,666, filed J an. 22, 1962 having the formula:

wherein R represents an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, etc., or a carboxyalkyl group, such as carboxymethyl, carboxyethyl, carboxypropyl, etc., or a sulfoalkyl group, such as sulfoethyl, sulfopropyl, sulfobutyl, etc.; Z represents the nonmetallic atoms necessary to complete a heterocylic nucleus of the benzoxazole series (including benzoxazole and benzoxazole substituted with substitutions such as methyl, ethyl, phenyl, methoxy, ethoxy, chlorine, bromine, etc.) or a nucleus of the benzoxazoles series which has a sulfo-substituent on the benzene ring as well as one or more of the above-mentioned simple substituents, such that when R represents an alkyl group, Z represents the sulfo-substituted benzoxazole nucleus and when R represents a carboxyalkyl group or a sulfoalkyl group, Z represents the nonmetallic atoms necessary to complete a benzoxazole nucleus; Q represents the nonmetallic atoms necessary to complete a heterocyclic nucleus of the sulfophenyl pyrazolinone series and n is an integer from 1 to 3. However, the invention is not limited to just those dyes coming within the general formulas of the above-mentioned copending applications, since as previously set forth any filter dye containing one or more sulfo or carboxyl groups can be employed. For example, the yellow dyes mentioned in Mader et al. US. Patent 3,016,306, issued Jan. 9, 1962, columns and 6.

Typical light-filtering dyes include, for example, bis(lbutyl 3 -carboxymethylhexahydro-2,4,6-trioxo-5-pyrimidine)-pentamethineoxonol, bis 1-carboxymethyl-3-cyclohexylhexahydro 2,4,6 trioxo-S-pyrimidine)pentamethineoxonol, bis(l butyl-3-carboxymethylhexahydro-2,4,6- trioxo 5 pyrimidine)trimethineoxonol, bis(l-carboxymethylhexahydro 3 octyl 2,4,6-trioxo-5-pyrimidine) meth'ineoxonol, 4 [(3 ethyl-2(3H)-benzoxazolylidine) ethylidene] 3 methylI-(p-sulfophenyl)-2-pyrazolin-5- one monosulfonated, 4-[4-(3-ethyl-2 (3H)-benzoxazolylidene) 2 butenylidene]-3-methyl-'1-(p-sulfophenyl)-2- pyrazolin 5-one monosulfonated, 4-[(3-;i-carboxyethyl- 2(3H) benzoxazolylidene)ethylidene] 3-methyl-1-(psulfophenyl) 2-pyrazolin-5-one, 4-[4-(3-p-carboxyethyl- 2(3H) benzoxazolylidene)-2-butenylidene]-3-methyl-1- (p-sulfophenyl)-2-pyrazolin-5-one, bis( 1-butyl-3-carboxy methyl-S-barbituric acid)trimethine oxonol, bis(l-butyl- 3-carboxymethyl-5-barbituric acid) pentamethineoxonol, bis[3 methyl l-(p-sulfophenyl)-2-py-razolin-5-one-(4)] methineoxonol, 'bis[3 me'thyl-l-(p-sul fophenyl)-2-pyrazolin 5 one (4)]trimethineoxonol, bis[3-methyl-1-(psulfophenyl) 2 pyrazolin 5 one (4)] pentamethineoxonol, bis[3 methyl l-(p-sulfophenyl)-5-pyrazo1one- (4)]pentamethineoxonol, and typical ultraviolet absorbing dyes include the 2,5-bis(substituted sulfophenyl)thiazolo[5,4-d]thiazole disodium salts of Sawdey U.S. Ser. 183,417, filed Mar. 29, 1962, such as 2,5-bis(o-methoxyxsulfophenyl)thiazolo[5,4-d]thiazole disodium salt, 2,5- bis(o hexyloxy-x-sulfophenyl)thiazolo[5,4-d] thiazole disodium salt, 2,5 -bis(o-decyloxy-x-sulfophenyl)thiazolo [5,4-d]thiazole disodium salt, 2,5-bis(o-methyl-x-sulfophenyl)thiazolo[5,4-d]thiazole disodium salt, 2,5-bis(5- butyl 2 methyl x-sulfophenyl)thiazolo[5,4-d]thiazole disodium salt, 2,5 bis(m-methyl-x-sulfophenyl)thiazolo [5,4-d]thiazole disodium salt, 2,5-bis(p-propyl-x-sulfophenyl)thiazolo[5,4-d]thiazole disodium salt, etc.; the ultraviolet absorbing dyes of Sawdey US. Patent 2,739,- 888, issued Mar. 27, 1956, such as 3-phenyl-2-phenylimino-5-o-sulfobenZal-4 thiazolidone sodium salt, 5 (4- methoxy 3 sulfobenzal)-3-phenyl-2-phenylimino-4-thiazolidone (sodium salt), 3-phenyl-2-phenylimino-5-[3-(3- sulfobenzamido)benzal1-4-thiazolidone (sodium salt), 3- benzyl 2 phenylimino 5-o-sulfobenzal-4-thiazolidone (sodium salt), 5 2,4-dicarboxymethoxybenzal -3phenyl- 2-phenylimino-4-thiazolidone sodium salt, etc., tartrazine, and the like filter dyes.

Hardening materials that may be used to advantage include such hardening agents as formaldehyde; a halogen-substituted aliphatic acid such as mucobromic acid as described in White U.S. Patent 2,080,019, issued May 11, 1937; a compound having a plurality of acid anhydride groups such as 7,8-diphenylbicyclo (2,2,2)-7- octene-2,3,5,6-tetra-carboxylic dianhydride, or a dicarboxylic or a disulfonic acid chlorine such as terephthaloyl chloride or naphthalene-1,5-disulfonyl chloride as described in Allen and Carroll US. Patents 2,725,294 and 2,725,295, both issued Nov. 29, 1955; a cyclic 1,2-diketone such as -cyclopentane-1,2-dione as described in Allen and Byers US. Patent 2,725,305, issued Nov. 29, 1955; a bisester of methane-sulfonic acid such as l,2-di(methanesulfonoxy)ethane as described in Allen and Laakso US. Patent 2,726,162, issued Dec. 6, 1955; 1,3-dihydroxymethylbenzimidazol-Z-one as described in July, Knott and Pollak, US. Patent 2,732,316, issued Jan. 24, 1956; a dialdehyde or a sodium bisulfite derivative thereof, the aldehyde groups of which are separated by 2-3 carbon atoms, such as ,B-methyl glutaraldehyde bis-sodium bisulfite as described in Allen and Burness, Canadian Patent No. 588,451, issued Dec. 8, 1959; a bis-aziridine carboxamide such as trimethylene bis(l-aziridine carboxamide) as described in Allen and Wester US. "Patent 2,950,197, issued Aug. 23, 1960; or 2,3-dihydroxydioxane as described in Jeffreys US. Patent 2,870,013, issued Jan. 20, 1959.

The photographic element utilizing my light-screening layers have light-sensitive emulsion layers containing silver chloride, silver bromide, silver chlorobromide, silver iodide, silver bromoiodide, silver chlorobromoiodide, etc., as the light-sensitive material. Any lightsensitive silver halide emulsion layers may be used in these photographic elements. The silver halide emulsion may be sensitized by any of the sensitizers commonly used to produce the desired sensitometric characteristics.

My invention is further illustrated by the following examples describing the preparation of preferred mordants and the use thereof in photographic elements.

EXAMPLE 1 Poly(vinyl pyridiniumacetate chloride) (A) 20 g. (approx. 0.17 mol.) of polyvinyl chloroacetate was dissolved in 200 ml. of acetone. Then 40 ml. (approx. 0.47 mol.) of pyridine was added and the mixture allowed to stand overnight at room temperature. Soft material had precipitated. The supernatant liquid was decanted. The residue was dissolved in methanol, precipitated in ether, washed, and vacuum dried. It was then redissolved in methanol and reprecipitated in ether, washed, and vacuum dried. Analysis of this product showed that it contained 2.8% by weight of nitrogen as compared with calculated theory of approximately 7% by weight of nitrogen for pure poly(vinyl pyridinium acetate) chloride. Accordingly, this derived polymer consisted essentially of about 40% by weight of recurring (vinyl pyridinium acetate) chloride units of the structure:

and the remainder of the polymer to make of recurring units of unreacted vinyl chloroacetate.

(B) A solution of 6.0 g. (approx. 0.5 mol.) of polyvinyl chloroacetate in 100 ml. of dimethyl sulfoxide was treated with 10 g. (approx. 0.13 mol.) of pyridine. The mixture was allowed to stand 5 days. The polymer was then precipitated in acetone, washed and vacuum dried. It was redissolved in methanol and reprecipitated in ether, washed and vacuum dried. The yield of product was 9 g. Analysis of this product showed that the derived polymer consisted essentially of about 77% by weight of recurring units of vinyl pyridinium acetate chloride and 23% by weight of recurring units of unreacted vinyl chloroacetate.

(C) Substantially 100% poly(vinyl pyridiniumacetate chloride) was obtained by using pyridine as the solvent and heating to 70 C. for about 2 hours.

EXAMPLE 2 A solution of 60.0 g. (approx. 0.57 mol.) of poly (vinyl chlorornethyl ketone) in 600 ml. of N,N-dimethylformamide was treated with 1.25 ml. (approx. 11.58 mol.) of pyridine. The mixture was allowed to stand for 6 days. A soft precipitate formed. The supernatant liquor gave no precipitate in ether and discarded. The residue was dissolved in 1510 ml. of methanol, precipitated in acetone, washed and vacuum dried. It was re-dissolved in methanol, reprecipitated in acetone and dried. The yield was 55 g. Analysis of this product showed that it contained 3.8%

by weight of nitrogen as compared with calculated theory of approximately 7.6% by weight of nitrogen. Accordingly, this derived polymer consisted essentially of about 49.8% by weight of recurring (vinyl pyridinium methyl ketone) chloride units of the structure:

and the remainder of the polymer molecule to make 100% of recurring units of unreacted vinyl chloromethyl ketone.

The use of my novel and valuable polymers as mordants in filter layers will be illustrated with the following examples.

EXAMPLE 3 To 1.0 cc. of 1 photographic gelatin melted at 40 C. was added 30 mg. of poly(vinyl pyridinium acetate) chloride dissolved in 10 cc. of water. The pH of the solution was adjusted to 4.5-5.0 with glacial acetic acid. To this was added 10 rngs. of bis[3-methyl-l-p-sulfophenyl-5- pyrazolone(4) ]pentamethene-oxonol dissolved in water with vigorous stirring. The pH of the melt was then readjusted to 60:0.1 with 2.5 N sodium hydroxide solution, a coating aid added, the total volume adjusted to 32 cc. with distilled water and the melt coated on a film support and dried.

No signs of dye bleeding out of the gel layer were noted when a portion of the dried coating was immersed in stagnant distilled water at 75 F. for 2 minutes, nor after a second 2-minute immersion in the water.

Another portion of the coating was treated in a conventional alkaline silver halide developer solution containing hydroquinone and p-methylaminophenol sulfate as the developing agents. The mordanted dye was completely bleached by this treatment. Following treatment in the developer, the coating was treated in a conventional sodium thiosulfate fixing bath and then Washed. No residual sodium thiosulfate was detected in the coating by the Ross-Crabtree method.

Similar results were obtained when coatings were made substituting the corresponding trimethineoxonol dye and the corresponding monomethine oxonol dye for the pentamethine-oxonol dye. Coatings were made in which each of the above dyes were mordanted with poly(vinyl pyridinium methyl ketone) chloride instead of poly(vinyl pyridinium acetate) chloride. Each of these coatings showed no bleeding of dyes on immersion in water, but complete dye bleaching in the developer solution. No residual sodium thiosulfate was detected by the Ross- Crabtree method in the developed, fixed and washed coatmgs.

EXAMPLE 4 This example shows the use of the :derived polymers of the invention as on ultraviolet absorbing overcoating layer over light-sensitive gelatino-silver halide emulsion layers, for example, over the emulsion layers of a multilayer color element of the type described in Mannes et al., US. Patent 2,252,718, issued Aug. 1 9, 1941.

A gelatin-mordant composition was prepared by mixing 200 g. of a 10% aqueous gelatin solution at 40 C. and 200 g. of a 15% aqueous solution of the polymeric mordant prepared according to Example .1(A) at 40 C. The clear solution obtained was then chilled, noodled, and washed with cold water in the normal manner for 6 hours, drained, remelted at 0 C. and (weighed.

A coating melt was then prepared as follows employing the above gelatin-mordant composition.

Coating melt Gelatin containing 7.7 g. of Example 1 polymer Sulfur dioxide hydroquinone clathrate g 0.32 Adjust solution pH=6.07 $0.07 with lauric acid Adjust solution pH=6.2 Distilled water (to make total melt) g 383 The sulfur dioxide hydroquinone clathrate is described by H. M. Powell, J. Chem. Soc. (1948), pages 61-73; CA. 42, 5293 (1948). This melt was then coated over the emulsion layers of the above rnentioned multilayer color element at 6 g./sq. ft. (containing 1.33% gelatin) to give a coating comprising 120 mg./sq. ft. of the polymeric mordant of Example .1 and 40 mg./sq. ft. of the filter dye in mg./sq. ft. of gel. On sectioning of the coated element and in photographs made therewith, no bleeding of the dye was noted. Allcaline processing conditions left no dye residue and yet no stain increase was noted, implying betaine formation of the mordant with internal charge compensation. Also, no detectable thiosulfate was retained in the fixed element.

My alkali-release polymeric mordants are also used to advantage in mordanting light-filtering dyes, such as a blue-light absorbing dye having one or more acid substitutents, in a filtering layer between the top blue-sensitive layer and over the green-sensitive and the red-sensitive layers of a multilayer color photographic element of the type described in Mannes et al. US. Patent 2,252,7 1 8, referred to previously. Alternatively, appropriate dyes of other colors can be used to advantage in mordanted filter layers between the green-sensitive and red-sensitive layers, or one or more appropriate dyes can be mord anted in an antihalation layer either between the light-sensitive layers and the support or on the side of the support away from the light-sensitive layers.

Examples 5 through 8 illustrate the use of the derived polymeric mordants of the invention in antihalation layers, and further illustrate the improvement obtained therewith in regard to hypo retention in the processed elements, as compared with an element prepared [with a known mordanting polymer and a non-mordanted control element.

In each of the following examples, the coating melts were prepared, in general, by the procedure described in above Example 4. The melt compositions, with the exception of the control example, were coated on an ordinary cellulose acetate film support and over this melt layer was coated in each case a fine-grained silver chlorobromide gelatin emulsion layer. For convenience, the filter dyes employed are listed as follows:

Dye A.--4-[(3-ethyl 2(3H) benzoxazolylidene)ethylidene] 3 methyl-l-p sulfophenyl-2-pyrazolin-5-one, monosulfonated Dye B.Bis(1 butyl-3-carboxymethyl-5-barbituric acid) tri-methineoxonol Dye C.4- [4- 3-ethyl-2( 3H -benzoxazolylidene -2-butenylidene] 3-methyl-1-p-sulfophenyl-Z-pyrazolin-5-one, monosulfonated Dye D.Bis(1-butyl-3-carboxymethyl-S-barbituric acid) pentamethineoxonol Dye E.--Bis[3 methyl-l-(p-sulfophenyl)-2-pyrazolin-5- one (4) -methineoxonol 11 Dye F.-Bis[3 methyl-l-(p-sulfophenyl)-2-pyrazolin-5- one- (4) ]-trimethineoxonol Dye G.Bis[3 methyl-l-(p-sulfophenyl)-2-pyrazolin-5- one 4) ]-pentamethineoxonol EXAMPLE 5 A control film element was coated having no antihalation undercoat.

EXAMPLE 6 A film element was coated having an antihalation undercoat comprising gelatin+poly(a-methylallyl-N-guanidyl-ketimine, glycolic acid salt) prepared in accordance with Minsk U.S. Patent 2,882,156, issued Apr. 14, 1959, as the mordant polymer (28 mg./ft. Dye A (2.4 mg./ ft. Dye B (1.6 mg./ft. Dye C (2.9 mg./ft and Dye D (2.5 mg./ft

EXAMPLE 7 A film element was coated having an antihalation undercoat comprising gelatin and the polymeric mordant of Example 1(A) (45 mg./ft. Dye A (2.4 mg./ft Dye B (1.6 mg./ft. Dye C (2.9 mg./ft. and Dye D (2.5 mg./ft.

EXAMPLE 8 A film element was coated having an antihalation undercoat comprising gelatin and the polymeric mordant of Example 1(A) (45 mg./ft. Dye E (5 mg./ft. Dye F (5 rug/ft?) and Dye G (5 mg./ft.

The film coatings of above Examples 5, 6, 7 and 8 were exposed on an intensity scale sensitometer, developed for 2 in a conventional alkaline developer solution using hydroquinone and p-methylaminophenol sulfate as the developing agents at 80 F., fixed in a conventional sodium thiosulfate fixing bath that was substantially neutral, washed and dried. The processed strips were analyzed for residual hypo. The following results were obtained:

Hypo

Relative Retention Example Speed 7 Fog (mg/in!) It will be noted from the above-tabulated results that the hypo retention by the film elements prepared with a polymeric mordant of the invention (Examples 7 and 8) was practically negligible in amount ranging only from 0.002 to 0.009 mg./iu. whereas the film element (Example 6) prepared with poly[u-methyallyl-N-guanidylketimine, glycolic acid salt] showed a hypo retention many fold greater than 0.032 mg./in.

Similar results are obtained by substituting the following mordants for poly(vinyl pyridiniumacetate chloride) in the preceding examples.

The above mordants are prepared according to the methods of the invention described in Examples 1 and 2 by reacting polyvinyl chloroacetate or poly(vinyl chloromethyl ketone) with the appropriate heterocyclic amine.

The use of my polymeric mordants in light-screening layers over light-sensitive silver halide emulsion layers,

and in antihalation undercoat layers, to produce improved photographic elements has been illustrated in the preceding examples. However, it will be apparent that the mordants of the invention can also be advantageously used in light-screening layers between two or more color sensitized silver halide emulsion layers, or in antihalation backing layers, or incorporated directly in light-sensitive silver halide emulsion layers, or they can be used to prepare imbibition dye transfer blanks of improved properties.

The invention has been described in detail with particular reference to preferred embodiments thereof but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.

I claim: 1. A compound selected from those having the formula:

0 R: I Z Ri(0)mi J H-Il E) R3 wherein m, R R Z and X are as defined previously.

2. A compound of claim 1 in which Z represents the atoms required to complete a nucleus selected from the class consisting of a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a thianaphtheno-7',6,4,5- thiazole nucleus, an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a selenazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, a thiazoline nucleus, a quinoline nucleus, an isoquinoline nucleus, a pyridine nucleus, an imidazole nucleus, 21 benzimidazole nucleus, a napththimidazole nucleus, a 3,3-dialkylindolenine nucleus, a 1,2,4-thiadiazole nucleus, a 1,2,4-triazole nucleus, and a tetrazole nucleus.

3. A resinous linear polymer derived from a monoethylenically unsaturated polymerizable compound and having periodically occurring groups attached to carbon atoms of the polymer chain of the structure:

wherein m represents an integer of from 1 to 2, R represents a member selected from the class consisting of the hydrogen atom, a lower alkyl group and a phenyl group, R represents a member selected from the class consisting of the hydrogen atom, an alkyl group and an aryl group, X represents an acid anion, and Z represents the nonmetallic atoms required to complete a heterocyclic nucleus selected from the class consisting of a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a thianaphtheno-7',6,4,5-thiazole nucleus, an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a selenazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, 21 thiazoline nucleus, a quinoline nucleus, an isoquinoline nucleus, a pyridine nucleus, an imidazole nucleus, a benzimidazole nucleus, a naphthimidazole nucleus, a 3,3-dialkylindolenine nucleus, a 1,2,4-thiadiazole nucleus, at 1,2,4-triazole nucleus, and a tetrazole nucleus.

4. A resinous copolymer which functions as an alkalirelease mordant for acid dyes consisting essentially of from about 25100% by weight of recurring polymerized units of the structure:

and from 750% by weight of recurring polymerized units selected from the class consisting of those having the formula:

wherein m in each occurrence represents the same integer of from 1 to 2, R in each occurrence represents the same member selected from the class consisting of the hydrogen atom, a lower alkyl group and a phenyl group, X in each occurrence represents the same acid anion, R represents a member selected from the class consisting of the hydrogen atom, an alkyl group and an aryl group, and Z represents the non-metallic atoms required to complete a heterocyclic nucleus selected from the class consisting of a thiazole nucleus, a benzothiazole nucleus, at naphthothiazole nucleus, a thianaphthen-7',6,4,S-thiazole nucleus, an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a selenazole nucleus, a benzoselenazole nucleus, a

naphthoselenazole nucleus, a thiazoline nucleus, a quinoline nucleus, an isoquinoline nucleus, a pyridine nucleus, an imidazole nucleus, a benzimidazole nucleus, a naphthimidazole nucleus, a 3,3-dialkylindolenine nucleus, a 1,2,4- thiadiazole nucleus, a 1,2,4-triazole nucleus, and a tetrazole nucleus.

5. A resinous copolymer which functions as a mordant for acid dyes consisting essentially of from about 25- 100% by weight vinyl pyridiniumacetate chloride units and from about 0% by weight of vinyl chloroacetate units.

6. A resinous copolymer which functions as a mordant for acid dyes consisting essentially of from about 25100% by weight of vinyl pyridiniummethyl ketone chloride units and from about 750% by weight of vinyl chloromethyl ketone units.

7. A non-sensitive element comprising a support material having thereon a hydrophilic colloid layer containing at least one compound of claim 1.

References Cited UNITED STATES PATENTS 5/1952 Cofiman 260-63 US. Cl. X.R.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2595225 *Feb 9, 1950May 6, 1952Du PontPolymeric poly-quaternary ammonium salts
US2972537 *Sep 3, 1957Feb 21, 1961Eastman Kodak CoCondensation products of polyvinylketones with hydrazides containing quaternary nitrogen groups
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4108802 *May 20, 1976Aug 22, 1978Ciba-Geigy AgQuaternary ammonium polymers and photographic materials containing same
US5470986 *Jun 27, 1994Nov 28, 1995E. I. Du Pont De Nemours And CompanyImidazolium hardeners for hydrophilic colloid
US5591863 *Jun 5, 1995Jan 7, 1997Sterling Diagnostic Imaging, Inc.Imidazolium hardeners for hydrophilic colloids
EP0561475A1 *Mar 18, 1993Sep 22, 1993Eastman Kodak CompanyBleachable polymeric filter dyes
Classifications
U.S. Classification526/257, 526/265, 548/304.4, 548/310.4, 548/302.1, 526/261, 526/263, 525/61, 548/343.1, 526/260, 526/258, 548/305.4, 548/325.5, 526/259, 548/306.4, 430/518, 525/330.5, 548/316.4, 548/312.7, 525/328.6
International ClassificationC07D213/20, G03C8/56, C07D277/22, C07D277/64, C07D213/30, C07D257/04, C07D277/84, G03C1/835, C07D277/62, C07D235/06, C07D293/06, C07D215/10
Cooperative ClassificationC07D277/62, C07D277/64, C07D293/06, Y10S430/142, C07D257/04, C07D213/30, C07D235/06, G03C8/56, G03C1/835, C07D213/20, C07D277/22, C07D277/84, C07D215/10
European ClassificationC07D277/84, G03C1/835, C07D215/10, C07D277/64, C07D213/20, C07D277/22, C07D293/06, G03C8/56, C07D213/30, C07D235/06, C07D257/04, C07D277/62