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Publication numberUS3459790 A
Publication typeGrant
Publication dateAug 5, 1969
Filing dateDec 20, 1965
Priority dateDec 20, 1965
Also published asDE1547765A1, DE1547765B2, DE1547765C3, DE1793660A1, DE1793660B2, DE1793660C3
Publication numberUS 3459790 A, US 3459790A, US-A-3459790, US3459790 A, US3459790A
InventorsDonald Arthur Smith
Original AssigneeEastman Kodak Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Polymerizable acrylic acid esters containing active methylene groups
US 3459790 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

3,459,790 POLYMERIZABLE ACRYLIC ACID ESTERS CON- TAINlNG ACTIVE METHYLENE GROUPS Donald Arthur Smith, Rochester, N.Y., assignor to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed Dec. 20, 1965, Ser. No. 525,272 Int. Cl. C07c 69/66, 69/54; C08f 3/66 US. Cl. 260-483 8 Claims where R is alkylene and X is aliphatic acyl or cyano; and R is alkyl, cycloalkyl, aryl or Where R is alkylene and X is aliphatic acyl or cyano, provided that one and only one of R, and R is always i -RaOC--CH2X In one aspect, polymers containing units of monomers of the above formula can be utilized to provide improved photographic compositions.

This invention relates to organic materials which are particularly useful in the photographic field. In one of its aspects, this invention relates to the preparation and use of such organic materials, particularly polymeric materials which can be incorporated into photographic elements and emulsions to obtain a desirable combination of properties. In another of its aspects, this invention relates to photographic materials, their preparation and use.

Photographic elements employed in photography, particularly in the graphic arts industry for the production of lithographic plates, must have good physical and photographic properties. Due to its unique properties, including its good dispersing property and its excellent protective colloid properties, gelatin has been used as the binding agent in layers of photographic elements for many years. Gelatin is however subject to dimensional change when subjected to varying temperature, humidity and like conditions. Many natural and synthetic materials have been proposed as substitutes for gelatin in one or more layers of a photographic element to improve dimensional stability. For example, as shown in US. Patent 3,062,674, issued Nov. 6, 1962 and U.S. Patent 3,142,568 issued July 28, 1964, vinyl or addition polymers are employed in binding agents in layers of photographic elements to improve physical properties, including dimensional stability. However, the use of such vinyl or addition polymers, either as solutions or as hydrosols, in layers of photographic elements, often adversely affects the hardness of the layers and their resistance to abrasion. It is evident, therefore, that a substitute for gelatin which is not subject to such defects will greatly enhance the art.

Accordingly, it is an object of this invention to provide a class of interpolymers that can be incorporated into photographic materials to obtain products exhibiting good physical and photographic properties.

States Patent 0 It is another object of this invention to provide monmeric materials which form a class of interpolymers that can be incorporated into photographic materials exhibiting good dimensional stability and resistance to abrasion.

It is another object of this invention to provide photographic elements and emulsions which exhibit goo physical and photographic properties.

It is still another object of this invention to provide photographic elements and emulsions in which the binding agent comprises gelatin and a film-forming, addition interpolymer containing active methylene groups.

Other objects of this invention will become apparent from an examination of the specification and claims which follow.

In accordance with this invention, it has been found that a film-forming, addition interpolymer containing at least about 0.1%, by weight, of active methylene groups in aliphatic side chains can be used in binding agents in photographic materials to give products having good dimensional stability and resistance to abrasion. A particularly effective class of interpolymers useful for this purpose is prepared from acrylic type esters having active methylene groups in the ester moiety or in a substituent alpha to the carbonyl group. Such compounds can be represented by the formula:

CH =Oi JO R2 1'1. where R is hydrogen, alkyl or o Ro( ioH2X where R is alkylene and X is aliphatic acyl or cyano and R is alkyl, cycloalkyl, aryl or Where R and X are as defined, provided that one and only one R and R is always The ethylenically unsaturated polymerizable monomers having the above formula can be prepared using any procedure suitable for this purpose. In general, the reaction of acid chlorides, acid anhydrides or mixed anhydrides containing active methylene groups with acrylic esters containing hydroxyalkyl substituents can be employed. A preferred synthesis for preparing the esters having an active methylene group in the ester moiety involves the reaction of a hydroxyalkyl ester of acrylic or an alphaalkyl acrylic acid with diketene or cyanoacetyl chloride. The esters having active methylene groups in the alphasubstituent in the above formula can be obtained by reacting the alpha-hydroxyalkyl substituted acrylic esters with diketene or cyanoacetyl chloride. Such reactions are not particularly pressure sensitive and, therefore, can be carried out at atmospheric, superatmospheric or subatmospheric pressure. The temperature range is subject to Wide variation depending, for example, upon the particular reactants employed, solvents and like considerations, but generally temperatures up to about C. and often temperatures in the range of about 35 to about 100 C. are suitable. The reaction can be carried out in the absence of solvent or using a suitable vehicle, for example, diethyl ether, ethyl acetate or the like and is generally completed in less than 20 hours, often less than 4 hours. The acrylic esters containing the active methylene groups are generally viscous liquids or oils and can be separated from the reaction medium by any means suitable for this purpose, for example, by distillation.

The interpolymers employed in photographic materials according to the practice of this invention are film-forming, addition interpolymers containing at least about 0.1%, generally about 0.1 to about 1.4%, by weight, of active methylene groups in aliphatic side chains of the interpolymers. Active methylene groups are methylene groups between two activating groups, for example electronegative groups such as carbonyl. Such methylene groups exhibit unusual chemical activity and are said to be active. Malonic esters, acetoacetic esters, cyanoacetic esters and 1,3-diketones are examples of compounds containing such groups. The active methylene groups are usually separated from the main polymer chain by at least three atoms and can be introduced into the side chains of an interpolymer by copolymerizing a monomer containing at least one active methylene group, for example a o o II it --COH2--G group, and an independently polymerizable unsaturated methylene group with at least one other copolymerizable monomer containing, for example, at least one group. Where reference is made to the fact that the active methylene groups are in aliphatic side chains of the interpolymers, this is intended to mean that the chain which links the active methylene group to the main polymer chain of the interpolymer is free of non-aliphatic groups, e.g. aromatic groups, i.e. the active methylene group is bonded to the main chain or backbone of the interpolymer through an aliphatic linkage. The molecular weights of the interpolymers employed in photographic emulsions and elements according to the practice of this invention are subject to wide variation, but are often in the range of about 5,000 to about 500,000.

A particularly useful class of polymers containing active methylene groups in aliphatic side chains and which can be employed as substitutes for gelatin in photographic emulsions and elements is prepartd by interpolymerizing at least one unsaturated polymerizable compound containing one or more CH =C groups with a different monomer having the formula:

where R and R are as defined hereinbefore. Useful gelatin substitutes include, therefore, interpolymers of acrylic monomrs having the above formula with other ethylenically unsaturated polymerizable monomers which form addition polymers, such as vinyl esters, amides, nitriles, ketones, halides, ethers, alpha-beta-unsaturated acids or esters thereof, olefins, diolefins and the like, as exemplified by acrylonit-rile, methacrylonitrile, styrene, alpha-methylstyrene, acrylamide, vinyl chloride, vinylidene chloride, methyl vinyl ketone, fumaric, maleic and itaconic esters, 2-chloroethyl vinyl ether, acrylic acid, methacrylic acid, dimethylaminoethyl methacrylate, 4,4, 9-trimethyl 8 oxo-7-oxa-4-azonia-9-decene-l-sulfonate, N-vinylsuccinamide, N vinylphthalamide, N vinylpyrazolidone, 'butadiene, isoprene, vinylidene chloride, ethylene and the like.

A preferred class of vinyl or addition interpolymers which can be employed as gelatin substitutes in photographic materials are interpolymers of (A) about 50 to about by weight, of a monomer (1) having the formula:

where R is hydrogen or methyl and R is alkyl, desirably containing up to about 10 carbon atoms, as exemplified by methyl, propyl, isobutyl, octyl, decyl and the like, (B) about 3 to about 20%, by weight, of a sulfoester monomer (2) having the formula:

where R is hydrogen or alkyl, desirably containing up to about 12 carbon atoms, often 1-8 carbon atoms, as exemplified by methyl, pentyl, octyl, dodecyl and the like, R has its valence bonds on ditferent carbon atoms and can be a divalent hydrocarbon radical or divalent aliphatic hydrocarbon radical in which a chain of carbon atoms joining the oxygen and sulfur atoms in the above formula is interrupted by an atom from Group IV-A of the Periodic Table having an atomic weight of less than about 33, i.e., at least one -O-- and/or -S radical interrupts the carbon chains and M is a cation and (C) about 2 to about 20%, by weight, of a monomer (3) having the formula:

oI-I2=C-iio1t 1'1. where R, is hydrogen, alkyl, desirably containing up to 12 carbon atoms as exemplified by methyl, n-butyl, octyl, dodecyl and the like, or

O -Rn--O(%CH2X where R is alkylene, desirably containing up to 10, preferably 1-8 carbon atoms, as exemplified by ethylene, tetramethylene, 1,3-isobutylene, octamethy-lene and the like and X is aliphatic acyl containing up to about 8 carbon atoms, such as alkyl carbonyl groups exemplified by acetyl, butyryl, caprylyl and the like, or cyano and R is alkyl, desirably containing up to about 10 carbon atoms, as exemplified by methyl, butyl, octyl, decyl and the like, cycloalkyl, desirably containing up to about 10 carbon atoms, as exemplified by cyclopentyl, cyclo'butyl, cyclohexyl and the like, aryl, desirably containing up to about 12 carbon atoms, as exemplified by phenyl and the like or 1 RaO(iCH2X where R and X are as defined hereinabove for this radical, provided that one and only one of R and R is always -R-O "JCH2X Where R in the sulfoester monomer (2) above is hydrocarbon, it can be any aliphatic, cycloaliphatic or aromatic radical and will generally contain up to about 12 carbon atoms. Preferred hydrocarbon R radicals are alkylene radicals, generally those containing 2-4 carbons. R can also be a divalent aliphatic hydrocarbon radical in which there is an O-- and/or S- radical and generally contains up to 12 carbon atoms. Such R radicals can, therefore, be saturated or unsaturated, although saturated divalent alkylene groups in which the carbon chain is interrupted by oxygen and sulfur atoms are preferred. Suitable R radicals include, for example, ethylene, 1,3- propylene, 1,2-propylene, tetramethylene, 1,3-isobutylene, pentamethylene, hexamethylene, octamethylene, phenylene, bisphenylylene, naphthylene, cyclopentylene, cyclohexylene, Z-butylene, butynylene, 2-oxatrimethylene, 3-

thiapentamethylene, and the like, M in the sulfoester monomer (2) is a cation, as exemplified by hydrogen, an alkali metal such as sodium or potassium, ammonium, the cation of an organic amine such as t-riethylene amine, diethanol amine and the like.

Another class of vinyl or addition interpolymers which can be employed as gelatin substitutes in photographic materials are interpolymers in which acrylic acid is used in place of the sulfoester monomer (2). These interpolymers are film-forming, addition interpolymers of (A) about 50 to about 90%, by Weight, of a monomer (1) having the formula:

where R and R are as defined hereinbefore for monomer (1), (B), about 3 to about 20%, by weight, of acrylic acid and (C) about 2 to about 20%, by weight, of a monomer (3) having the formula:

where R, and R are as defined hereinbefore. The preferred class of interpolymers containing sulfoester units preferably contain, in polymerized form, at least about 65%, by weight, of monomer (1), at least about 3%, by weight, of sulfoester monomer (2) and at least about 2%, by weight, of monomer (3). The preferred class of interpolymers containing acrylic acid units preferably contain, in polymerized form, at least about 65%, by Weight, of monomer (1), at least about by weight, of acrylic acid and at least about 5%, by weight, of monomer 3).

The temperature at which the interpolymers described herein are prepared is subject to wide variation since this temperature depends upon such variable features as the specific monomer used, duration of heating, pressure employed and like considerations. However, the polymerization temperature generally does not exceed about 110 C., and most often it is in the range of about to about C. The polymerization can be carried out in a suitable vehicle, for example, water or mixtures of water with Water miscible solvents, as exemplified by methanol, ethanol, propanol, isopropyl, alcohol, butyl alcohol, and the like. The pressure employed in the polymerization, if any, is usually only sufficient to maintain the reaction mixture in liquid form, although either superatmospheric or subatmospheric pressures can be used. The concentration of polymerizable monomer in the polymerization mixture can be varied widely with concentrations up to about 40%, by weight, and preferably about 20 to about 40%, by weight, based on the Weight of the vehicle, being satisfactory. Suitable catalysts for the polymerization reaction include, for example, the free radical catalysts, such as hydrogen peroxide, cumene hydroperoxide, water soluble azo type initiators and the like. In redox polym erization systems the usual ingredients can be employed. If desired, the polymer can be isolated from the reaction vehicle by freezing, salting out, precipitation or any other procedure suitable for this purpose.

As indicated in U.S. Patent 3,142,568, issued July 28, 1964, it is sometimes advantageous to include a surface active agent or compatible mixtures of such agents in the preparation of vinyl or addition polymers and in coating photographic materials containing such polymers. Suitable wetting agents include the non-ionic, ionic and amphoteric types as exemplified by the polyoxyalkylene derivatives, amphoteric amino acid dispersing agents, including sulfobetaines and the like. Such Wetting agents are disclosed in U.S. Patent 2,600,831, issued June 17, 1952; U.S. Patent 2,271,622, issued Feb. 3, 1942; U.S. Patent 2,271,623, issued Feb. 3, 1942; U.S. Patent 2,275,727, issued Mar. 10, 1942 and U.S. Patent 2,787,604, issued Apr. 2, 1957; U.S. Patent 2,816,920, issued Dec. 17, 1957, and U.S. Patent 2,739,891, issued Mar. 27, 1956. It has been found that a particular type of non-ionic wetting agent will give outstanding results when so employed. It is particularly convenient to use the non-ionic wetting agents described hereinafter in the formation of the interpolymers containing active methylene groups in their side chains and then incorporate the reaction mixture into a photographic emulsion or element. The Wetting agents are generally employed in the polymer preparation in concentrations in the range of about 1% to about 5% based on polymerizable monomer and in coating photographic elements at concentrations in the range of about 0.1 to about 5%, by Weight, based on binding agent. Particularly suitable non-ionic wetting agents or coating aids are disclosed in Belgian Patent 652,862 as having the formula:

TABLE I CHz-CHOHOH2OH Position Position No. R of R R of R x l (CHs)sCC5H10 p (CHaMCCsHm 0 9 l 2 (CH3)3CCH2C(CH3)2 p H 4 l 3 (CH3)3GCII2C(CH3)2 p (CHmCCH2C(CHa)z 0 8 CrzHss p H 5 C 'H m H 8 p 0101121 0 6 CsHn p -CaHi1 0 l0 5 n p COHm 0 10 (CHa)sC C5H10 p H 10 H21 p OH:; 0 7 0 0112 p C3II7 0 8 12 C 5H37 p -CH3 0 12 13 C5Hu p 013301106113 0 7 l 14 CH3 1) CHsCHC10H2 0 8 The above surface active materials, when incorporated in photographic hydrophilic colloid coating compositions and hydrophilic colloid coatings which can, but need not, contain photographic silver halide, increase the ease and efficiency of the coating process and provide a favorably high degree of surface roughness and excellent developer rewettability on coated layers having few or no repellen cies, without adversely affecting the photographic properties of the final product. These coating aids are compatible with both acid and lime-processed gelatin as Well as a wide variety of photographic emulsion addenda such as hardeners, antifoggants, mordants, couplers, antistatic agents, and the like.

Dispersions of the photographic silver halide containing the film-forming, addition interpolymers containing active methylene groups, in combination with photographic binding agents, such as gelatin, can be made in a variety of Ways. For example, an aqueous gelatin dispersion of the photographic silver halide can be mixed with an aqueous dispersion or solution of the interpolymer. Alternatively, the photographic silver halide can be precipitated in an aqueous dispersion or solution of the interpolymer with or without another colloid, depending upon the dispersing characteristics of the interpolymer. In this case, a water-soluble silver salt such as silver nitrate is admixed with a water-soluble halide such as potassium bromide in the presence of the mixture. In still another procedure, the photographic silver halide is precipitated in an aqueous gelatin solution and digested in the conventional manner known to the art. After digestion, but prior to coating. there is added to the emulsion an aqueous dispersion of the interpolymer containing active methylene groups in its side chains. The bulk of the resulting dispersion can be increased by the addition of more of the interpolymer and/or natural or synthetic colloids or other binding agents suitable for use in photographic silver halide emulsions. Satisfactory colloids include, for example, gelatin, protein derivatives e.g. carboxy methylated proteins, colloidal albumin, cellulose derivatives, synthetic resin such as polyvinyl compounds e.g. polyacrylamide and the like.

The gelatin substitutes described herein can be employed in the binding agent in one or more layers of a photographic silver halide element. However, photographic silver halides are generally precipitated in the presence of binding agents such as gelatin or other colloids which exhibit very good peptizing action. Therefore, the photographic silver halide emulsions or layers of this invention will generally contain some binding agent such as gelatin which exhibits this very good peptizing action. Generally, the concentration of the interpolymers described herein will be in the range of about 20 to about 85%, often in the range of about 50 to about 85%, by weight, based on total binding agent (dry weight), employed in photographic emulsions, photographic emulsion layers or other layers of a photographic element. In the preferred case, the remainder of the binding agent is gelatin, although other colloids also give good results. Where the polymers are used in photographic elements in layers other than the emulsion layers, for example, in filter layers, antihalation layers, antiabrasion layers, antistatic layers, barrier layers, receiving layers for diffusion transfer processes and the like; they can be used as the sole vehicle or in admixture with natural or synthetic colloids such as are mentioned hereinbefore. The silver halide employed in the preparation of light sensitive coatings described herein includes any of the photographic silver halides as exemplified by silver bromide, silver chloride and silver iodide, or mixed silver halides such as silver chlorobromide, silver bromoiodide, and the like. Very good results are obtained with high contrast silver halide emulsions in which the halide comprises at least 50 mole percent chloride. Preferred emulsions of this type contain at least 60 mole percent chloride; less than 40 mole percent bromide and less than mole percent iodide.

The photographic compositions described herein can be coated on a wide variety of supports. Typical supports include polymeric films such as cellulose acetate film, polyvinyl acetal film, polystyrene film, polypropylene film and other polyolefin film, polycarbonate film, polyethylene terephthalate film and other polyester film as well as glass, paper, wood and the like. Supports such as paper which are coated with alpha-olefin polymers, particularly polymers of alpha-olefins containing 2-l0 carbon atoms, as exemplified by polyethylene, polypropylene, ethylenebutene copolymers and the like give good results.

The emulsions containing the interpolymers can be chemically sensitized with compounds of the sulfur group, noble metal salts such as gold salts, reduction sensitized with reducing agents, and combinations of these. Furthermore, emulsion layers and other layers present in photographic elements made according to thi invention can be hardened with any suitable hardener such as aldehyde hardeners, such as formaldehyde, mucochloric acid and the like, aziridine hardeners, hardeners which are derivatives of dioxane, oxypolysaccharides such as oxystarch, oxy plant gums and the like. Such hardened layer will have a melting point in Water greater than about F. and preferably greater than 200 F.

The emulsion can also contain additional additives, particularly those known to be beneficial in photographic emulsions, including for example, stabilizers or antifoggants, particularly the water-soluble inorganic acid salts of cadmium, cobalt, manganese and zinc as disclosed in U.S. Patent 2,829,404, the substituted triazaindolizines as disclosed in U.S. Patents 2,444,605 and 2,444,607, speed increasing materials, absorbing dyes, plasticizers and the like. Sensitizers which give particularly good results in the photographic compositions disclosed herein are the alkylene oxide polymers which can be employed alone or in combination with other materials, such as quaternary ammonium salts, as disclosed in U.S. Patent 2,886,437 or with mercury compounds and nitrogen containing compounds, as disclosed in U.S. Patent 2,751,299.

The interpolymers containing at least about 0.1%, by weight, of active methylene groups in their side chains can be used in various kinds of photographic emulsions. For example, they can be used in direct positive silver halide emulsions, X-ray and other non-spectrally sensitized emulsions as well as in orthochromatic, panchromatic and infrared sensitive emulsions, particularly those sensitized with merocyanine dyes, cyanine dyes, carbocyanine dyes and the like. Furthermore, these polymers can be used in emulsions intended for color photography, for example, emulsions containing color forming couplers or emulsions to be developed by solutions containing couplers or other color generating materials. In addition, these polymers can be used in photographic emulsions containing developers, e.g. polyhydroxybenzenes as well as in emulsions intended for use in diffusion transfer processes which utilize the non-developed silver halide in the non-image areas of the negative to form a positive by dissolving the undeveloped silver halide and precipitating it on a receiving layer in close proximity to the original silver halide emulsion layer. Such processes are described in Rott U.S. Patent 2,352,014, Land U.S. Patent 2,543,181 and Yackel et al. U.S. Patent 3,020,155. The polymers described herein can also be used in color transfer processes which utilize the diffusion transfer of an image-wise distribution of developer, coupler or dye from a light sensitive layer to a second layer while the two layers are in close proximity to one another. Color transfer processes of this type are described in Yutzy U.S. Patent 2,856, 142, Land et al. U.S. Patent 2,983,606, Whitmore et al. British Patents 904,364 and 840,731 and Whitmore et al. U.S. application Ser. No. 392,471. These polymers can also be used in unhardened colloid layers, particularly those designed for processing in hardening developers, as disclosed in British Patent 825,544, published Dec. 16, 1959. Silver halide emulsions containing these polymers can be processed in monobath processes such as described in Haist et al. U.S. Patent 2,875,048 or in stabilization type processes.

This invention can be further illustrated by the following examples of preferred embodiments thereof although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention unless otherwise specifically indicated.

Example 1 Twenty-seven grams of 2-hydroxyethyl methacrylate is mixed with 20 g. of diketene. After the addition of 1 g. of hydroquinone (polymerization inhibitor) the mixture is heated to 100 C. After four hours the mixture is distilled in vacuo and the fraction boiling at 100-130 C./ 1 mm. is collected. This fraction is redistilled from hydroquinone and the principal fraction is collected at 110- 120 C./ 0.3 mm. There is obtained 30 g. of Z-acetoacetoxyethyl methacrylate.

Example 2 A solution of 24 g. of Z-hydroxyethyl acrylate and 17 g. of diketene in 100 ml. of ethyl acetate is treated with 0.2 g. of triethylamine. The temperature rises gradually to 33 C. over one hour. The solution is heated at reflux for two hours and concentrated in vacuo to an oil which is submitted to molecular distillation at 9 microns. A yield of 15.8 g. of 2-acetoacetoxyethyl acrylate is obtained at a pot temperature of 73 C.

Example 3 To a solution of 82 g. of freshly distilled diketene in 400 ml. of ethyl acetate is added 127 g. of ethyl or- (hydroxymethyl)acrylate. One gram of p-(p-toluenesulfonamido) diphenylamine (polymerization inhibitor) is added and the solution stirred at room temperature. In the course of three hours the temperature gradually rises to a maxmium of 47 C. The solution is kept for approximately 15 hours at room temperature, treated with 2 g. of anilinophenol and submitted to molecular distillation. Several fractions, shown to be similar by infrared spectroscopy, are collected between 84 C. and 94 C. at 500- 505 microns. The total weight of the fractions, which are substantially ethyl a-acetoacetoxymethyl acrylate is 107 g.

Example 4 A suspension of 104 g. of phosphorus pentachloride in 200 ml. of ether is cooled to 10 C. and treated dropwise with 42.5 g. of cyanoacetic acid in 450 ml. of diethylether. The resulting clear solution is concentrated in vacuo to a weight of 54 g. of crude cyanoacetyl chloride. The crude cyanoacetyl chloride is added to a solution of 65 g. of 2-hydroxyethyl methacrylate in 125 ml. of diethyl ether containing 25 g. of acrylonitrile. After two hours at room temperature the solution is refluxed for 1 /2 hours and concentrated to an oil in vacuo. Molecular distillation at 12l3 microns yields 60.5 g. of colorless oil at 8385 C. The infrared analysis, Nuclear Magnetic Resonance and elemental analysis confirmed the structure of the material as being 2-cyanoacetoxyethyl methacrylate.

Example As already indicated, compounds of the type prepared according to Examples 1-4 will polymerize with other monomers to form interpolymers containing active methylene groups in the side chains of the interpolymers. To ilustrate, one hundred seventy-five ml. of water is swept with nitrogen for ten minutes and placed in a three-necked flask in a bath at 80 C. To this is added 2 ml. of Triton 770 (a 40% solution of a surfactant composition composed of a sodium salt of an alkyl aryl polyether sulfate in isopropanol), 0.5 g. of potassium persulfate and 0.05 g. of sodium bisulfite. To this mixture the following two solutions are added simultaneously with stirring:

(a) 51.5 grams of butyl acrylate, 6.75 g. of acrylic acid, and 10.0 g. of Z-acetoacetoxyethyl acrylate.

(b) 0.1 gram' of sodium bisulfite and 2 ml. of Triton 770 in ml. of water.

The addition is completed in ten minutes under a constant stream of nitrogen with the flask maintained at C. After heating for an additional fifteen minutes, the latex is cooled. The copolymer latex has the molar composition of 75.7% butyl acrylate, 14.9% acrylic acid, and 9.4% Z-acetoacetoxyethyl acrylate and is prepared at two pH levels5.0 and 6.2.

Example 6 A solution of 4 ml. of Triton 770 in 375 ml. of water is purged with nitrogen and heated to C. 1.0 g. of potassium persulfate and 0.1 g. of sodium bisulfite are added with stirring, followed immediately by the gradual addition from two funnels of the following:

(a) 112.8 g. of methyl acrylate and 5.9 g. of 2-acetoacetoxyethyl acrylate.

(b) A solution of 6.3 g. of 3-acryloyloxy-1-methyl propane-l-sulfonic acid sodium salt, 0.23 g. of sodium bisulfite and 4 ml. of Triton 770 in ml. of water.

During the simultaneous addition, which is complete in 12 minutes, the polymerization proceeds briskly with reflux of methyl acrylate. The heating is continued for approximately one hour to obtain a latex of copoly (methyl acrylate-sodium 3-acryloyloxy l-methyl propane-1-sulfonate-2-acetoacetoxyethyl acrylate) which is adjusted to pH 5.

Example 7 A solution of 7.5 g. of ethyl acrylate, 2.0 g. of acrylic acid and 1.0 g. of Z-acetoacetoxyethyl methacrylate in 10 ml. of dioxane is mixed with 0.05 g. of 2,2'-azobis(2- methylpropionitrile) and kept at 80 C. for one hour. The copoly(ethyl acrylate-acrylic acid-Z-acetoacetoxyethyl methacrylate) is isolated by precipitation in Water.

Example 8 A solution of 4.0 ml. of Triton 770 in 350 ml. of water is swept with nitrogen and heated to 80 C. 1.0 g. of potassium persulfate and 0.1 g. of sodium bisulfite is added. The following two solutions are added simultaneously over ten minutes with stirring:

(1) 90 g. of methyl acrylate, 25 g. of acrylic acid and 10 g. of ethyl a-acetoacetoxymethyl acrylate.

(2) 150 ml. of water containing 4.0 ml. Triton 770 and 0.2 g. of sodium bisulfite.

The resulting latex of copoly(methyl acrylate-acrylic acid ethyl OL'HCCtOBCEllOXY methyl acrylate) is kept at 80" C. for two hours and cooled to room temperature. A portion of the latex is diluted with an equal volume of water and treated with sodium hydroxide (10% solution) to give a solution at pH 5.0 containing 9.8% solids.

Example 9 As previously pointed out, surface active compounds of the type listed in Table I can be employed during the preparation of a polymer. To illustrate, a solution of 4 ml. of surface active compound No. 9 of Table I in 365 ml. of distilled water purged with nitrogen is heated to 94 C. To this solution is added 1.0 g. of potassium persulfate and 0.1 g. of sodium bisulfite. Immediately after this addition there is begun the simultaneous addition of the following two solutions:

(a) 114 g. of butyl acrylate and 5.0 g. Z-acetoacetoxyethyl methacrylate.

(b) 6 g. of acryloyloxypropane sulfonic acid sodium salt, 4 ml. of surface active compound No. 9 of Table I, and 0.2 g. of sodium bisulfite in ml. of nitrogen-purged water.

This addition is completed in ten minutes with the reaction temperature being maintained in the range of 93-97 C. Stirring and heating are continued for several minutes to complete the polymerization and to destory residual catalyst. The resulting latex contains copoly (butyl acrylate sodium acryloyloxy propane sulfonate-Z-acetoacetoxyethyl methacrylate).

Example 10 The procedure of Example 9 is followed employing the following reactants: 222 g. of methyl acrylate, 12 g. of sodium acryloyloxypropane sulfonate, 16 g. of 2-acetoacetoxyethyl methacrylate, 2.0 g. potassium persulfate, 0.6 g. sodium bisulfite, 16 ml. of surface active compound and a total of 1000 ml. of water. A latex having 19.8% solids and pH 3.5 is obtained. This latex is adjusted to pH 5.0 with dilute sodium hydroxide before coating in photographic materials. The latex comprises coply(methyl acrylate sodium acryloyloxypropane sulfonate 2 acetoacetoxyethylmethacrylate) Example 11 To a solution of 2 ml. of Triton 770 in 190 ml. of water at 95 C. is added 0.5 g. of potassium persulfate and 0.05 g. sodium bisulfite. Immediately thereafter there is added simultaneously the following two solutions over a period of ten minutes:

(a) 47.5 g. of methyl acrylate, 12.0 grams of acrylic acid and 3.13 g. of Z-methacryloyloxyethyl cyanoacetate.

(b) 2 milliliters of Triton 770 and 0.1 g. of sodium bisulfite in '60 m1. of water.

After twenty minutes additional heating, the latex is cooled, diluted with an equal volume of water and converted to a solution at pH 6.5 by the addition of 10% sodium hydroxide solution.

Example 12 As previously indicated, interpolymers containing active methylene groups in the side chains can be incorporated into photographic materials to improve resistance to abrasion. To illustrate, copoly(methyl acrylate/ sodium 3- acryloyloxy-l methylpropane-l sulfonate/Z-acetoacetoxyethyl acrylate) latex of Example 6, is incorporated into a fine grain silver chlorobromide emulsion (80 mole percent chloride). The emulsion contains 70 g. of gelatin and 70 g. of copolymer per mole of silver halide. The emulsion is coated on conventional polyester film support at a silver coverage of 412 mg./ft. of support (Coating 1) with formaldehyde hardening agent. For comparison purposes copoly(methyl acrylate-sodium 3-acryloyloxypropane-1- sulfonate) (95:5 weight percent) is incorporated into another sample of the emulsion and coated in the same manner (Coating 2). The coatings are exposed on an Eastman 1b sensitometer, developed in Kodak DK-SO developer for approximately minutes at 68 F., fixed in Kodak F-5 fix for approximately minutes and washed.

The resistance to abrasion for the coatings is determined by drawing a pointed stylus under constant pressure across the surface of the coating which is wet with developer, fix or wash water. The resistance to abrasion is rated as follows:

(1) The coating is easily punctured by the stylus and easily tears away from the support.

(2) The coating is punctured by the stylus and tears away from the support with little difliculty.

(3) The coating is punctured by the stylus and scratches away from the support with some difiiculty.

(4) The coating is not punctured by the stylus and will not scratch away from the support.

The results obtained with the above coatings are as follows:

Similar good resistance to abrasion is exhibited when copoly(butyl acrylate-acrylic acid-2-acetoacetoxyethyl acrylate), copoly(ethyl acrylate-acrylic acid-Z-acetoacetoxyethyl methacrylate) copoly(methyl acrylate-acrylic acid-ethyl u-acetoacetoxymethyl acrylate) and copoly- (acrylamide-2 acetoacetoxyethyl methacrylate) (:10, weight percent) as described herein, are used in the binding agent in the above procedure. Furthermore, each of the coatings show improved dimensional stability in comparison to coatings employing gelatin as the sole binding material.

Example 13 The use of the interpolymers described herein in photographic materials has no substantial adverse effect on photographic properties. To illustrate, copoly(methyl acrylate-sodium 3 acryloyloxypropane 1 sulfonate-2- acetoacetoxyethyl methacrylate) latex of Example 10 is incorporated into a portion of a coarse grain gelatin, silver bromoiodide emulsion which is panchromatically sensitized. The emulsion portion is coated (Coating B) on conventional cellulose acetate film support at a coverage of 460 mg. of silver and 1040 mg. of gelatin/ft. of support. For comparison purposes, another portion of the emulsion containing no copolymer is coated in the same manner (Coating A).

Each film coating is exposed on an Eastman 1b sensitometer, developed for 5 minutes in Kodak DK-50 developer, fixed, washed and dried. The photographic speed, gamma and fog are as follows:

The interpolymers described herein can be used in layers other than photographic silver halide emulsion layers. To illustrate, copoly(methyl acrylate-sodium-3-acryloyloxypropane 1 sulfonate 2 acetoacetoxyethyl methacrylate) latex, prepared according to Example 10, and copoly(butyl acrylate-sodium-3-acryloyloxypropane 1- sulfonate 2 acetoacetoxyethyl methacrylate) latex, prepared according to Example 9, are mixed with an equal quantity of gelatin and coated on a conventional polyester film support at 674 mg. of vehicle per square foot of support. These coatings are designated 4 and 8, respectively, in the following table. For comparison purposes, coatings are prepared using copoly(methyl acrylate sodium 3 acryloyloxypropane 1 sulfonate) (:5 wt. percent), (designated Coatings 1-3 below) and copoly(butyl acrylate sodium 3 acryloyloxypropanel-sulfonate) (95:5 Wt. percent) (designated Coatings 5-7 below) in place of the copolymers in Coatings 4 and 8. All coatings contain formaldehyde hardener.

The coatings are immersed in Kodak DK-50 developer (2 minutes), Kodak F-5 Fix (3 minutes) and wash water (10 minutes). The resistance to abrasion is determined using the procedure of Example 12. The results are as follows:

Formaldehyde (percent by Resistance to abrasion welght, based on Coating total vehicle) Developer Fix Wash Formaldehyde, Resistance to abrasion gJlOO g. of Coating gelatin (dry wt.) Developer Fix Wash 13 modifications can be efiected without departing from the spirit and scope of the invention.

I claim: 1. A compound having the formula:

where R, is a hydrogen atom, an alkyl group containing up to 12 carbon atoms, or

wherein R is an alkylene group containing up to 10 carbon atoms and X is alkylcarbonyl containing up to 8 carbon atoms, provided that one and only one of R and R is always ti Rto-ooH2X 2. A compound according to claim 1 wherein X is an acetyl group.

3. A compound according to claim 1 wherein R is an ethylene group.

4. A compound having the formula:

wherein R is an alkylene group containing up to 10 carbon atoms, R is a hydrogen atom or an alkyl group containing up to 12 carbon atoms and X is an alkylcarbonyl group containing up to 8 carbon atoms. 5. A compound having the formula:

6 CH2=CCOR5 wherein R is an alkyl group containing up to 10 carbon atoms, a cycloalkyl group containing up to 10 carbon atoms or a phenyl group, R i an alkylene group containing up to 10 carbon atoms, and X is an alkylcarbonyl group containing up to 8 carbon atoms.

6. 2-acetoacetoxyethyl acrylate.

7. 2-acetoacetoxyethyl methacrylate.

8. Ethyl a-acetoacetoxymethyl acrylate.

References Cited UNITED STATES PATENTS 8/1954 Wesp et a1. 260--465.4 X

JOSEPH P. BRUST, Primary Examiner S. T. LAWRENCE, Assistant Examiner US. Cl. X.R.

zigz g? UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent -3.169.790 Dated ugust i. 1969 Inventofl Donald Arthur Smith It is certified that error appears in the above-identified patent and that said Letrers Patent are hereby corrected as shown below:

r- Column 2, lines 1-2, "monmeric" should read --monomeric--.

Column 3, lines 21-214., formula reading 0 SHOULD READ O I! H -C-CH -CH -C-CH -CN line 1+7, "prepartd" should read --prepared line 59, "monomrs" should read monomers--; lines 70-71, "N-vinylpyrazolidone" should read N-vinylpyrrazolidone Column l lines 12-114., formula readlng 9 9 CHZZCYLC-O-RB-SO3M should read CH2=C-C-O-R3SO3M Column 7, line 31, after coating", should read Column 9, line 39, "maxmium" should read -rnaximum--. Column 11, line 1, "destory" should read --destroy--; line 15, "coply(methyl" should read copolyhnethyl SIG NED AND SEALED APR281970 (SEAL) Attest:

Edward M. Fletcher, 1:. x mm JR WILLIAM E. CI

L Attesnng Officer Commissioner of Patanta

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Classifications
U.S. Classification560/178, 558/442, 430/510, 430/281.1, 560/130, 558/400, 560/220, 560/205, 554/122, 560/174, 430/527, 526/318, 568/608, 526/298, 554/223, 526/321, 524/24, 526/319, 526/287
International ClassificationG03C8/00, C08F2/22, C07C69/54, C08F12/22, G03C1/053, G03C8/02, G03C1/06, C08F220/10, C08F20/28, C08F220/18, G03C1/76, C08F220/12, C09D133/06, G03C8/28
Cooperative ClassificationG03C1/76, C08F20/28, C07C255/00, C09D133/062, G03C8/00, G03C8/02, C08F220/12, G03C8/28, G03C1/053
European ClassificationC07C255/00, G03C1/76, C08F20/28, G03C8/00, G03C1/053, G03C8/02, G03C8/28, C09D133/06B, C08F220/12