US3340806A

US3340806A - Premordanted imbibition dye printing blank

Info

Publication number: US3340806A
Application number: US568142A
Authority: US
Inventors: Weyerts Walter John
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1966-07-27
Filing date: 1966-07-27
Publication date: 1967-09-12
Anticipated expiration: 1984-09-12
Also published as: BE701699A; GB1195255A; DE1671538B1

Description

United States Patent of New Jersey No Drawing. Filed July 27, 1966, Ser. No. 568,142

25 Claims. (Cl. 101-450) layer, thereafter removing the colloid from the support in the regions not exposed by light. The resultant colloid relief image is then dyed. The element obtained is referred to as a matrix. The dye image of the matrix is transferred to a blank by imbibition. The blank comprises a support having a colloid coating containing mordant. In this manner, subtractively color dye images may be obtained which faithfully reproduce a colored subject.

When using blanks containing diffusible basic mordants, there appears to be a tendency for the mordant or constituents thereof, to diffuse out of the blank into the matrix. The result is that as repeated dye transfers are made from a given matrix, more mordant diffuses from the blank into the matrix, combines with some of the dye and is held there. The matrix then takes up more dye than it should when it is re-dyed. When a transfer is made from the re-dyed matrix more dye is imbibed onto the blank than originally and the color balance of a print is seriously altered. After a number of transfers, the matrix may become clogged resulting in a drop in the higher densities with repeated transfers. This problem is referred to herein as matrix poisoning. A further result is that since the diffusible constituents of the blank appear to diffuse back not only into the matrix but also are adsorbed by the bared areas of the matrix support representing the highlights of the picture, the final print contains undesirable dye density in the highlight region.

Previously it has been suggested to apply acidic polymers over the surface of mordanted blanks to avoid the problems noted above. However, the specific acidic polymers proposed have caused either sticking or slipping between the matrix and blank, or have resulting in undesirably low dye transfer definition or density after successive transfers. It therefore appears highly desirable to provide a class of materials which effectively prevent matrix poisoning, and which do not cause undesirable sticking or slipping between the matrix and blank, and which further provide good dye transfer definition and density after several successive transfers.

One object if this invention is to provide improved, novel blanks. Another object of this invention is to provide improved, novel imbibition blanks which are treated to prevent matrix poisoning. Still another object of this invention is to provide imbibition blanks treated to substantially eliminate mordant diffusion. Another'object of this invention is to provide novel imbibition blanks which do not stick or slip when pressed against a matrix film. A further object of this invention is to provide imbibition blanks which give good dye density and transfer definition, even after a number of transfers. Still another object of this invention is to provide a process for preparing such improved imbibition blanks. Another object of this invention is to provide an improved relief imbibition printing process. Other objects of this in- Patented Sept. 12, 1967 ice vention will be apparent from the following disclosure and the appended claims.

In accordance with one embodiment of this invention,

of the invention. At the same time, good dye transfer definition and density are obtained without problems of sticking or slipping.

In another embodiment of the invention, an improvement is provided in a relief imbibition printing process that includes transfer of a soluble acid dyestutf from a colloid relief image to a colloid blank containing a diffusible, basic mordant and fixing the dyestuff in the blank. This improvement features treating the surface of the blank with certain sulfated or sulfonated compounds defined more fully below.

In still another embodiment of this invention, the definition of the transferred dye image is improved by contacting the surface of the colloid relief image with an acid prior to contact with the colloid blank which has been treated with sulfonated or sulfated compound in accordance with this invention.

In a further embodiment of this invention, the novel blanks and processes of this invention are further characterized by employing a combination of sulfated or sulfonated compound together with an acid salt of an alkyl or aryl substituted polyalkoxy ether. It has been found that this combination effectively prevents occurrence of any scummy film on blanks after dye transfer. This scummy fil-m sometimes appears when certain less Water soluble sulfated or sulfonated compounds are employed in accordance withthis invention. The scum can be prevented by the addition of certain ionic or non-ionic wetting agents. I

The compounds which may be employed in this invention include the sulfated or sulfonated derivatives of monomeric esters or carboxylic acid amides (the carboxyl groups of which can be esterified) which contain ballasting substituents to prevent diffusion of the compound through hydrophilic colloids. Advantageously, the compounds employed herein are sulfated or sulfonated derivatives of 1) A monomeric ester formed from a polycarboxylic acid and an alcohol;

(2) A monomeric ester formed from a polyol and a monocarboxylic acid; or,

(3) A polycarboxylic acid amide, which compounds contain at least one free unesterified acid group and a ballasting substituent. Preferably, the ballasting substituents of the present compounds include at least one alkyl or alkenyl radical containing from 5 to 30, and preferably from 8 to 18 carbon atoms. When the compound used is an ester formed from a polycarboxylic acid and an alcohol, the alcohol portion of ester advantageously comprises'an alkyl or alkenyl radical having a chain length sufiicient to provide ballasting. Similarly, in esters formed from a polyol and a monocarboxylic acid, the acid portion of the ester contains an alkyl or alkenyl radical having a chain length suflicient to provide ballasting. The esters can be mono, di or tri esters. When the compound employed is a polycarboxylic acid amide, it advantageously contains an N-alkyl or N-alkenyl substituent to provide ballasting. The carboxyl groups can be esterified.

The free, unesterified acid substituent in the above compounds can be either a carboxylic acid substituent, a sulfonic acid substituent or a sulfate group. Salts of these acids are useful, such as the alkaline earth or alkali metal salts. The polycarboxylic acids useful in forming esters operable herein include a wide variety of common diand tri-carboxylic acids, generally containing a total of 4 to 6 carbon atoms, such as maleic, succinic, fumaric, tricarballylic, citraconic, mesaconic, and aconitic acids. At least one alcohol portion of such esters, as indicated above, can contain from to 30, and preferably from 8 to 18 carbon atoms. Typical useful alcohols which can be used to form the esters include l-octanol, l-tridecylol, etc.

Monomeric esters formed from a polyol and a monocarboxylic acid, which are useful in this invention, are advantageously formed from polyols containing from 2 to 4 hydroxyl groups and at least one carboxylic acid having a carbon chain, which may be unsaturated, containing from 5 to 30, and preferably 8 to 18 carbon atoms. Typical useful acids include lauric, tridecanoic, palmitic, etc. Representative useful polyols are glycerol, 1,4-butanediol, 1,3-propanediol, etc.

Acid amides useful in this invention can be prepared from the same polycarboxylic acids referred to above, and advantageously contain an N-alkyl or an N-alkenyl substituent of 5 to 30, or preferably 8 to 18 carbon atoms. The carboxyl substituents (one or all) of these compounds can be esterified, such as with alcohols containing up to 30 carbon atoms.

The most useful compounds in accordance with this invention are the sulfonic acid substituted mono-, diand triesters of polycarboxylic acid containing from 2 to 3 carboxyl groups, the alcohol portion of such esters being composed of a radical containing from 8 to 18 carbon atoms.

The following specific compounds are representative of the useful sulfonated or sulfated compounds useful in the practice of the present invention: dioctyl ester of sulfo-succinic acid, sodium salt; di-tridecyl sodium sulfosuccinate; sulfonated polyester commercially available as Nekal WS21 and Nekal WS-25 (General Dyestuff Corp); tetrasodium N-octadecyl, N-(1,2-dicarboxylethyl)sulfosuccinamate; a complex fatty acid derivative of an aliphatic sulfonate commercially available as Emcol 4150 (Witco Chemical Co.), disodium N-octadecyl sulfosuccinamate; and, sulfoacetates of monoor diglycerides, e.g., a compound having the following formula:

The sulfated or sulfonated compounds employed in this invention can be applied to mordanted blanks in any convenient solution or dispersion. Best results are obtained with aqueous solutions or dispersions adjusted to pH of about 4.0 to 5.0 using concentrations of about .05 to about 1.5 weight percent sulfated or sulfonated compound. Complete solution of the sulfated or sulfonated compound is not required. Good results are obtained with dispersions.

Solubility, or dispersibility can be increased with the usual non-ionic wetting agents, such as alkylated aryl polyether alcohol (Triton X100) or sorbitan monolaurate polyoxyethylene (Tween 20'). A scummy film on the blank occurs under given conditions with certain of the sulfated or sulfonated compounds used herein. This film can be avoided by using, in combination with such compounds, and in a concentration effective to prevent scumming, the acid salts of an alkyl or aryl substituted polyalkoxy ethers, such as the alkali metal and ammonium sulfate, sulfonate and carboxylic acid salts of alkyl substituted polyalkoxy ethers. Good results are obtained with such salts which have from 1 to 100, and preferably 1 to 5 alkoxy groups, each alkoxy group containing from 2 to 4 carbon atoms. An especially useful class of compounds are acid salts of polyalkoxyalkyl substituted aryl ethers. Preferred aryl groups are phenyl and naphthyl. The most useful class of acid salts employed in the invention has the following general formula:

wherein R represents hydrogen or a straight or branched chain alkyl substituent (including substituted alkyl and alkoxy) containing from 1 to 30, and preferably from 4 to 16 carbon atoms such as butyl, butoxy, pentoxy, amyl, hexyl, heptyl, p-tertiary octyl, nonyl, decyl, decyloxy, dodecyl, pentadecyl and triacontanyl; n represents an integer of from 1 to 100, and preferably 1 to 5; B represents an aryl nucleus, such as phenyl or naphthyl; m represents a positive integer of from 1 to 2; and, X represents an acid salt selected from the group consisting of the sulfate, sulfonate and carboxylic acid alkali metal, triethanolamine, and ammonium salts. When In is 1, R is an alkyl substituent. Generally, solutions containing from .05 to about 1.5 percent by weight of such compounds effectively prevent the scummy film.

The following acid salts of substituted polyalkoxy ethers are useful in this invention: Stepanol B129, nonylphenoxypolyethylene oxide sulfate, sodium salt; Stepanol B153, ammonium alkylphenoxypolyoxyethylene sulfate; Steol 4N, ethoxylated fatty alcohol sulfate where the fatty alcohol base is lauryl alcohol and the cation is sodium; Steol 4T, same as 4N except cation is triethanolamine; Steol CS460, same as 4N except fatty alcohol is stripped coconut; Steol CA460, same as CS-460 except cation is ammonium salt; Triton 770, sodium salt of ptert octylphenoxy (ethoxy) -ethyl sulfate; Triton W-30, sodium salt of an alkylarylpolyether sulfate; Triton X 202, sodium salt of alkylarylpolyether sulfate; Triton X-301, sodium salt of an alkylarylpolyether sulfate; Triton X200, p-tert-octylphenoxy ethoxy ethyl sulfonate sodium salt; Sipon ES, sodium lauryl polyethoxy sulfate; Sipon EA, ammonium lauryl polyethoxy sulfate; Sipex EST, sodium salt of tridecyl ether sulfate; Sipex EA, ammonium salt of a lauryl polyethoxy sulfate; Cellopal 40, polyethoxyalkylphenol sulfonate, sodium salt; Cellopal 100, polyethoxyalkylphenol sulfonate, triethanolamine salt; Alipal CO433, sodium salt of a sulfate ester of an alkylphenoxy-poly(ethyleneoxy)ethanol; Alipal CO- 436, same as CO433 except ammonium salt; Alipal E0- 526, sodium salt of a sulfated alkylphenoxypoly(ethyleneoxy)ethanol; Alipal 10-436, ammonium salt of a sulfated straight chain-alkylphenoxypoly(ethyleneoxy)ethanol; Sulfotex BTS, straight-chain-alkylphenolethoxylate sulfo salt; Sulfotex DHS, sulfated alkylphenolethoxylate; Sulfotex LMT, fatty alkylethoxylate sulfo salt; Sulfotex NTS, sulfated alkylphenolethoxylate. The preferred compounds are the soluble salts of p-tert.-octyl-phenoxyethyl sulfonate; nonyl phenoxypolyethoxide sulfate and laurylpolyethoxy sulfate.

Especially good transfer dye image definition is achieved without loss in transfer dye density, when the dyed matrix is bathed in acidic solutions prior to contact with blanks treated in accordance with the invention. A wide variety of acids may be used, such as acetic, sulfamic, sulfuric, etc. Dilute aqueous acidic solutions are preferred, such as .5 to 1 weight percent aqueous sulfuric acid solutions. Residence time for effective improvement in definition depends on concentrations of acid, but generally is quite short. Contact times of a few seconds, such as 3 to 10 seconds, are generally sufficient. The acid is preferably uniformly distributed on the matrix, and any excess is removed, e.g., with an air squeegee, prior to contact with the blank.

The invention will be more clearly understood from the following description. Low molecular Weight mordant particles wander out of the gelatin layer of the blank and diffuse into the dye relief image of the matrix when the blank and matrix are contacted to permit dye transfer or imbibition. As mentioned, this diffusion may clog the relief image, and adsorbed mordant on the matrix surface results in staining the highlight region of the print.

When the blanks of the invention are substituted for untreated blanks, the defects attributed to mordant diffusion are avoided. The blank is conveniently prepared by mordanting the colloid layer with a suitable basic mordant. For example, the mordant is dispersed in a suitable quantity of colloid, such as gelatin with hardener and coated on a support. Thereafter, the blank is bathed for a short time in a solution of sulfated or sulfonated compound in accordance with the invention. The pH of the solution is adjusted to about 4.0 to 5.0 (e.g., with sodium hydroxide solution). If desired, the sulfonated or sulfated compound may be coated over the colloid surface from such a solution which may in addition contain a vehicle such as gelatin. This treatment of the blank appears to deposit the compound in high concentration as a coating or in an outer stratum of the blank. When such blanks are used for receiving transfers of dye images from dyed relief images, photographic quality is improved. The diffusible mordant particles are effectively prevented or in hibited from diffusing to the matrix. The dye molecules in the matrix transfer undisturbed and are fixed on mordant particles in the blank by reaction therewith.

This invention is applicable to dye imbibition blanks containing any basic mordant. Typical useful basic mordants are described in Sprague et al. US. Patents 2,548,- 564 and 2,484,430. Especially useful basic mordants are described in Minsk US. Patent 2,882,156, issued Apr. 14, 1959. The mordants described in the Minsk patent are derived from carbonyl-containing polymers and aminoguanidi-ne, such as a vinyl polymer containing from about 30-90% by weight of the recurring unit having the structure:

wherein n represents or 1, R represents a hydrogen atom or an alkyl group of from 1 to 4 carbon atoms and X represents the acid radical of an inorganic acid such as hydrochloric acid or an organic acid such as lactic acid, glycolic acid, alkanesulfonic acids containing from 1 t0 4 carbon atoms such as methanesulfonic acid, n-butanesulfonic acid, etc. or of a monobasic saturated aliphatic carboxylic acid containing from 2 to 4 carbon atoms such as acetic, propionic or butyric acids, the remaining 70 to 10% of the resin molecule being unreacted vinyl oxocompound, for example, acrolein, v-methyl acrolein or vinyl alkyl ketone or combinations of these with styrene or an alkyl methacrylate in the proportions of from about 10-15% by weight of the unreacted vinyl oxo-compound to from about 90-85% by weight of the styrene or alkyl methacrylate, where the starting copolymer contains these components in about a 1:1 molar ratio.

Mordanted blanks treated in accordance with this invention are useful for receiving acid dyes from hydrophilic colloid relief images according to prior art techniques. Any suitable acid dyestulf may be transferred to the treated blanks of the invention, such as Anthracene Yellow GR (400% pure Schultz No. 177), Fast Red S Conc. (Colour Index 176), Pontacyl Green SN Ex. (Colour Index 737), Acid Blue Black (Colour Index 246), Acid Magenta 0 (Colour Index 692), Naphthol Green B Conc. (Colour Index 5), Brilliant Paper Yellow Ex. Conc. 125% (Colour Index 364), Tartrazine (Colour Index 640), Metanil Yellow Conc. (Colour Index 138), Pontacyl Carmine 63 Ex. Conc. (Colour Index 57), Pontacyl Soarlet R Conc. (Colour Index 487) and Pontacyl Rubine R Ex. Conc. (Colour Index 179).

Gelatin and other hydrophilic colloids can be employed in the blanks of the invention, such as polyvinyl alcohol and any of the colloids (or dispersing agents) referred to in Beavers US. Patent 3,039,873, issued June 19, 1962, column 13.

This invention will be further illustrated by the following examples. Examples 1 through 8 demonstrate the superior results achieved using the dye imbibition printing processes and materials in accordance with the invention.

EXAMPLE 1 Dye imbibition blanks were prepared by soaking 454 g. of gelatin in 5360 cc. of distilled water until well swollen, and the mixture then heated to 40 C. to dissolve the gelatin. There were then added some saponin solution as a coating aid, 65 cc. of 50% aqueous glycerine and g. of a 10% solution of the resinous mordant produced according to Example 1 of Minsk US. Patent 2,882,156 (issued Apr. 14, 1959), in dilute acetic acid. The pH of the mixture was adjusted to approximately 4.2 and 27 cc. of 10% formaldehyde solution was added. The resulting solution was coated onto a cellulose acetate film support at the rate of approximately 1.25 g. of gelatin (dry weight) per square foot. The blanks thus obtained were prewet for one minute in distilled water, and the excess water was blown off by means of an air squeegee. The blanks were then dipped for approximately 3 seconds in a solution of 1.0 percent (active agent) of dioctyl ester of sulfosuccinic acid, sodium salt, plus 0.5 percent citric acid, with the pH of the solution adjusted to 4.2 with sodium hydroxide. A series of six transfers were made to these blanks using a gelatin relief matrix containing an acid yellow dyestuff (e.g., Anthracene Yellow GR, Schultz No. 177). The yellow dye stain in the minimum density areas of the matrix after the six transfers was only 0.03; measured through an appropriate blue filter. Stain of the matrix is expressed as the difference in minimum density areas of the used and an unused matrix, measured through a blue filter. There was no loss of dye transfer density and the definition was better, than transfer made with a control. In a control experiment, the same imbibition blank was employed but the process was altered by omitting treatment with the aqueous sulfonated compound solution. The yellow dye stain in the control was 0.12.

EXAMPLE 2 The procedure of Example 1 was followed except that after the prewetting treatment in distilled water, the blanks were dipped for approximately 3 seconds in a 0.25 percent aqueous solution-dispersion of di-tridecyl sodium sulfosuccinate at. a pH of 4.2. After six transfers as in Example 1, the yelow dye stain in the matrix was less than 0.01.

EXAMPLE 3 The procedure of Example 2 was repeated, except that the solution dispersion in which the blanks were dipped also contained 0.25 percent sodium laurylpolyethoxy sulfate (Sipon-ES, manufactured by Wrolac Chemical Corp). Again, the dye stain in the matrix, after six transfers, was less than 0.01. However, the scummy film which appeared on the dyed blanks obtained in Example 1 was eliminated due to the presence of the acid salt of the polyalkoxy ether sulfate.

EXAMPLE 4 The procedure of Example 1 was repeated except that the active ingredients employed in the-solution was a sulfonated polyester (Nekal WS-21 in one sample, Nekal WS-25 in another sample, both compounds manufactured by General Dyestuff Corp.) at a concentration of 0.5 percent. The yellow dye stain after six transfers in the matrix used in dying blanks treated with either sample was less than 0.01.

7 EXAMPLE The procedure of Example 4 was repeated except that the active ingredient in the solution was tetrasodium N- octadecyl, N-(1,2-dicarboxyethyl) sulfosuccinamate at a concentration of 0.25 percent by weight. Again, after six transfers, yellow dye stain in the matrix was less than 0.01.

EXAMPLE 6' The procedure of Example 5 was repeated except that the acid dye used in the matrix was an acid magenta dyestuif (e.g., Acid Magenta 0, CI 692); the solution in which the blanks were dipped contained 0.3 percent by weight tetrasodium N-octadecyl, N-(1,2-dicarboxyethyl) sulfosuccinamate and 0.3 percent by weight acetic acid. Matrix stain (determined as in Example 1 but using a green filter) after six transfers was less than 0.01. Control was 0.06.

EXAMPLE 7 A matrix was prepared as in Example 6 using an acid magenta dye. The matrix after dyeing was rinsed 15 sec- .onds in running water, air squeegeed and the dye was transferred to a blank. The blank was prepared for receiving the transfer by dipping in an acid stop bath (pH 4.2) for 16 seconds washing in running water for 16 seconds, and dipped in distilled water for 45 seconds. Just before the transfer operation, the blanks were squeegeed and dipped for 3 seconds in an aqueous solution containing by weight 0.1% di-tridecyl sodium sulfosuccinate, 0.5 percent sodium laurylpolyethoxysulfate (Sipon-ES, Alcolac Chemical Corp.) and 0.3 percent acetic acid. After 6 transfers, the matrix stain (measured through a green filter) was less than 0.01. With this treatment, generally no further treatment of the blanks is required after the first dye is transferred.

EXAMPLE 8 The procedure of Example 7 was repeated except that the matrix, just before each transfer operation, was rinsed for 5 seconds in a 0.1 percent aqueous sulfuric acid solution and air squeegeed to remove excess surface acid before transferring. Again, the matrix stain was less than 0.01. However, there was an unexpectedly significant improvement, readily visible, in the definition of the transferred image. The acid treatment of the dyed matrix produces this improved definition. This treatment also improves definition of other dyes, such as yellow and cyan.

The following examples show the unsatisfactory results obtained when imbibition blanks are treated with the polymeric acids proposed in the prior art.

- EXAMPLE 9 The procedure of Example 1 was followed except that after the blank was prewet with water, it was dipped for approximately 3 seconds in a 1 percent solution of sodium polyacrylate at a pH of 4.2. The matrix stain after six transfers was reduced to only 0.09 density. Higher concentrations of sodium polyacrylate were viscous and slippery and caused trouble in transfer operations, such as bad sticking between matrices and blanks.

EXAMPLE 10 The procedure of Example 9 was followed except that the blank was dipped, after being prewet with water, in a 1 percent solution (pH 4.2) of low viscosity carboxymethyl cellulose. Matrix stain after six transfers of yellow dye was 0.04 density. However, the images obtained had a much lower transfer definition than those obtained in accordance with Example 1.

EXAMPLE 1 l The procedure of Example 10 was followed except that the blank was dipped, after being prewet with water, in a one percent solution of a sulfionated polystyrene (Lustrex 770). After six transfers, the matrix stain was 0.03,

but there was an undesirable lowering of transfer density with each successive transfer.

The unobvious nature of the present invention is further illustrated by the fact that closely related compounds, such as aryl sulfonic a-cids or alkali metal sulfates (e.g., sodium sulfate) cannot be satisfactorily used in the dye imbibition process to prevent matrix poisoning. Aryl sulfonic acids cause an undesirable reduction in dye density in the transferred image, and alkali metal sulfate fail to prevent matrix poisoning.

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 described hereinabove and in the appended claims.

I claim:

1. A dye imbibition blank comprising a support having coated thereon a hydrophilic colloid layer containing a basic mordant which tends to diffuse through said colloid, at least the outer stratum of said colloid layer containing, in a quantity effective to prevent diffusion of the mordant rout of said colloid layer, a compound selected from the group consisting of the sulfated and the sulfonated derivatives of monomeric esters and carboxylic acid amides, said compound containing an alkyl or alkenyl radical having from 5 to 30 carbon atoms to prevent diffusion =of said compound through the hydrophilic colloid, and said compound containing at least one free, unesterified acid group.

2. The dye imbibition blank of claim 1 wherein said monomeric ester is selected from the group consisting of (1) esters formed from a polycarboxylic acid containing from 2 to 3 carboxyl groups, and an alcohol containing from 5 to 30 carbon atoms, and (2) esters formed from a polyol containing from 2 to 4 hydroxyl groups and a carboxylic acid containing from 5 to 30 carbon atoms; and, said carboxylic acid amide c-ontains a substituent on the amido nitrogen atom selected from the group consisting of alkyl and alkenyl substituents containing from 5 to 30 carbon atoms.

3. The dye imbibition blank of claim 1 wherein said compound is a sulfonated derivative of a monomeric ester selected from the group consisting of the mono-, diand tri-esters formed from a polycarboxylic acid containing three carboxyl groups and an alcohol containing from 8 to 18 carbon atoms.

4. The dye imbibition blank of claim 2 wherein said basic mordant is a vinyl polymer compound consisting of from 50-85% by weight of a recurring structural unit represented by the following general structure:

wherein R represents an alkyl group containing from l-4 carbon atoms and X represents the radical of an acid selected from the group consisting of hydrochloric acid, lactic acid, glycolic acid, and alkanesulfonic acid containing from 1-4 carbon atoms and a monobasic saturated aliphatic carboxylic acid containing from 2-4 carbon atoms, and conversely from 50-15% by weight of a recurring vinyl alkyl ketone unit wherein the alkyl group contains from 1-4 carbon atoms and is the same alkyl radical as the said R radical.

5. The dye imbibition blank of claim 4 wherein said monomeric ester is di-tridecyl sodium sulfosuccinate.

6. The dye imbibition blank of claim 4 wherein said monomeric ester is the di octyl ester of sulfosuccinic acid, sodium salt.

7. The dye imbibition blank of claim 4 wherein said carboxylic acid amide is tetrasodium N-octadecyl, N-(1,2- di-carb oxyethyl sulfosuccinamate.

8. The dye imbibition blank of claim 1 wherein said colloid layer contains, in a concentration sufficient to prevent a scumming film on the dyed blank, an acid salt of an alkyl or aryl substituted polyalkoxy ether, said alkyl group containing from 1 to 30 carbon atoms.

9. The dye imbibition blank of claim 8 wherein said ether is sodium laurylpolyethoxyether sulfate.

10. In a relief imbibition printing process wherein a soluble acid dyestutf is transferred from a colloid relief image to a blank having a colloid coating thereon containing basic mordant which tends to diffuse through said colloid, the process of fixing said dyestutf in the colloid of said blank, and preventing diffusion of mordant from said blank to said colloid relief image, which comprises contacting said colloid relief image with said colloid blank, said colloid blank having on the surface thereof a compound selected from the group consisting of the sulfated and the sulfonated derivatives of monomeric esters and carboxylic acid amides, said compound containing an alkyl or alkenyl radical having from to 30 carbon atoms to prevent diffusion of said compound through the hydrophilic colloid, and said compound containing at least one free, unesterified acid group, said compound being present in a quantity effective to prevent diffusion of the mordant out of said colloid blank.

11. The relief imbibition printing process in accordance with claim wherein said monomeric ester is selected from the group consisting of (l) ester-s formed from a polycarboxylic acid containing from 2 to 3 carboxyl groups, and an alcohol containing from 5 to 30 carbon atoms, and (2) esters formed from a polyol containing from 2 to 4 hydroxyl groups and a carboxylic acid containing from 5 to 30 carbon atoms; and, said carboxylic acid amide contains a substituent on the amide nitrogen atom selected from the group consisting of alkyl and alkenyl substituents containing from 5 to 30 carbon atoms.

12. The relief inbibition printing process in accordance with claim 10 wherein the dyed colloid relief image, prior to contact with said blank, is uniformly contacted with a suflicient quantity of an acid to improve the image definition of the transferred dye without loss in transfer dye density.

13. The relief imbibition printing process in accordance with claim 12 wherein the colloid relief image is contacted with a dilute aqueous solution of sulfuric acid.

14. The relief imbibition printing process of claim 10 wherein said compound is a sulfonated derivative of a monomeric ester selected from the group consistingofthe mono-, diand tri-esters formed from a polycarboxylic acid containing three carboxyl groups and an alcohol containing from 8 to 18 carbon atoms. V

15. The relief imbibition printing process of claim 10 wherein said monomeric ester is di-tridecyl sodium sulfosuccinate.

16. The relief imbibition printing process of claim 10 wherein said monomeric ester is the dioctyl ester of sulfosuccinic acid, sodium salt.

17. The relief imbibition printing process of claim 10 wherein said carboxylic acid amide is tetrasodium N-octadecyl, N-( 1,2-dicarboxyethyl) sulfosuccinamate.

18. The relief imbibition printing process of claim 10 wherein the surface of the colloid coating of said blank, prior to contacting With said colloid relief image, has applied thereto in a concentration sufficient to prevent a scumming film on the dye blank, an acid salt of an alkyl or aryl substituted polyalkoxy ether, said alkyl group containing from 1 to 30 carbon atoms.

19. The relief imbibition process of claim 18 wherein said ether is sodium laurylpolyethoxyether sulfate.

20. The relief imbibition process in accordance with claim 18 wherein the dyed colloid relief image, prior to contact with said blank, is uniformly contacted with a sufficient quantity of an acid to improve the image definition of the transferred dye without loss in transfer dye density.

21. The relief imbibition printing process in accordance with claim 10 wherein said basic mordant is a vinyl polymer compound consisting of from 50-85% by weight wherein R represents an alkyl group contaning from 14 carbon atoms and X represents the radical of an acid selected from the group consisting of hydrochloric acid, lactic acid, glycolic acid, and alk'anesulfonic acid containing from l-4 carbon atoms and a monobasic saturated aliphatic carboxylic acid containing from 2-4 carbon atoms, and conversely from SO -15% by weight of a recurring vinyl alkyl ketone unit wherein the alkyl group contains from 1-4 carbon atoms and is the same alkyl radical as the said R radical.

22. The relief imbibition printing process in accordance with claim 12 wherein said basic mordant is a vinyl polymer compound consisting of from 50-85% by weight of a recurring structural unit represented by the following general structure.

wherein R represents an alkyl group containing from 1-4 carbon atoms and X represents the radical of an acid selected from the group consisting of hydrochloric acid, lactic acid, glycolic acid, and alkanesulfonic acid containing from 1-4 carbon atoms and a monobasic saturated aliphatic carboxylic acid containing from 2-4 carbon atoms, and conversely from 50-15% by weight of a recurring vinyl alkyl ketone unit wherein the alkyl group contains from 1-4 carbon atoms and is the same alkyl radical as the said R radical.

23. In a relief imbibition printing process wherein a soluble acid dyestuff is transferred from a gelatin relief image to a blank having a gelatin coating thereon containing as mordant a vinyl polymer compound consisting of from 50-85% by weight of a recurring structural unit represented by the following general structure:

wherein R represents an alkyl group containing from 1-4 carbon atoms and X represents the radical of an acid selected from the group consisting of hydrochloric acid, lactic acid, glycolic acid, and alkanesulfonic acid containing from 1-4 carbon atoms and a monobasic saturated aliphatic carboxylic acid containing from 2-4 carbon atoms, and conversely from -15 by weight of a recurring vinyl alkyl ketone unit wherein the alkyl group contains from l-4 carbon atoms and is the same alkyl radical as the said R radical, the process of fixing s'aid dyestuif in said blank, and preventing diffusion of said 0 mordant to said gelatin relief image, which comprises (1) bathing said blank for about 3 seconds in an aqueous solution containing from about .05 to about 1.5 percent by weight tetrasodium N-octadecyl-N-(1,2- dicarboxyethyl) sulfosuccinamate, the pH of said solution being adjusted to about 4.0 to 5.0;

(2) bathing said gelatin relief image, which contains soluble acid dyestutf, for about 5 seconds in a 0.1 percent aqueous solution of sulfuric acid; and (3) contacting said gelatin relief image with the gelatin 7 coating on said blank to transfer the acid dyestutf to said gelatin coating on said blank. 24. In a relief imbibition printing process wherein a soluble acid deystutf is transferred from a gelatin relief image to a blank having a gelatin coating thereon containing as mordant a vinyl polymer compound consisting 1 1 of from 50-85% by weight of a recurring structural unit represented by the folowing general structure:

wherein R represents an alkyl group containing from 1-4 carbon atoms and X represents the radical of an acid selected from the group consisting of hydrochloric acid, lactic acid, glycolic acid, and alkanesulfonic acid containing from 1-4 carbon atoms and a monobasic saturated aliphatic carboxylic acid containing from 2-4 carbon atoms, and conversely from 50-15% by weight of a recurring vinyl alkyl ketone unit wherein the alkyl group contains from 1-4 carbon atoms and is the same alkyl radical as the said R radical, the process of fixing said dyestuif in said blank, and preventing difiusion of said mordant to said gelatin relief image, which comprises (1) bathing said blank for about 3 seconds in an aqueous solution containing (a) from about .05 to about 1.5 percent by weight of bis-tridecyl sodium sulfosuccinate and (b) from about .05 to about 1.5 percent by weight sodium lauryl-polyethoxy sulfate, the

12 pH of said solution being adjusted-to about 4.0 to 5.0;

(2) bathing said gelatin relief image, which contains soluble acid dyestuff, for about 5 seconds in a 0.1 percent aqueous solution of sulfuric acid; and,

(3) contacting said gelatin relief image with the gelatin coating on said blank to transfer the acid dyestuff to said gelatin coating on said blank.

25. The relief imbibition printing process of claim 10 wherein said carboxylic acid amide is disodium N-octadecyl sulfosuccinamate.

References Cited UNITED STATES PATENTS 1,517,200 11/1924 Donisthorpe 101l49.1 2,548,575 4/1951 Weycrts 101149.1 2,821,821 2/1958 Yen 101-149.1 2,882,156 4/1959 Minsk 1O'1149.1

20 ROBERT E. PULFREY, Primary Examiner.

WILLIAM B. PENN, Examiner.

J. A. BELL, Assistant Examiner.

Claims

10. IN A RELIEF IMBIBITION PRINTING PROCESS WHEREIN A SOLUBLE ACID DYESTUFF IS TRANSFERRED FROM A COLLOID RELIEF IMAGE TO A BLANK HAVING A COLLOID COATING THEREON CONTAINING BASIC MORDANT WHICH TENDS TO DIFFUSE THROUGH SAID COLLOID, THE PROCESS OF FIXING SAID DYESTUFF IN THE COLLOID OF SAID BLANK, AND PREVENTING DIFFUSION OF MORDANT FROM SAID BLANK TO SAID COLLOID RELIEF IMAGE, WHICH COMPRISES CONTACTING SAID COLLOID RELIEF IMAGE WITH SAID COLLOID BLANK, SAID COLLOID BLANK HAVING ON THE SURFACE THEREOF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF THE SULFATED AND THE SULFONATED DERIVATIVES OF MONOMERIC ESTERS AND CARBOXYLIC ACID AMIDES, SAID COMPOUND CONTAINING AN ALKYL OR ALKENYL RADICAL HAVING FROM 5 TO 30 CARBON ATOMS TO PREVENT DIFFUSION OF SAID COMPOUND THROUGH THE HYDROPHILIC COLLOID, AND SAID COMPOUND CONTAINING AT LEAST ONE FREE, UNESTERIFIED ACID GROUP, SAID COMPOUND BEING PRESENT IN A QUANTITY EFFECTIVE TO PREVENT DIFFUSION OF THE MORDANT OUT OF SAID COLLOID BLANK.