US2449230A - Liquid printing ink containing a lignin compound - Google Patents

Description

Elmira HQ 9 LIQUID PRINTING INK CONTAINING LIGNIN COMPOUND 1 Clarence E. Irlon, Essex Fells, N. 3., assignor, by

mesne assignments, to Margot Corporation, N ew York, N. 2., a corporation of New York No Drawing. -Application July 25, 1945, Serial No. 607,081

' s Claims. (oi. 10.6-30) and to thesheetmaterIaI to be printed that the provide new and improved printing inks which obviate important limitations or shortcomings of known printing inks. More particularly, this invention is to provide printing inks which are useful for high speed printing of good quality at much less expense than the known inks used for such work. Another object is to improve high speed printing'operations by the provision of printing inks which give the effect of quick drying and form prints of high quality without requiring the forced volatilization of a solvent, or the oxidation or polymerization of a drying oil varnish, or the use of a metallic drier, or the application of a precipitating medium, or the use of heating or other complex or expensive equipment with the printing press.

Another object of my invention is to provide improved printing inks which will produce printed matter of high quality at either high or low printing speeds, and by which prints may be formed having distinct printed characters of desired P"1OI or gloss and free not only from smudging and offsetting but also from the formavention will be set forth particularly in the appended claims.

My invention involves a recognition and utilization of the principle that if printing inks are made with a liquidcarrier and a resinous binder for coloring matter'in such relation to each other binder ordinarily will be held dispersed in the carrier, and that the binder has a strong afllnity for said material and is not skin-forming in nature but freely releases the liquefying component of the carrier to said material upon contact therewith, and that the liquid thus released is readily absorbed or spread out and disseminated by said material, the inks so obtained will form prints of good quality by setting immediately to a smudgeand rub-resistant state equivalent to' dryness, without requiring any further operation.

The inks so made in effect break upon con- 1 tact with the sheet material, such that the [binder and the pigment adhere to the material, without bleeding, as rub-resistant films in the forms of the printing elements from which they were impressed, while the liquefying component is released and quickly disseminated or absorbed away to a harmless state beneath or around these films. The bulk of the liquid thus disseminated from the printed ink bears such a minute relation to the bulk of the sheet material printed that it does not materially affect the quality of the printed matter, and since the printed films immediately attain thequality of dryness the printed matter can beimmediately backed up, folded. stacked, bound or otherwise handled without damage. If it is desired in any particular case, of course, the disseminated liquid or moisture can be largely removed after the printing by allowing it to become volatilized or dissipated by natural processes, or by artificial heating or other treatment.

According to this invention, therefore, printing inks are provided which set quickly by contact with the paper or other fabric being printed. Their liquefying component is released to the paper or fabric, which absorbs or disseminates it from the printed films so as to leave imprints of coloring matter bound to the surface of the paper by a suitably hard, adherent resinous substance. Since this drying action is not dependent upon other treatment, the printing and. immediate handling of the printed matter can be carried out with facility at high printing press speeds. The inks embodying my invention set more rapidly even than conventional newspaper inks, but, in contrast to the poor quality of prints made from at 0pm.

these principles and advantages can be obtained by employing lignin or a derivative or equivalent or lignin having its characteristic molecular structure as an essential resinous substance of the binder for the coloring matter, and dispersing the binder and the coloring matter in a. liquid carrier having a solvating or solubilizing action upon lignin so as to form an ink of the desired body and printing quality.

I have also found that the liquid carrier to be employed can be composed advantageously of a thin liquid or diluent, such as water, which has a distinct amnity for cellulosic material or the like and which alone will not dissolve or disperse enough of the resinous binder to make a printing ink, together with an organic substance. a solubilsynthetic organic polymers possessing the characteristic molecular structure or nucleus of lignin, may be used for the same purpose. The term a lignin from fiber liberation" is used hereinto mean lignin or any of these equivalent substances. The printing and drying qualities of inks using a lignin from fiber liberation .according to my invention are believed to result basically from electrostatic relationships between the lignin from fiber liberation and components of the liquid carrier, on the one hand, and between them and the sheet material upon which the inks are printed, on the other.

Among the known lignins from fiber liberation which have been found satisfactory are lignin in I its various fomis, such as soda, sulphate or other izer for lignin, which is soluble in or miscible with the diluent and which renders the whole carrier capable of taking up and dispersing the binder.

hibited, if to a lesser degree, between lignin from fiber liberation on the one hand and the paper and other sheet materials ordinarily used for printing, on the other. Paper, paperboard and cotton textiles are all cellulosic materials, and so are regenerated cellulose, cellulose acetate, cellulose nitrate and various other substances used for making sheet materials or fabrics. Printing inks employing a .lignin from fiber liberation as a binder according to my invention exhibit the properties required to print well on these materials and also on sheet materials coated with substances which are cellulosic in character or with substances which have a pronounced affinity for paper or like cellulosic material, such as coatings containing clay or other fillers in starch or other base material that adheres to paper.

In addition to its distinct afflnity for or adhesiveness to such sheet materials, a lignin from fiber liberation as'used in inks according to my invention exhibits the further desired properties of permitting free release or migration of liquefying components across the boundaries of the printed ink films to the paper or other sheet material when the inkis printed, of being sufficiently open or non-sealing in nature to permit this dissemination of liquid and avoid skin formation that would entrap the liquid, and yet when printed of forming film-s which are dense, hard and strong enough for high quality printing. Further, the lignin from fiber liberation permits the body or printing consistency of the ink and the gloss or color of the print to be controlled as desired by methods or formulation such as disclosed hereinafter, or by others known to the printing ink art.

The usefulness of lignin for the present purpose is attributable to its characteristic molecular structure, namely, it is an organic polymer containing a multiplicity of hydroxy and methoxy radicals in themacromolecule. Other resinous substances of the same nature, 1. e. natural or lignins derived .from hardwood, softwood,'straw, corncobs or the like and precipitated lignin from waste sulphite. liquor such as lignosulfonates. Others which may be used include lignin complexes, such as methanol lignin, butanol lignin, ethanol lignin, phenol lignin, glycol lignin, acid lignin, reduced lignin, extracted lignin and soda or sulphate lignin products; products derived from wood which consist principally of pyro-lignin or its derivatives; and resinous materials containing lignin, such as certain precipitated wood extracts, enriched wood pulps and other like substances containing lignin structures either naturally or as an addition to other matter. Soda and sulphate lignins are each obtainable in two forms, of which one is a precipitated or water-insoluble lignin and the other is a water-soluble lignin.

To obtain the basic characteristics of the new inks and yet modify their minor qualities to advantage for certain printing .uses, a lignin from fiber liberation may be blended or reacted with other compatible organic plastics or resins, either natural or synthetic. The binder of the ink in such embodiments is a composite resinous substance containing a lignin from fiber liberation. For example, I have found composite substances useful which are made by cooking or fusing a, lignin from fiber limitation with a thermoplastic resin such as gum,,wood rosin, ester gum, Batu gum, damar gum, alkyd-type resins modified by chemical combination with natural resin acids, or the like. In this way the qualities of the films produced by printing the inks may be regulated as to gloss, adhesion to coated papers, water resistance Or the like, or blending may be utilized to regulate the consistency of the ink for difierent methods of printing or difierent printing press speeds.

The liquid carrier of the new inks may be composed of substances selected from a wide variety, although the range of selection for particular formulations may vary with the particular lignin from fiber liberation employed or with particular qualities that may be desired to be emphasized especially in certain inks. In general, the substances useful as solubilizers for dispersing lignins from fiber liberation are organic compounds which exert solvating action upon waro'mfilfm lar structures such as lignin, brmilring lr'iuiii up or dispersing them to a state of solvation by the action of polar groups in molecules of relatively small size as compared with the lignin macromolecules. Of this nature are compounds among the following: amino compounds, including cyclic and alkyl-hydroxy amino compounds and their esters: keto compounds inclu ing amides. lactones. ke ones. lactams a d a dehydes. inc uding hydroxy and methoxy aldehydes: and hydroxy compounds including alkyl nitro-hydroxy comethers and'esters.

' produce printedfllms satisfactorily binding the pigment or other coloring matter to the paper. I have found that water peculiarly meets the rethinness or fluidity and amnityior paper or the like but also has the important advantages of extreme cheapness, non-inflammability and relativestability against chemical action or evaporation on the printing press.-

In embodiments using water as the-diluent, the solubilizer employed may be a watch-miscible organic substance which in water acts as a solvating agent for lignin. In general its structure contains or has the basic character of a substance containing one or more polar groups corresponding to some polar groups contained in lignin. Thus it may be a keto compound, a polyhydroxy compound on a cyclic or alkyl amino compound of the nature stated. i

I have further discovered that particularly desirable inks containing a lignin from fiber liberation as a hinder or bodying substance and water as a carrier component can be produced by the use of alkyl aminohydroxy compounds and esters thereof as solubilizers, such as 2-amino-2- methyl-1, 3-propanediol, 2-amino-2-ethyl-1, 3- propanediol, z-amino z-methyl 1 propanol. 2- amino-2, d-pentanediol, tris (hydroxymethyl) amino methane, and the like. The first and last mentioned of these are normally solids, while the others normally are liquids.

These particular solubilizers facilitate the production oi.smooth, clear dispersions of enough lignin from fiber liberation in water to secure inks having almost any desired printing qualities when colors have been incorporated. They are so eiiective thatthe desired content ofcresinous binder can be dispersed in water, to obtain a dispersion of thin body, by using between about and 20% of the solubilizer. This avoids having the quality of the ink restricted too much by the necessity of using a large proportion of solubiiizer, which would enhance costs and in some cases entail a sacrifice of non-infiammability, gloss, or printing quality. The body or printing consistency of inks using these solubllizers generally can be adjusted to suit the requirements of any particular printing press or type of printing work by regulating the ratio of the solubilizer content to the content of ligninlfrom fiber liberation in the ink. To increase the solubilizer content gives a thinner body with the same content of lignin from fiber liberation.

The following further exemplify s'olubilizers which are useful pursuant hereto in various formulations of inks containing a lignin from fiber liberation: Lactones, such as 4-hydroxy pentanoic acid lactone; aliphatic .ketones, such as acetone and methylethyl ketone; aliphatic alcohols;

such as ethyl alcohol and higher aliphatic alcohols; l,3-ketols or beta-hydroxy ketones, such as 4 hydroxy-4-methyl pentanone; nitro-aliphatic alcohols, such as 2-nitro 2 methyl-l-propanol, Z-nitro-I-butanol, l-nitro-Z-butanol, 2-nitro-lpentanol, 3-nitro-3-methyl-2-pentanol, 2-nitro- 3-hexanol, 3-nltro-4-heptanol and 5-nltro-4-ocas ethylene glycol, dipropylene glycol, etc., ethers all) thereof such as the mono ethyl, mono methyl and mono butyl ethers of diethylene glycol (carbitols) and the corresponding ethers of ethylene lycol (cellosolves); and esters thereof, such as their acetates, propionates, etc.; and alkyl aromatic dicarboxylic acidesters, such as dimethyl quirements. It not onlypossesses the requisite phthalate. 1

A preferred procedure for making the new inks is to mix or dissolve the solubilmer in the diluent to obtain a carrieror solvating liquid, then add the resinous binder and disperse it thoroughly, with the aid of agitation or heat or of'both if desired, and thereafter mill in or otherwise incorporate the coloring matter.

When a strong solubilizer'is employed in the new inks it tends to render the printed ink films insufilciently water resistant for many uses. The lignin from fiber limitation may be washed oil the paper with water, even though not-soluble in water. I have discovered, however, that water resistance can be imparted to the inks when desired by the addition of a waterproofing agent. I have found further that organic compounds may be used as waterproofing agents which fall into several classes, including: First, those having little or no solvating power for lignin which are insoluble in water and yet stay dispersed in an aqueous dispersion of lignin with the aid of a third substance, such as the solubilizer used to eilect dispersion or the lignin; second, those which are soluble in water and havelittle or no solvating power for lignin; and third, those which normally are liquid and have sumcient solvating power for lignin to serve as a dispersing liquid or solubilizer in the carrier of the ink. The useful waterproofing agents are all organic compounds possessing such afllnity for the macromolecules of lignin that they adhere to them aspart of the printed ink films and render those films water resistant. They would precipitate lignin from an aqueous dispersion. thereof if added to such dispersion in unlimited amount.

In the use of such non-solvating compounds as components of water-containing lignin inks, a limited amount of the water proofing'agent between 1 and 20% of the weight of the ink generally is employed. This preferably is added after the lignin from fiber liberation has been dispersed in the aqueous liquid carrier, or during its dispersion, so as to be incorporated with the aid of the solubilizer present.

Where water-containing inks are made to contain waterproofing compounds of the second and third types above-mentioned, the remarkable situation may obtain or having all liquid ingredients of the ink water-like or water soluble .to some degree, and yet of achieving water resistance or water-prooiness in the printed ink films as their liquefying component or carrier is disseminated away by the sheet material printed.

Waterproofing compounds of the third type may constitute substantially the entire liquid carrier of an ink in cases where water is not used; but lignin-containing inks of this type are less useful than the others because they are more expensive and they exhibit slow drying qualities.

Among the organic compounds which Ihave tanol; aliphatic hydroxy and amino :aldehydes containing 6 or less carbon atoms: aldehydeand amino-alcohols; aminc-glycols; hexamethylenefound useful as waterproofing agents are hydroxy .romatic, hydroxy fatty acid, keto and oxime :ompounds'that lack solvent power for lignin.

The compounds useful as waterproofers include, more particularly, beta-hydroxy aldehydes or aldols, glycerol aldehydes, dihydroxy aldehydes, dihydroxy ketones, amino-keto compounds, meth'oxy-keto compounds, hydroxy dialdehydes, dihydroxy aldehyde ketones, hydroxy diketones, dialdehyde ketones and aldehyde diketones; for example, beta hydroxy ethanal, beta-hydroxy propionaldehyde, aldol, glycol acetol. hydroxy lactones, urea, paraformaldehyde,

rier and cause its liquefying component to pene- 1 trate or disseminate faster in the paper or other gammavalerolactone, glyoxal, and methylene disalicylic acid. Such compounds may be monoor poly-hydroxylated, and they may be aliphatic V I or aromatic, depending upon the particular composition desired. Useful aromatichydroxy compounds are the benzene diols, such as 1,3-benzenediol (resorcinol) and 1,4-benzenediol (hydroquinol); also the benzenetriols, such as 1,2,4- benzene triol, pyrogallol and phloroglucinol; also higher homologous benzene derivatives of corresponding structure, such as 1,5-dihydroxynaph thalene, alizarin, anthragallol, rufigallol, vanillin (4-hydroxy-3-methoxy benzaldehyde) and parahydroxyacetophenone; and also methoxy ph'enols, such as hydroquinone monomethyl ether.

According to some embodiments hereof, fast drying inks which form waterproof prints are made by first dispersing water-insoluble lignin in a carrier composed of water and a solubilizer as above mentioned, e. g. an amino-hydroxy compound or a polyhydroxy compound such as ethylene glycol. Then a waterproofer having little or no solvating power for lignin, for example, paraformaldehyde, hydroquinone monomethyl ether, 1,5-dihydroxynaphthalene, p-hydroxyacetophenone, resorcinol, pyrogallol, ruflgallol, anthragallol, methylene disalicylic acid, or anothersuch waterproofer as above mentioned, is incorporated in the dispersion to obtain a vehicle into which the desired pigments are milled or ground.

According to other embodiments, fast drying inks are made with a dispersion of water-soluble lignin in an amino ketone, such as formamide, or a like compound which both disperses the 118- nin and renders the printed ink waterproof, Wa-

ter is added to this dispersion to produce a homogenous vehicle for the ink pigments which has the consistency and the fast drying quality desired in the finished inks.

According to still other embodiments of my invention, an amino ketone such as formamide, to serve in a dual capacity as liquid carrier. and waterproofer, is used to make a dispersion of water-insoluble lignin, and water which otherwise would precipitate this lignin is added in conjunction with an organic solubilizer or couplin'g" agent. The latter preferably is an amine such as the oyclohexylamines, alkylaminoethanolscases, to reduce the surface tension of the car-- sheet material when released from the binder as the ink is printed. Higher molecular polar-nonpolar compounds, such as sulfonated fatty alcohols, long-chain amines, hydrogenated fatty acids or chlorinated alcohols may be used for this purpose; for example, polyoxyalkylene hexanepentol laurate. Y

The new inks may contain various other components or substituents, as may be desired, such as aqueous substances or oils, organic solvents or diluents and-various types of coloring matter. According to some embodiments water soluble lignin is used to take advantage of its limited solubility in water. In other embodiments water insoluble lignin, such as precipitated lignin obtained from hardwood soda black liquor or hardwood sulphate liquor, is employed with a larger proportion of organic solubilizer, to take advantage of its particular qualities.

The following examples illustrate formulations of inks embodying my invention. Precipitated soda lignin and precipitated sulphate lignin can be used interchangeably with little or no change of these formulations.

Example I I Parts by weight Water 47 2-amino-2-methyl-1,3-propanediol 16 Precipitated soda lignin 23 Dieth'ylene glycol monobutyl ether 2 Carbon black 12 This makes an ink of medium body which is noninflammable and does not bleed in oil or paraflln. It is not waterproof, The 2-amino-2- methyl-1,3-propanediol is dissolved in the water to produce a carrier or composite liquid used for dispersing the lignin to produce a, varnish. Then the diethylene glycol monobutyl etheris added and the pigment is incorporated by grinding.

This is a fast drying yellow ink. It has greater water resistance than Example 1.

Example III I Parts by weight Water soluble soda lignin 25 Formamide 36 Water 18 Urea 5 Waxy starch-"Amioca"- -..1 2 Carbon black 14 Here the ink has a binder of water soluble lignin, and yet it forms water-repellant prints. This composition is good for printing on coated 0r magazine paper stock.

This example contains pigment and a binder of precipitated lignin dispersed ina carrier conamass taining water, an amino-hydroxy compound solubilizlng the iignin in the water, and a lactone as a waterproofing agent.

The four examples next following (VI to IX) respectively illustrate the employment of an aliphatic polyaldehyde, an aromatic polyhydroxy compound, an aromatic aldehyde, and a hydroxyketone as waterproofing agents.

. Example W I 1 Parts by weight 2-amino-2-methyl-1,3-propanedio1 10.00 Water 51.00 Paraformaldehyde 4.50 Precipitated soda lignin 20.00 Diethylene glycol monobutyl ether l 1.80 Peacock blue-.. 12.70

This is a blue ink formulated for high speed newspaper printing. It is fast drying and has fair water resistance. A similar ink of red color is obtained by substituting para red for the peacock blue.

Example VII Parts by weight Precipitated soda lignin 22.75 Diethylene glycol monoethyl ether 34.50 Water 25.00

Dihydroxynaphthalene-1,5 V 7.25 ,Carbon black 10.50

This makes a good printing ink of heavy body useful for printing on coarse absorbent materials such as cotton textiles.

Example VIII Parts by weight Precipitated soda lignin 21 Diethylene glycol monoethyl ether 32.2 Water 4-hydroxy-3-methoxy-benzaldehyde 7 Carbon black 9.8

Example A! I arts by weight Precipitated soda lignin-- 22.75 Diethylene glycol monoethyl ether 84.5 Water 25.00 p-Hydroxyacetophenone 7.25 Carbon black 10.5

Example X Parts by weight Precipitated soda lignin 15.00 2-amino-2-methy1-1,3-propanediol 11 Water 54 Hydroquinone monomethyl ether..-- 5 Carbon black 14 Toner L a 1 This makes an ink of thin body adapted for rotogravure printing.

Example XI Parts by weight Precipitated soda lignin .15

2-amino-2-methy1-1,3-propanediol 10 Water 35 Ethylene glycol 19 Paraformaldehyde 5 Carbon black 14 Toner n l Tetradecylamine '1 This composition is adapted for printing on newsprint or similar absorbent material. When the ,lignin content is increased to 23% and the water contentis reduced to 27% a heavier bodied ink is obtained which is suitable for printing on ordinary calendered paper (uncoated).

Example XII Parts by weight Blended lignin-resin (precipitated soda lignin,

34%.; W. W. gum rosin, 66%) 20 2-amino-2-methyl-1,3-propanediol 12 Water 54 Carbon black 14 This composition makes a very fast drying ink of good gloss and medium body, not waterproof.

Example XIII Parts by weight Blended lignin-resin (precipitated soda lignin, 30%; Batu gum (natural resin) "l0% 20 Z-amino-Z-methyl-1.3-propanediol 12 Water 54 Carbon black 14 This composition makes a very fast drying ink of thin body which forms water-resistant prints.

Example XIV 4 v Parts by weight Precipitated soda lignin 26 Formainide 34 Water 16 2-.methy1-2,4-pentanedio1 4 Hexamethylene tetramine 5 Carbon black 14 Triethanolamine 1 This ink has excellent water resistance.

assailed uent oi said binder being a lignin from fiber liberation. V

'7. A liquid printing ink consisting essentially of coloring matter and a binder dispersed in a composite liquid carrier containing water, and 2-amino-2-methyl-1-propanol dispersing said binder in said carrier, the predominant constituent of said binder being a lignin from fiber This ink has good water resistance and is especially formulated for low shrinkage on hard papers.

Example XVI I Partsby weight 2-amino-2-methyl-1,3-propanedlol 10 Water 37 1,2,3,4,5,6-hexanehexol 10 Paraiormaldehyde 5 Precipitated soda lignin Carbon black 14 Toner 1 The amount of lignin from fiber liberation utilized in the inks oi the present invention is ordinarily between 12 and 30% of the total ink composition. The water content of the inks generally is in the range of to 55% of the total ink composition;

It will be understood that the foregoing details and examples are presented to illustrate the invention and are not to be regarded as restrictive except as may be required by a fair construction of the appended claims. A wide variety of compositions or formulations may be prepared by those skilled in the art to' embody features and principles disclosed above and claimed here inafter as my invention.

I claim:

1. A liquid printing ink consisting essentially oi coloring matter, and a binder dispersed in a hydrophilic liquid carrier containing water, the predominant constituent of said binder being a lignin from fiber liberation. I

2. A liquid printing ink consisting essentially of coloring matter and a binder dispersed in' a hydrophiiic liquid carrier containing water. the predominant constituent of said binder being a soda lignin.

3. A liquid printing ink consisting essentially of ,coloring matter and a binder dispersed in a hydrophilic liquid carrier containing water, the predominant constituent of said binder being a sul- Iate lignin. I

. 4. A liquid printing ink consisting essentially oi coloring matter and a binder dispersed in a hydrophilic liquid carrier containing water, the predominant constituent of said binder being a lignosulionate precipitate from waste sulfite liquor.

5. A liquid printing ink consisting essentiallyof coloring matter and a binder dispersed in a composite liquid carrier containing water and a lower hydroxyalkane containing 8."NH2 group dispersing said binder in said carrier, the predominant constituent of said binder being alig nin from fiber liberation.

6. A liquid printing ink consisting essentially liberation. V

8. A liquid printing ink consisting essentially of coloring matter and a binder dispersed in a composite liquid carrier containing water, and tris (hydroxylnethyl) 'aminomethane dispersing said binder in said carrier, the predominant constituent of said binder being a lignin Irom fiber liberation.

9. A liquid printing ink consisting essentially oi coloring matter, a binder and a hydrophilic liquid carrier containing water, a lower hydroxyalkane containing 9. NH: group dispersing said binder in said carrier, and a lower aliphatic aldehyde that enhances the water resistance of the printed ink, the predominant constituent of said binder being a lignin from fiber liberation.

10. A liquid printing ink consisting essentially of coloring matter, a binder and a hydrophilic liquid carrier containing water, a lower hydroxyalkane containing a NH2 group dispersing said binder in said carrier, and paraiormaldehyde that enhances the water resistance or the printed ink, the predominant constituent of said binder being a lignin from-fiber liberation.

11. A liquid printing ink consisting essentially of coloring matter, a binder and a hydrophilic liquid carrier containing water, a lower hydroxy alkane containing a -NH: group dispersing said binder in said carrier, and glyoxal that enhances the water resistance of the printed ink, the predominant constituent of said binder being a lignin from fiber liberation.

I 12. A printing'ink comprising coloring matter, approximately 12-30 percent of alignin from fiber liberation. water, and approximately 5-20% of a lower hydroxyalkane containing a NH: group,

I by weight of the ink.

14. A liquid printing ink consisting essentially of coloring matter and a binder dispersed in a composite liquid carrier containing water and a lower hydroxyalkane containing a -NH: group dispersing said binder in said carrier,.-the predominant constituent of said binder being precipitated soda lignin.

15. A liquid printing ink consisting essentially of coloring matter and a binder dispersed in a composite liquid carrier containing water and a lower hydroxyalkane containing a --NH= group dispersing said binder in said carrier, the predominant constituent of said binder being sulfate lignin.

16. A liquid printing ink consistingessentially of coloring matter and a binder dispersed in a composite liquid carrier containing water and a lower hydroxyalkane containing a NH2 group dispersing said binder in said carrier, the predominant constituent of said binder being a lignosuli'onate precipitate from waste sulfite liquor.

, l4 narnnsncas CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name 7 Date Ludwigsen May 24, 1932 Phillips Feb. 28. 1933 Lawrence Apr. 10, 1934 Lohmann Feb. 5. 1935 Wallace May 20. 1941 Meunier June 5. 1945