US2150954A

US2150954A - Mineral dye and method of making same

Info

Publication number: US2150954A
Application number: US156951A
Authority: US
Inventors: Clarence B White
Original assignee: Individual
Current assignee: Individual
Priority date: 1937-08-02
Filing date: 1937-08-02
Publication date: 1939-03-21
Anticipated expiration: 1956-03-21

Description

Patented Mar. 21, 1939 I UNITED sTATas PATENT OFFICE Clarence a. White, Montclalr, N. J.

No Dravlng. Application august 2, 1931,,

Serial No. 150,951

10 Claims.

This invention relates, generally, to dyes, and

the invention has reference, more particularly, to

a novel mineral dye composition and the method of making the same, the said dyecomposition comprising essentially one or more chromium salts of carbohydrate acids, and being especially suitable for use either singly or in admixture with additional ingredients for dyeing or ior printing textile materials and the like;

Heretoiore, the only compound 01 chromium that could be satisfactorily used in mineral dyeing of textile materials was chromous acetate and the use-of this compound was attended with serious obstacles, among which may be mentioned the following: ilrstly, chromous acetate can only be completely precipitated, as chromic hydroxide among the fibres of the textile material treated, after long continued boiling with caustic alkali, a condition which renders mass production quite impossible and results in the bleeding" or dis-' persion of a portion of the chromous acetate, thereby weakening the resulting shade of the textile material and rendering such shade variable or smeary; secondly, to avoid variations in shade, it is necessary to put the dye saturated textile material through a highly expensive aging or oxidizing process during which the textile material is treated with a mixture of high pressure steam and atmospheric oxygen in an ager, wherein the chromous salt is partiallyhydrolyzed and oxidized to a chromic state, in which condition it is much more rapidly reactive in the presence oi caustic alkalies; and thirdly, chromous acetate can only be obtained in a condition of limited concentration when in solution, i. e; about eight per cent of chromium oxide, and this concentration more soluble chromic salts such as the nitrate,

chloride, and sulphate of chromium, but these have not proven practicable because of the tendency of the chromium salts to hydrolze and set free the acid ions, which in turn tender or weaken thefabric. JI'his tendency, while it renders chromium salts invaluable as mordants in the dyeing of wool, at the same time causes them to be useless in the dyeing of cotton. When a' cotton" fabric thus impregnated is-dried on the cans, the chromic sulphate or chloride is decomposed, and sulphuric or hydrochloric acid, as the case may be, is liberated and rapidly tenders or even destroys thefabric.

a This application is a continuation, in part, of

my copending application for. Mineral dye and method of making same, filed January 14, 1935, Serial No. 1,701, Patent No.' 2,091,539.

The principal object ofthe present invention is to provide a dye composition comprising one or more compounds of chromium, which compounds overcome the above recited disadvantages of the known compounds of chromium, i. e. the compounds of this invention are sumciently soluble to permit a concentration great enough to insure the proper depth of shade with but a single dyeing, so that even or matched shades are easily obtainable; the compounds of this invention are suillciently reactive to the insolubilizing medium to permit the formation of the insoluble chromium dyeing compound immediately upon contact with the insolubilizing bath, without bleeding out in the bath, thereby entirely eliminating the customary aging" process; and the compounds of acid ions that will'tend to disintegrate the fabric when the same is dried on the cans.

Another objector the present invention lies in the provision of a novel chromium dye composition 01' the above character that is miscible with iron and other metallic salt dye liquors and which will not precipitate any such salts with which it is mixed, the said composition being suillciently stable when used alone or in conjunction with other mineral dyeliquors, so that no precipitation or clodding (clotting) or the formation of insoluble residues shall take place before or during the application of the dye liquor to'the fabric being processed.

Still another object of the present invention is to provide a novel dye composition of the above character that may be easily and cheaply produced on production basis.

Other objects of this invention, not at this time more particularly enumerated, will be understood,

from the following detailed description of the same.

The novel composition of this invention comprises a mineral dye liquor consisting essentially of one or more chromium salts of such carbohydric acids as gluconic, glucoronic, saccharic, glycolic and tri-hydroxy butyrlc acids, all 01' which are possible reaction products of the reaction of alkali bichromates on monosaccharoses in the presence of hydrochloric and sulphuric acids, with or without association with certain soluble fatty acids, e. g. acetic or formic acid, the sulphuric or hydrochloric acid being present in quantity sumcient to decompose the alkali bichromate, but not in suiiiclent quantity to form chromium salts with the chromium'present in the alkali bichromate. These compounds can be readily preparedin a condition of great concentration,

' this invention do not, upon hydrolyzing, set free exceeding under certain conditions a content of 20% chromic oxide equivalent. Sodium bichromate or potassium bichromate are preferably cheapness I prefer to make use of cane sugar or sucrose, cane sugar molasses, beet sugar, beet sugar molasses, and black strap molasses or dextrine. All of these materials are classed as polysaccharoses, or polysaccharose compounds, and all are capable of being hydrolyzed by means of dilute acids into monosaccharoses, or simple hexoses of either aldo-hexose or keto-hexose type, or both. a

When a polysaccharose preparation of the desired chromium carbohydrate compound, it is, necessary that it be hydrolyzed into monosaccharoses by means of dilute acids. Polysaccharoses are divided into two classes: firstly, di-saccharoses or hexo-bioses, and also tri-saccharoses, which are true sugars, and secondly, polysaccharoses that are not true sugars, such as starch, dextrine, amylose and cellulose. All of the polysaccharoses, whether true sugars or not, are equally susceptible of reduction by means of hydrolysis to mono-saccharoses or simple hexoses, and this hydrolysis or reduction is the first step of the invention.

-Cane sugar, with which may also be included cane sugar molasses, hydrolyzes into a molecule of glucose and a molecule of fructose, in accordance with the following reaction:-

CHaOH-(CHOH) 4-CHO glucose (aldo-hexose) CHzOH-(CHOH) aCO-CH2OH fructose (keto-hexose) Upon oxidation, the aldehyde sugars (aldohexoses) yield hydroxy mono-basic acids, and hydroxy di-basic acids of the same number of carbon atoms. When a ketone sugar (ketohexose) is similarly oxidized, the original carbon chain is broken at the ketone group, and the resulting acids have a smaller number of carbon atoms than the carbohydrate from which they were derived.

glucose (aldo-hex'ose) CHzOH-(CHOH) 4COOH gluconic acid penta-hydroxy-hexan-oic acid CHzOH-(CHOH) 3COCH2OH+ O- is employed in the chromium tri-hydroxy-butyrate and chromium glycolate.

Beet sugar molasses is an important raw material in the production of chromium carbohydrate compounds, this material containing a large proportion of the tri-saccharose, rafilnose. Upon hydrolysis, rafllnose splits first into the monosaccharose (fructose, a keto-hexose) and a di-saccharose (melli-biose), which in turn hydrolyzes into glucose and galactose, both aldohexoses. The range of chromium compounds produced when beet sugar molasses, or beet sugar, is employed are consequently similar to the compounds produced when cane sugar (sucrose) is employed, because-in both cases an aldo-hexose and also a keto-hexose is oxidized by .the alkali bichrornate.

The nomenclatin'e of the carbohydrates is somewhat vague, indefinite and involved. However, glucose is also known under the names dextrose, grape sugar and starch sugar, while fructose is also known as levuloseor fruit sugar. Maltose or malt sugar, and milk sugar or lactose are both isomeric with sucrose or cane sugar, but maltose splits upon hydrolysis into two molecules of glucose, while lactose splits into one molecule of glucose and one 'molecule of galactose, both being aldo-hexoses.

The steps involved in the production of the mineral dye liquors that are the subject of this invention are three in number:

1st. The hydrolysis and splitting of a polysaccharose into a monosaccharose (simple hexose) which is either a keto-hexose (e. g. fructose) 'or an aldo-hexose (e. g. glucose or galactose).

2nd. The oxidation of a keto-hexose or an aldo-hexose, or both, by means of an alkali bichromate into a carbohydric acid. In the case of a keto-hexose, the resulting acids are, respectively, tri-hydroxy-butyrlc acid and glycolic acid,

and in the case of an aldo-hexose, gluconic acid,

capable'of further oxidation to saccharic acid.

3rd. The reaction by which a chromium compound of the carbohydric acids produced by the oxidation of the monosaccharoses (keto-hexoses and aldo-hexoses) is formed. The acids thus formed are gluconic, saccharic, tri-hydroxy butyric, and glycolic, which uniting with the contained ,chromium form the glycolate, gluconate, tri-hydroxy-butyrate and saccharate of chromium, respectively. I

In carrying out the processes of the present invention, I dissolve or mix in water to which from three to five per cent of hydrochloric or sulphuric acid has been added, a polysaccharose such asstarch dextrine, cane sugar, cane sugar molasses, beet sugar or beet sugar molasses, and then digest the whole at a temperaturepreferably exceeding degrees, centigrade, maintaining this temperature until the polysaccharose has been completely hydrolyzed and converted into simple monosaccharoses (aldo-hexose o'i' keto-hexose, or both, as the case may be). Additional .hydrochloric or sulphuric acid is now added to the completely hydrolyzed solution in amount sumcient (molecular proportion) to break down the alkali bichromate to be later added. This addition is not critical, it'be'ing possible to exceed this amount by from ten to twenty per cent, without thereby causing risk of damage to the goods to be dyed with this liquor. This addition' completed, a quantity of an organic acid, preferably a soluble member of the fatty acid series. such as acetic or formic acid. is now added and the temperature of the whole is raised to about '70 degrees, cent. The presence of the acetic, or equivalent acid, increases the solvent power of the resulting liquor for chromium salts, ensuring greater concentration, and at the same time stimulates the reaction that takesplace' The chromium trioxide at once oxidizes the aldohexose present (glucose or galactose) to gluconic acid (CH2OH-(CHOH) 4-COOH), thereby being itself reduced to chromic oxide, which in turn reacts with the gluconic acidthat has been formed to form chromium gluconate. Where a keto-hexose (e. g. fructose) is present, the chromium trioxide ox dizes such keto-hexose into a molecule of glucolic acid (COOl'-ICH=OH) and an additional molecule of tri-hydroxy-butyric acid (CH2OH- (CHOH) 2-COOH) both of which acids react with the chromic oxide to form the tri-hydroxy-butyrate and the glycolate of chromium, respectively.

As specific examples of the actual manufacture of the mineral dye composition of this invention, the following ingredients are employed in the proportions given by weight.

\ Pounds (1) Cane sugar or beet sugar 100 Water 620 Sulphuric acid 100 to 110 Acetic acid '75 Sodium bi-chromate 300 or (2) Cane sugar, or beet sugar molasses 150 Water 620 Sulphuric acid 100 to 110 Acetic acid 75 Sodium bi-chromate 300 Inasmuch as the above carbohydrates are converted by hydrolysis into aldo-hexoses and also keto-hexoses, the chromium compounds formed will comprise glycolate, tri-hydroxy-butyrate and gluconate of chromium.

The above materials hydrolyze asaldo-hexoses,

' mostly glucose, and the chromium compounds produced will be mostly gluconate of chromium.

In carrying out the process of manufacture of the dye composition, I add 35 pounds of sulphuric acid (or its molecular equivalent of hydrochloric acid) to about '75 gallons ('620 lbs) of water and into this acid solution I mix or dissolve the stated amounts of the respective carbohydrates mentioned above (cane sugar and molasses, beet sugar and beet molasses, dextrine, starch or corn syrup) or other suitable carbohydrate compound. These compounds may be employed separately, or they may be mixed, e. g.

cane sugar and cane molasses, cane sugar and beet molasses or glucose, etc. I then heat the resulting solution to a temperature of at least 70.degrees, cent., maintaining the temperature at or above this figure until the carbohydrate has been hydrolyzed and converted into its appropriate hexose or monosaccharose. The time required for this conversion will vary in accordance,

with the carbohydrate used as the basic raw material, being relatively long in the case of starch (one to three hours), and much shorter in the case of cane sugar, and other true sugars.

At this Stage the remaining sixty-five pounds of sulphuric acid (or its molecular equivalent in hydrochloric acid) as well as the whole of the acetic acid is added, and the temperature of the solution raised to about 88 degrees, cent., after which the 300 pounds of sodium bichromate (or its equivalent in another alkali bichromate) is added to the solution. The addition of the sodium bichromate is effected in a gradual mannen' care being taken that theseadditions should n t cause a violent rise in temperature that would result in the liquid boiling violently, th reby causing or resulting in a loss of material. While it is desirable that the temperature should be maintained at as high a point as possible violent ebullition and consequent foaming must be avoided atall times. The reaction. unless controlled, is apt to be exceedingly violent. but inasmuch as the reaction itself is strongly exothermic, it becomes possible to control the temperature within adesired range by the iudicious addition of the alkali bichromate. ca e being taken to distribute the latter as evenly as possible in the bath. As the reaction approaches its close, the temperature rise after each such addition of alkali bichromate becomes progressively less. until it flnally becomes necessary (in general) to apply external heat in order that the reaction may not become arrested and the alkali bichromate fail to become completely reduced.

'Lack of complete reduction of the alkali bichromate is revealed by a brown color in the liquor,

whereas complete reduction results in the mixture assuming a decidedly green color.

When the operation is definitely complete. the resulting dye liquor will contain an alkali sulphate, or an alkali metal salt of the acid utilized in decomposing the bichromate com ounds. to gether with the chromium contents of the alkali bichromate as a carbohydric compound of chromium, that is, as a gluconate, glycolate. trihydroxy-butyrate or related compound. The dyeing liquor is very weakly ionized. and even if hydrolyzed, exerts no iniurious or dama ing efi'ect upon cellulose, itself a member of the car bohydrate family.

If desired, the sodium bichromate (or equivalent) may be dissolv'ed in water before. mixture with the acid-sugar solution. For example. the 300 pounds of sodium bichromate (or equivalent) may be dissolved in water ('75 gallons) and the whole heated to 88 degreescent., whereupon the acid saccharose solution which has previously been heated to approximately 70 degrees cent. is slowly added to the alkalibichromate solution, care being taken that the temperature shall not rise with sufficient rapidity to cause violent ebullition and consequent loss of material. The color of the liquor at the close of the reaction should be a clear olive-green, but should it remain brown it will become necessary to add additional quantitles of the acid-saccharine solution until the, color has become permanently green. It is essential to maintain the intermixed solutions at as high -a temperature as possible during the whole of the reaction. The reaction is facilitated by the presence of acetic acid, or equivalent, including saccharic acid as an equivalent.

The novel mineral dye solution thus produced may be diluted with water in any desirable degree, so as to give various shades of green, or they can beapplied in such a degree of concentration that even deep shades can be secured with but a single immersion and padding of the-textile material. The carbohydrate compounds or chromium which make up the dye liquor being already in an oxidized state, require no further oxidation when padded into the fabric. These compounds react rapidly with hot caustic alkaiies, becoming immediately insolubilized, and without any manifestation of bleeding" or solution of the same in the-precipitating medium or hot caustic bath, as is the case with most chromium salts. The cellulose or cotton component of the textile"material, being itself a carbohydrate, does not react chemically with carbohydric compounds of chromium, so consequently there is no tendency manifested to tender or disintegrate the fabric as is the case when inorganic salts of chromium are employed.

a. While the general shade of a chrome dyed fabric is markedly on the order of green, the chromium compounds of the present invention may be intermixed with other dye materials, of which pyrolignite of iron is an exceedingly important member, thereby securing such additional shades or colors as those denominated "Mineral Pearl, Battleship Grey", Sand Shades", "Hong Kong, "Khaki and Iron Buff", iron pyrolig nite being selected for this purpose because of its chemical inertnes with regard to cellulose. The carbohydric compounds of chromium pos sess a very low hydrogen ion concentration, consequently having no strong tendency to tender fabrics as is the case with inorganic compounds of chromium, and at the same time their carbohydric acid radicals are easily replaced by the acid radicals of sulphuric and hydrochloric acids. It is therefore possible, without incurring danger of tendering the fabric to replace a part of the iron 'pyrolignite by such compounds as ferrous sulphate and ferric sulphate, thereby lowering the cost of the mineral dye liquor and even improving its quality in certain respects.

The following are typical minsral dye liquors based on the chromium carbohydrate compounds of this invention:

1. "All-mineral Pearl". 'All-mineral Battieship Grey". Aqueous solution of carbohydrate compounds of chromium, e. g. glycolate, gluconate, etc. of chromium. Ten to twenty per cent chromic oxide equivalent.

'2. "All-mineral Khaki". All ingredients on basis of 5% oxide equivalents.

Gallons Carbohydrate compounds of chromium--- 25 Black iron liquor 37% Ferrous (or ferric) sulphate solution 37% 3. All-mineral Khaki".

' Gallons Chromium carbohydrate solution 25 Black iron liquor '15 4. Chromium Brown." Chromium carbohydrate sohition-- gallons Manganese acetate pounds 3 The novel chromium carbohydrate compounds of this invention, when accompanied by aslight excess of carbohydrate reducing agents such as glucose and other aldo-hexoses, e. g. galactos'e, or keto-hexoses (e. g. fructose), exert a distinct solvent action on certain of the so-called vat" dyestuffs, i. e. derivatives in general of anthracene and anthraquinone bases, thereby making it possible to introduce such dyestuffs into the mineral dye liquor, whether the latter be composed entirely of chromium compounds or chromium compounds in admixture with salts of iron and manganese. The introduction of "these dyestufls into the mineral dye liquor makes possible the production of a great variety of shades, of which the majority are very fast to alkali and light, and possess a much greater resistance to' exposure than straight vat" dyes. In application, the mineral dye liquor carrying a certain proportion of "vat" dyestuil' is padded'directly on the fabric, squeezed and dried, the anthracene dyestuff being oxidized and fixed on the cloth in an insoluble condition during the drying operation. The chromium content of the dyed,

fabric is then insolubilined in the normal manner, 1. e. by passing the fabric through a hot bath of caustic alkali.

The dye composition of this invention may also be used in conjunction with the so-called sulphur dyestuifs. The sulphur dyestuffs are dissolved in the usual alkaline dye bath of sodium sulphide, care being taken to provide an excess of sodium sulphide with which to effect the insolubilization of the chromium compounds deposited upon and within the fabric. In application, the fabric to be dyed is first impregnated in the bath of chromium mineral dye liquor, then squeezed and dried. The dried fabric is then passed through the hot sodium sulphide dye bath containing the sulphur dyestuffs in solution, and' the latter are deposited upon and absorbed by the, fabric simultaneously with the insolubilization of the chromium compounds already padded into the fabric. This operation can either be carried out in an ordinary jigger, or as a continuous operation in continuous sulphur dyeing in the conventional "box machine, or sulphur dye run.

In the claims, the words carbohydrate and carbohydric refer to that group of compounds containing carbon combined with hydrogen and oxygen according to the formula 010-) g, in

which a: may be 5, 6 or 12, and y may be 5, 8 or 11.

What is claimed is:

1. In a mineral dye of the character described. a saccharose derivative of the group consisting of chromium glycoiate and chromium tri-hydroxy-butyrate.

2. A mineral dye liquor comprising an aqueoussolution of achromium salt of a carbohydric acid, said salt being formed by the oxidation of the reaction product of the hydrolysis of a polysaccharose of the group consisting of cane sugar,

cane sugar molasses,- beet sugar and beet sugar molasses.

-3. A mineral dye liquor comprising an aqueousvsolution of a mixture. of a saccharose derivative 4. A mineral dye liquor comprlsing an aqueous solution of a mixture of a saccharose derivative of the group consisting giycolate,

and chromium tri-hydroxy-butyrate with pyrolignite of iron and sulphate of iron.

5. A mineral dye liquor comprising an aqueous solution of a mixture of a saccharose derivative of the group consisting of chromium glycolate,-

chromium gluconate and chromium tri-hydroxybutyrate with a Water soluble salt of manganese.

6. In a mineral dye of the character described, a saccharose derivative of the group consisting of chromium glycolate, chromium tri-hydroxybutyrate and chromium gluconate together with a vat dyestuff.

7. The steps in the method of making a mineral dye consisting in hydrolyzing a polysaccharose into a monosaccharose of the group consisting of keto-hexose and aldo-hexose, and completely oxidizing the monosaccharose so formed by use of an alkali bichromate.

8. The method of making a mineral dye, comprising mixing an alkali bichromate with an aqueous solution of a polysaccharide of the group consisting of cane sugar, cane sugar molasses, beet sugar, beet sugar molasses, corn syrup and glucose, said aqueous solution being acidulated by a mineral acid of the group consisting of sulphuric and hydrochloric acids, the amount of v said mineral acidbeing just suflicient to displace the alkali metal radical and without producing a chromium salt of the acid, and with the addition of an acid of the fatty acid series of the group consisting of acetic and formic acids, the amount of said fatty acid not exceeding fifty per cent by weight of the mineral acid employed, care being taken to maintain the temperature of the reacting mixture as high as possible without undue ebullition.

9. The method of making a mineral dye, comprising hydrolyzing a polysaccharose carbohydrate of the group consisting of cane sugar, cane sugar molasses, beet sugar, beet sugar molasses and corn syrup, oxidizing the hydrolyzed poly-' saccharose carbohydrate by the addition of an alkali bichromate, adding only suiflcient mineral acid of the group consisting of hydrochloric and sulphuric acid to the solution to displace the alkali metal radical of the alkali bichromate, introducing an amount of a water soluble acid of the fatty acid series of the group consisting of acetic and formic acids, the amount of said fatty acid not exceeding one half of the amount of gether with suflicient mineral acid of the group consisting of hydrochloric and sulphuric acids to combine with the alkali metal component, but

not sumcient to form a salt of chromium with such acid, adding thereto an acid of the fatty acid series of the group consisting of acetic and formic acids in an amount not exceeding one half of the mineral acids employed, forming in such mixture simultaneously chromium trioxide and carbohydric acids, both of which unite to form a compound of chromium.

CLARENCE B. WHITE.