US 3925007 A
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D United States Patent 11 1 1111 8 3,925,007
Gurtler 51 Dec. 9, 1975 1 1 DISPERSE DYE CONCENTRATE WITH 1.854,363 4/1932 Aisen 8/79 SAWDUST 2,000,120 5/1935 Bush 1 8/615 ux 2,486,562 11/1949 lamarino 1 1 i 1 i v. 8/79 X Inventor: filt Gurtl r. 24 Neusatzweg, 3,174.165 3/1965 Dunn 6181. 1. 8/158 swtzerland OTHER PUBLICATIONS  Asslgnee: CIBA'GEIGY B35611 Cooley, Practical Science for the Dry Cleaning lndus- Swflzsrland try, 1930, pp. 126-128, 133-138.  Filed: Sept. 21, 1972 Primary Examiner-Benjamin R. Padgett [2|] Appl' N04 29l104 Assistant Examiner-B. Hunt  Published under the Trial Voluntary Protest Attorney Agent, Firm joseph Kolodny; Edward Program on January 28, 1975 as document no. Roberts; Prabodh Almaula B 291 ,104
ABSTRACT  Foreign Application Priority Data Product for use as a textile processing agent in a tex- Sept. 30, 1971 Switzerland i, 14209/71 tile extraction Process Comprising from 9 to 75% y weight of the product of a textile processing agent car- 52 us. Cl. 8/91; 8/65; 8/79 s an substrate of from 90 I9 15% y weight 51 Int. c1. D06P 1/46 of the P Said Substrate being insoluble in  Field 6: Search 8/79, 158, 91, 6.5 extraction medium having negligible affinity and sorption capacity for said textile processing agent, and 5 References Cited from 0 to 10% by weight of the product of an adhesive UNITED STATES PATENTS adapted to assist in bonding the textile processing 223 019 2/1879 V h X agent to the-substrate and to provide a product subaug an 253,230 2/1882 Sansone i. 8/14 X stanuany free from dust. 253.286 2/1882 Sansone 8/14 1 Claim, No Drawings DISPERSE DYE CONCENTRATE WITH SAWDUST The invention relates to new solid preparations containing dyestuff, textile auxiliaries, optical brighteners and/or finishing agents, to a process for their preparation, to their application to the finishing of textile materials by the extraction process, and to the textile material, as an industrial product, treated according to the present invention.
The dyeing of synthetic materials with dispersion dyestuffs is performed usually from a dye liquor containing the dyestuff in very fine dispersion. These processes have the disadvantage that prior to their use the dispersion dyestuffs have to be converted to a form easily dispersible in water according to per se known, but nevertheless intractable and relatively expensive processes utilizing dispersing agents. During the dyeing process, the presence of suitable dispersing agents in the dye liquor is essential for the maintenance of the fine dyestuff dispersion.
The dispersion dyestuffs used for conventional dyeing are offered in a constant tinctorial strength to the consumer. This tinctorial strength is adjusted by the dyestuff manufactrer by incorporation of the appropriate amount of the required dispersing agents and, if necessary, of extenders. All dispersing agents and extenders employed in the production of these dyestuffs preparations must be soluble in the dye liquor.
Synthetic materials can also be dyed by the use of dispersion dyestufi's in the extraction process. With this method of dyeing, the dyestuff does not come into direct contact, as a dispersion in the dye liquor, with the material being dyed, but is deposited in a suitable extraction device and the dye liquor is continuously circulated through it.
By this process, the dyestuff, which is preferably difficultly soluble in the cold state, is dissolved by an extraction process to a degree governed by the solubility of the dyestufi' at the temperature of the liquor, and by this process comes into contact with the material to be dyed in dissolved form. Until now this extraction process required suitable preparations which for example also permit the dyeing of commercial quantities in desired shades and are suited for the dyeing of textile materials from aqueous as well as from organic medium.
Accordingly, the technique described above can be used for any type of active substances, such as textile auxiliaries, optical brighteners and finishing agents.
The present invention thus relates to new solid preparations which avoiding the difiiculties and disadvantages mentioned are suited for the dyeing, optical brightening and, finishing of textile materials by the extraction process in desired strength. These preparations are characterised in that they contain:
a. 9 to 75%, preferably 40 to 70%, of at least one active substance,
b. 90 to 15%, and particularly 80 to 30%, and advantageously 50%, of an inert carrier substance, and,
c. to 10 percent of an adhesive.
By active agents, above, are meant textile finishing agents such as dyestuffs, textile auxiliaries, optical brighteners and finishing agents.
Preferably dyestuffs, especially dispersion dyestuffs, are used as active substance according to the invention, i.e. those containing no acid, salt-forming, watersolubilising groups. They can belong to the most diverse classes of dyestuffs such as, e.g., the nitro, acridone, methine, perinone, naphthoquinoneimine, metalfree, phthalocyanine, heavy-metal-containing phthalocyanine, monoazo, disazo, metal-containing monozao, metal-containing disazo and anthraquinone dyestuffs; and they can moreover contain a fibre-reactive group. Preferred are monoazo, disazo-, and anthraquinone dyestuffs. All thse dyestuffs are known and can be produced by known methods.
The textile auxiliaries usable according to the invention include softeners; examples of these are:
l. phthalic acid esters such as dioctylphthalate, dimethylphthalat, diethylphthalate, dibutylphthalate possibly combined with diethylphthalate, dicyclohexylphthalate, as well as high-molecular phthalic acid esters from decyl and tridecyl alcohol, als mixed phthalic esters such as butyloctyl phthalate, butyldecyl phthalate, butylbenzyl phthalate, diamyl phthalate, diethylhexyl phthalate, dimethyl glycol phthalate and dicapryl phthalate;
2. phosphates such as tricresyl phosphate, triphenyl phosphate, triphenyl phosphate combined with tricresyl phosphate and phthalates, diphenylcresyl phosphate, dimphenyl-Z-ethylhexyl phosphate, tri-( 2-ethylhexyl )-phosphate and tris-( butoxyethyl )-phosphate;
3. aliphatic dicarboxylic acid esters, particularly esters of adipic acid and sebacic acid, such as dioctyladipate, didecyladipate, dicapryladipate, dibutylsebacate and butylbenzylsebacate;
4. fatty acid esters such as butyl oleate, and butyl stemate,
5. citric acid esters such as acetyltributylcitrate.
All these softeners are known. One of the tradenames under which particularly valuable types are supplied is Sapamine.
A further class of active substances applicable according to the invention is formed by the optical brighteners, especially derivatives of diaminostilbenedisulphonic acid, benzidine, benzimidazole, diimidazole, diphenylimidazolone, phenylbenzothiazole, derivatives of 4-aminonaphthalene-l ,S-dicarboxylic acid amide, substituted methylcoumarins, oxazole, oxacyaninel ,3- diphenylpyrazoline derivatives, as well as thiophene derivatives such as 2,5-(benzoxazole-2-yl)-thiophene.
Other applicable active substances usable according to the invention are finishing agents such as antistatic agents, dirt'repellents and fungicides. In the case of antistatic agents, these are non-ionic, cation-active or anion-active substances. Examples of these are oils, glycols, polyalcohols, poly glycol ethers or quaternary ammonium compounds.
Suitable inert carrier substances are inorganic and organic substances which are preferably insoluble in the treatment medium, and which possess a particle size rendering impossible the passage of these substances through the pores of the filter in the extraction process; and which have no or negligible affinity and absorption capacity with respect to the active substance. They are to hold the active agent(s) solely by mechanical means and not change their structure during the treatment process.
It is clear that the strength of the active substance can be adjusted to a specific value depending on the percentage thereof present.
Examples of suitable inert carriers which may be employed are: diatomaceous earth (kieselguhr in the form of powder), calcium carbonate powder, plastics, sugar, asbestos, silica powder, and wood chips such as, in particular, sawdust, which have a particle size" of about 3 to 0.6 mm.
Suitable adhesives are nonvolatile solid or fluid prod- :ts which are not decomposed by the treatment meum but which are preferably soluble therein. They rve to fix the active substance and to prevent any distegration of the preparation, as well as to ensure the )tainment of the preparation free from dust or convining ver little dust.
The following, for example may be used: natural roducts and synthetic products. e.g., mineral oils, nulsifiable mineral oils such as Essotex, oleic acids, 1m arabic, carboxymethylcellulose, glycerin, ethylene ycol, and sorbitan fatty acid esters such as sorbitan :squioleate.
The preparation of the preparations according to the Ivention follows per se known methods, for example, follows:
a. the active substance in the forrnla powder is homoeneously mixed in the dry state with the carrier sub- .ance, and, optionally, the obtained mixture moist ned in a suitable apparatus, e.g., in a turbulent-chamer coating apparatus, with an adhesive; or
b. the active substance in the form of a powder is mixed dry with the inert carrier substance, and addition ien made to this mixture of a solution containing the dhesive either emulsified in water, or dissolved in an rganic liquid, e.g in aliphatic halogenated hydrocarons such as perchloroethylene, the moist mass subseuently homogeneously mixed and finally dried, or
c. the press cake of the active substance, moistened rith water, is homogeneously mixed with a water-solule or emulsifiable adhesive and the carrier substance; nd the obtained mixture subsequently dried.
The same result is obtained when the dry active subtance is emulsified with water or mixed with an oranic liquid, optionally containing the adhesive in the .issolved state, and the mixture then homogeneously llXBd with the carrier substance and dried.
The drying of the preparation is performed in all ases by known methods; e.g., in vacuo at about 50C, r at elevated temperature around 80C, e.g. in a heatig cupboard or in a roller drier or belt drier.
The preparations have a dust content from zero to a cry small amount; they can moreover be produced imply and cheaply, since no special predispersion of he active substance is required.
With the use of granular substances there is obtained free-flowing preparation of which the dust content anges from zero to a very small amount. And with the .se of pulverulent carrier substances there are obtained Iaky or pulverulent preparations of which the dust ontent likewise ranges from zero to a very small .mount.
The preparations according to the invention are eslecially suited for the finishing, especially dyeing of extile mate rials, especially textile materials of synhetic fibers, by the extraction process as described, .g., in DOS No. 1,938,792.
Suitable synthetic textile materials are, in particular, iydrophobic fibres, such as fibre material made from lnear high-molecular esters of aromatic polycarboxylic cids, with polyfunctional alcohols such as polyethylne glycol terephthalate fibres, also textured polyester naterials, cellulose-diand -triacetate fibres, and synhetic polyamide fibres, as well as polyacrylonitrile and nodified polypropylene. These materials are treated with the said preparations by the extraction process;
e.g., by circulation or an organic liquor such as per chloroethylene, or an aqueous liquor.
Compared with the conventional application processes with dispersion dyestuffs, optical brighteners and finishing agents, the process comprising the use of the preparations according to the invention applying the extraction technique has the following advantages:
no special and expensive fine dispersion of the active substance is necessary; for the production of the preparations, the active substance can be employed in the form of the water-moistened press cake, or as dry powder, and there is no pollution of the effluent since the carrier substance is insoluble in the treatment medium and no dispersing agents are required.
The following examples illustrate the invention, without this being limited by the given examples. The term parts denotes parts by weight, and the temperatures are expressed in degrees Centigrade.
A. PRODUCTlON OF THE PREPARATIONS EXAMPLE 1 8 Parts of the dyestuff of the formula are mixed together with 11 parts of wood sawdust, A solution of 1 part of oleic acid in 14 parts of tetrachloroethylene is then added to the mixture, and the mass homogeneously mixed. A moist loose mass is formed, which is dried in vacuo at 50. A granular dust-free preparation is obtained containing 40% of dyestuff, 5% of oleic acid and 55% of wood sawdust.
EXAMPLE 2 if instead of the dyestuff of example 1 or oleic acid equivalent amounts of the dyestuff of the formula SCH CH OH or Essotex are used, the procedure being otherwise analogous to that described in Example 1, then a granular, dust-free product is obtained.
EXAMPLE 3 8 Parts of the dyestuff of the formula CH CH CN CH CHCH -OH CN 2 and 11.8 parts of sawdust are mixed together. A solution of 0.2 parts of Essotex in 13 parts of tetrachloroethylene is added to the said mixture, and the mass homogeneously mixed. The moist loose mass is dried in vacuo at 50. A granular product containing negligible dust is obtained.
EXAMPLE 4 20 Parts of the dyestuff according to Example 3 and 27.5 parts of wood sawdust are mixed together. An emulsion of 30 parts of water and 2.5 parts of Essotex" is added to the above mixture, and the resulting mass homogeneously mixed. A moist loose mass is obtained, which is dried at 50 in vacuo to obtain a granular, dust-free product.
EXAMPLE 5 If equivalent amounts of the dyestuff according to Example 2 is employed, with otherwise the same procedure as that in Example 4, then a granular, dust-free product with analogous properties is likewise obtained.
EXAMPLE 6 4 Parts of the dyestuff according to Example 1 are triturated with a solution of 7 parts of tetrachloroethylene and 0.5 parts of paraffin oil to form a fluid paste. An addition is then made of 5.5 parts of wood sawdust, and the resulting mass homogeneously mixed. A moist loose mass is thus obtained, which is then dried at 50 in vacuo. The resulting product is granular and has a negligible dust content.
EXAMPLE 7 4 Parts of the dyestuff according to Example 2 are triturated with a solution of 6.5 parts of isopropanol and 0.5 parts of Essotex" to produce a fluid mixture. An addition is made to this of 5.5 parts of wood sawdust, and the resulting mass further processed as in Example 6. A dyestuff granulate with a low dust content is obtained.
EXAMPLE 8 4 Parts of the dyestuff according to Example 2 are mixed with an emulsion of 6 parts of water and 1 part of Essotex. An addition is then made of 5 parts of Kieselguhr powder (Hyflo"); the whole is homogeneously mixed, and dried at 80 in a thin layer. The resulting product is a soft-granular mass, which can be easily converted into a dust-free powder.
EXAMPLE 9 2 Parts of the dyestuff according to Example 1 are homogeneously mixed in the dry state with 8 parts of kieselguhr powder (Hyflo"), without the use of an adhesive. A practically dust-free preparation containing 20% by weight of dyestuff is obtained.
EXAMPLE A procedure analogous to that described in Example 8 is applied, with the use, however, of the dyestufi according to Example 1, and the addition of equivalent amount of calcium carbonate instead of kieselguhr powder. After drying at 80, a brittle mass is obtained, which can easily be converted into a dust-free powder.
EXAMPLE 1 l 4 Parts of the dyestuff according to Example 1 are mixed together with parts of calcium carbonate powder; a solution of 5 parts of tetrachloroethylene and 1 part of Essotex is added, and the whole triturated to form a homogeneous slurry, which is then dried in a thin layer at 50 in vacuo. There is obtained in this manner a soft-granular mass, which can be easily converted into a dust-free powder.
EXAMPLE 12 If, instead of Essotex, sorbitan sesquioleate (Arlacel 83) is used, with otherwise a procedure analogous to that described in Example 1 l then here too a soft-granular mass is obtained, which can be readily converted into a dust-free powder.
EXAMPLE l3 4 Parts of the dyestuft" according to Example I are mixed with 5.5 parts of calcium carbonate powder; a solution of 5.5 parts of tetrachloroethylene and 0.5 parts of oleic acid is then added, and the resulting mass processed as described in Example 1 l. A soft-granular mass is obtained, which can be easily converted into a dust-free powder.
EXAMPLE l4 7 Parts of the dyestufi according to Example I are mixed together with 2 parts of kieselguhr powder (Hyflo); a solution of l3 parts of tetrachloroethylene and 1 part of sorbitan sesquioleate (Arlacel 83) is added, and the whole processed as in Example ll. A softgranular mass is obtained, which can be easily converted into a dust-free powder.
EXAMPLE l5 EXAMPLE 16 7.4 Parts of the dyestuff of the formula OCH CH OH O OH as a water-moistened press cake having a 54% solid material content, are homogeneously mixed with 1.5 parts of water and 1 part of glycerin. An addition is then made of 5 parts of wood sawdust; the whole is subsequently homogeneously mixed, and dried at 50 in vacuo. A granular, dust-free product is obtained.
EXAMPLE l7 1 Part of 2,5-(benzooxazole-Z-yl)-thiophene powder is homogeneously mixed dry with 9 parts of kieselguhr powder (l-Iyflo"), without the addition of an adhesive. A practically dust-free preparation containing 10% by weight of optical brightener is obtained.
EXAMPLE l8 2 Parts of a softener according to the Swiss Pat. No. 320,205 are homogeneously mixed in the dry state with 8 parts of kieselguhr powder (Hyflo), without the addition of an adhesive. A preparation containing 20% by weight of softener and having a very low dust content is obtained.
B. APPLICATION OF THE PREPARATIONS IN THE EXTRACTION PROCESS EXAMPLE 19 a. The dyestuff preparation is contained in an extraction holder made from glass fibre; for example a Soxhlet apparatus; the liquor employed is tetrachloroethylene for the dyeing of a knitted fabric made from tex tured polyester material, Examples l to l 5, or water for the dyeing of polyamide material with the dyestuff preparation prepared according to Example l6.
A combination dyeing with 0.25% of the dyestuff preparation according to Example 4, 0.55% of the dye stuff preparation according to Example 5, 0.20% of the dyestuff preparation according to Example 6, on a knitted fabric made from texture polyester in tetrachloroethylene, dyed in the "Bowe-solvent-drum-dyeingmachine LFM 12" by the extraction method, produces a dyeing displaying excellent fastness nonstreaky olive to moisture, rubbing, sublimation and light.
b. The preparation according to Example 17 is placed in the glass-fibre holder of a Soxhlet apparatus; polyester Crimplene is then treated for one hour in the extraction process with an aqueous liquor, the liquor containing as carrier 5 ml/l of o-dichlorobenzene, and an emulsifier (ratio of goods to liquor i240). There is obtained on the substrate a very good optical brightening effect.
c. The preparation according to Example 18 is placed into the glass-fibre holder of a Soxhlet apparatus; and polyacrylonitrile fabric (Orlon) treated for one hour, in the extraction process, with a tetrachloroethylene liquor (ratio of goods to liquor 1:10). There is obtained on the substrate a pronounced softening elTect.
1. A composition for use as a textile dyeing agent in an extraction process consisting essentially of 40 to by weight of a disperse dyestuff carried on to 30% by weight of wood sawdust and 0 to l0% by weight of an adhesive selected from mineral oil, glycerin, sor
bitan fatty acid ester or carboxymethylcellulose.