DE2312352A1 - THICKENED COLORANT SOLES AND THEIR USE FOR COLORING AND PRINTING FABRICS - Google Patents

Description

General Mills Chemicals, Inc. Minneapolis, Minnesota, V.St.A.

Our Ar. 18 530

Thickened dye brines and their use for Dyeing and printing of fabrics

The invention relates to thickened, borax-containing cationic dye sols and a method for dyeing and printing of fabrics using these sols, the derivatives certain as thickening agents contained by polygalactomannans.

Polygalactomannans such as guar gum and Hobinia pseudoacacia Gums are excellent thickeners and have many uses. The term "polygalactomannans" used here encompasses the general class of polysaccharides comprising both galactose and mannose units contain. The "polygalactomannans" become common in the endosperm segments of Löguiainose seeds such as Guar, Robinia pseudoacacia, Sara, Honey Bean, Flaaiaienbaum and Cassia occidentalis (guar, locust bean, tara, honey bean, flametree and cassia occidentalis)

309844/1026

hit. Polygalactomannans are under alkaline Conditions networked by the boron. - .;

Beioi industrial dyeing or printing of fabrics, the dyeing of carpet tufting, halftone printing a and Other types of dyeing processes are the dye solutions thickened to give the dyes on dea yarn or hold the fabric until the dye gets into the yarn or the tissue can penetrate and be fixed by steam treatment. Once the dye is fixed, it will be the local solvent and the thickener washed out of the yarn or fabric. There are three Types of dyes, anionic dyes, nonionic dyes, and cationic dyes.

The cationic dyes, sometimes called basic Dyes are referred to contain a cationic charge. They usually make hydrochloride, zinc chloride, Qxazine chloride, aluminum chloride or quaternary ammonium chloride salts of dyes with basic groups. They are generally in concentrations of about 0.2-5% by weight of the sol. These dyes were used earlier used to dye animal fibers. They are now also used to dye synthetic polymer fibers are used containing anionic groups, e.g. modified hylon. Commercially available cationic dyes sometimes contain substantial amounts of borax, namely from about 10-85% by weight of the dye. That Borax can be present as an impurity as a result of the manufacturing process to improve the dispersibility of the dye, to prevent caking of the dye, which is in powder form or to adjust the intensity of the dye, direction-modified polygalactotaannans cannot be used

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Thickening dye solutions are used, which contain cationic dyes, as the borax present crosslinks the rubber and forms a gel. The special cationic dye used plays for the networking of the Polygalacto & a nna ne no role. The borax present is responsible for the crosslinking in these dye concentrations.

It has now been found that selected water-soluble folygalactoaannane derivatives for thickening kationi-r see dye solutions that can be used are formulated with borax. With these polygalactoaiannan derivatives, which are suitable as thickeners for solutions of cationic dyes, it is to carboxyalkyl ethers of polygalaetomannans, in which the alkyl radical contains 1 to 2 carbon atoms, including carbamyl ethyl ether of polygalactomannans and hydroxyalkyl ethers of polygalactomannans, in which the alkyl radical contains 2-3 carbon atoms. The molar Substitution of the derivatives is at least about 0.1. The preferred range is about 0.1-1.0. The molar substitution represents the numerical average of the moles of the substituting radical per mole of anhydrohexose unit of the polygalactomannangumaiis. The selected derivatives of the polygalactomannan are preferably used in concentrations of about 0.15-2% by weight of the cationic dye sol is used.

Carboxyalkyl ethers of polygalactomannans are commercially available. Process for the preparation of carboxyalkyl ethers of polygalactomannans are described in U.S. Patent 2,520,161.

Also the hydroxyalkyl ethers of polygalactoaannans are available in the stores. You will be through implementation of

3 0 9 Γ, Λ 4/1 0 2 6

Polygalactomannan made with alkylene oxide in the presence of an alkali catalyst. The catalysts are generally aluminum metal or alkaline earth metal hydroxides, such as sodium, potassium or calcium hydroxides. Amraonia can also be used as well as more basic complexes. * Catalysts, such as Benzyltrimethylaomoniurahydroxid. It can very low levels of catalyst as low as 0.05 wt.% Of Polygalactoiaannans be used. In general, it is not necessary to exceed 10% by weight of the polygalactomannan, although larger amounts could be used. Usually about 2 to 3% by weight of the polygalactoaiannan is used. The reaction can be carried out at room temperature or at elevated temperatures. In general, the reaction is carried out in the temperature range of about 17 - 10O ⁰ G effected. Although higher temperatures of, for example, up to 125 ° C. can be used, this generally does not provide any advantage. The reaction can be effected at ambient temperatures, under reflux, or at elevated pressures in a closed reaction vessel. The exact pressure is not critical and, although higher pressures can be used, the reaction will normally be carried out at the pressure developed during the reaction. In general, these intrinsic pressures are in the range from about 2.1 to 8.8 atmospheres.

The reaction can essentially take place in the absence of water or solvent (no added water) can be carried out, although if no water is added, the efficiency of the reaction is very low is. The reaction generally becomes the same performed in the presence of v / ater to get a better one To achieve efficiency. In the absence of others

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Solvents are used catalytically in quantities of water in the order of about 3 Ws 8, based on the polygalactomannan. These small amounts are generally used at the higher temperatures and elevated pressures, while larger amounts of water are used when lower temperatures and atmospheric pressure are suitable for use. Examples of such organic solvents are isopropanol (water-miscible) and heptane (water-immiscible). Other non-reactive organic solvents can be used, although the above two are preferred. Such other organic solvents are common aliphatic hydrocarbons of 5 to 10 carbon atoms which are commercially available, for example pentane and hexane, alcohols higher than methanol containing 2 to 10 carbon atoms can also be used, for example tert-butanol, provided that the solvent is essentially inert If larger #assenaengen If used, the water should be enough to swell the guar gum slightly, making it more reactive. When used in conjunction with a solvent such as isopropanol or heptane, about 10 to 80 % water based on the weight of the guar gum is used. The preferred Mange Nasser is about 30 to 70 % for the water-miscible solvents and 20 to 50% for the water-immiscible solvents.

.When organic solvents are used, are they are generally present in amounts up to eight times the weight of the rubber, although larger amounts can also be used

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can be used., icönaen, if so desired. In general, the water-miscible solvents are used in the same to three times the amount of gum weight. In the case of solvents which are not miscible with water, the amount is usually three to five times the weight of the rubber. The weight ratio of water to organic solvent is preferably in the range of about 0.05-0 »5». For the «» water-miscible organic solvents, the preferred range is about 0.2-0.45 and for the water-immiscible organic solvents about 0.1-0.2. In general, any non-reactive organic solvent can be used. At the lower ratios, add water. organic. Solvent, the reaction is slower. With the. higher ratios slow down the recovery of the product by filtration.

The manufacture of carbamyl ethyl ether of the poly- galactomannan is made by implementing. Acrylamide with the polygalactomannan in the presence of an alkaline Catalyst. The preferred catalyst is lithium hydroxide. In general, alkali metal or alkaline earth metal hydroxides such as sodium, potassium or calcium hydroxide can be used · Also Ammonia can be used. The catalysts are usually used in amounts of about 2-3% by weight dea Polygalactomännans used. The acrylamide becomes the Mixture of polygalactomannan and catalyst added. The reaction is usually carried out at barely a temperature of up to about 70.degree. The acrylamide molar ratio to polygalactomannan is about 0.25 to 1.0 and usually about 0.5 · Can be used as a solvent system

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uses the same as in the manufacture the Hydroxftalkylpolygalactomannans.

The above-mentioned thickeners are used in the dye sols in amounts of about 0.15-0.30% by weight of the sol and in printing pastes in amounts of about 0.15-2 % . The amount of the cationic dye

cfi «

and the borax in sol or paste is desired by / Intensity of the dye and the particular Fab9 formulation certainly.

example 1

The data listed below show the relative effectiveness of boraxion, selected polygalactocaannane derivatives to network.

The sols were made by 'making the rubber and the borax in the concentrations given in (Table 1 dispersed in water. The pH-nert of Brine was adjusted to 6.8. The gumai were left for about Hydrate for 5 hours. The brine was pH-adjusted to 5 then brought to the values given in Table 1 by adding trisodium phosphate. The examples include- guar gum and Eobinia pseudoacacia gum, which were not converted into derivatives, as well as 2,5-BpoxypropyltrimethylguargumEtti. These examples are representative of gums that are opposed to crosslinking the polygalactomannans are not resistant.

The degree of crosslinking was measured in spring pail 1 hour after the addition of the alkali. A fat penetrometer was used for the measurement, which was provided with an Aliwainium cone weighing $ 4- .7 g and a stainless steel cone weighing 10 2.1 g. The koni were upside down

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to their normal position when measuring fat. The outer surface of the tip of the cone was attached to the arm of the penetrometer so that the base of the cone touched the crosslinked BoI first. In this position, the cone was allowed to fall freely into the sol for 5 seconds. sink. The penetration depth was measured in G.10 aim units. The results obtained are shown in Table 1.

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Table 1
Relative tolerance towards the boration

rubber Rubber-
concentrate
tration
in the sol, 1 2 0.75 i> added pH-der
Disper
sion
with
borax Borax (Na ₂ B ₄ 0 ₇ .10H ₂ 0) 5 % added borax care
Disper
sion
with
borax (Ha _? B.0 ₇ .10H _p 0)
2 4 7 2 Sindring
depth of
Steel cone,
l / l0 mm 1 1 Viscose
ity of
Sols before
the to
giving the
borax 10.6 Unmistakable
depth of
Alumini
umkonus,
1 / 1O ma Binding
depth of
Steel cone,
1/10 mm Viscose
ity of
Sols before
the to
giving the
borax 9.3 ! Are ring
depth of
Alumini
umkonus,
1/10 mm 30th Guar gum 1 4275 10.4 44 140 3900 9.6 13th 58 Kobinia
copseudo-
* - 'acacia gum 1 3125 10.0 55 173 3200 9.0 24 52 j ^ propyltri-
• ^ methylguar-
O
N ^ carboxy 1 1700 10.1 92 165 1800 9.0 23 438+ nia pseudo-
acacia gum 1 725 10.6 438+ 438+ 750 9.1 438+ 438+ Carboxyethyl
guar gum 2000 10.5 410 438+ 2075 - * 231 Carboxymethyl
guar gum 190 10.1 438+ 438+ - ** 8.7 -J * CO
438+ ■ £ Carboxymethyl
guarguflfflii 2225 10.4 93 270 2300 9.2 195 CO
119 p Carbamylethyl
guar gum 650 406 438+ 900 44

Continuation of TaljeXXe 1

.- 0.75

concentration in SoX,

Hydroxy

ethyl guar

rubber

_ω Hydroxy- _O propylguar ~ co rubber

not approved »

Viscosity of the brine before adding «d« B Borax

2200

32ΟΟ

pH the

üieper ~ fcion old borax

10.7

10.6

Penetration * Mndrin ^ -

deep ate depth of the

Alumini- Steblkonua

utnkonus, t / 10 on 1/10 OB

523

296

$ 5> sugefiM jtee borax (ίϊ R ₂ B ₄ O ₇ , 10H ₂ O) Intrusion Viscose pH the Bindrinff- depth of do the Diaper depth of steel cone, SoXs before eion AXumini— I / IO mm the access with vunkoauB, g & fee dea borax I / IO π »

9.7

9.3

26th

37

91

co

N) CO

απ

as from those listed in Table 1. penetrating depths can be seen, formed Guarguaami and Robinia pseudoacacia gum, which are not in! derivatives convicted "rare, with biting borax concentrate" ion gels. The carboxyalkyl ethers of Folygalscto-.aatmana remained at both borax concentrations ia essentially liquid. The Carbastyläthylatcer and the Hydroa ^ alkyl ethers of the Polygalactosaannane waxea. at the Borasdton concentration of 0.75% by weight of the rubber much more flowable than the folygalactoraannane. At the Boraxkronzentratioii of 5 wt.% Des Goaads were the brine of carbamyl ether and the Hydroxy alkyl ethers of polygalactomaonan more fluid than the JE-olygalactomaanan which has not been converted into derivatives "

Example 2

This example illustrates the use of the Carboxyäthyläthers of Guarguauai in conjunction with a 'commercial cationic dye * 3 S of the Carboxyäthyläthers of Guargusuai (prepared from ö _t> moles acrylonitrile per mole Polygalactoaannan) were dispersed in one liter of water "The dispersion had when it was slightly acidic, a viscosity of 50 centipoise. 100 ml of the dispersion was added to 0.1 g of a cationic dye * The cationic dye was Sevron Yellow R, Color Index Basic Yellow Hr. 11 with the following structure! * Orjael 1

OC,

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The fabric sample contained 76 »!? % Boration, expressed as MSLgBqPyIORpO. The actual irora dea Borationa was not known. The pH of the dispersion was adjusted to 8.1. There was no cancellation.

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Claims (6)

23-2352 Claims 1 * Thickened borax containing canonical dye sol, characterized in that it in an amount of about 0 »2 the cationic dye - 5 ° wt _t% of the sol and the borax in a Senge of about 10-85 Gear.!. % of the cationic dye contains, the thickener from carboxyalkyl ethers of lolygalactosiannanes, where—. in the alkyl radical contains i - 2 carbon atoms, hydroxyl alkyl ethers of polygalaetoaanaanes, the alkyl radical containing 2-3 carbon atoms, or carbaylethyl ethers of polygalactoraannanes and the molar substitution by the substituting component is at least 0.1. 2 Composition according to claim 1, characterized in that the thickener _r about 0.15 Göw 2.0 '% constitutes the kationiechen Farbstoffsols. 5. iäusaaua & ns & tzuag according to claim 1 ,. characterized, that the thickener is carboxymethylguarguaai is. 4, Zussi & siensetaung according to claim 1, characterized in, that the thickener is carboxyethylguarguaad. is. 5. Composition according to claim 1, characterized in that that the thickener Carbaayläthylguargua & i is. 30Si: 44/1026 6. Composition according to claim Ί, characterized in that that the thickener is a carboxy- ethyl ether of Robinia pseudoacacia gum is. 7 · Zixsaiuaensosition aacix Aaspimcii 1, thereby, gekena— show that the Yerdicfcaagsalttel Hyaroaqjrproijylguargumaii is. 6 * Zusa ^ aiensetziiag according to claim i, & ει3ιΐΓοίι characterized, that the Yerdifckangsmitfeel Hydroxyäthylguargtuami is. 9- Procedure for. Dyeing of fabrics, characterized in that a cationic dye sol according to claims 1-8 is used. For General Mills Chemicals Inc. Minneapolis, Minnesota, Y.St.A. I Dr RXWolff Lawyer 9844/1026