DE1153719B - Process for fixing direct dyes on cellulose-containing material dyed or printed therewith - Google Patents

Description

INTERNAT. KL. D 06 ρ

GERMAN

PATENT OFFICE

U6305IVc / 8m

REGISTRATION DATE: JUNE 26, 1959

NOTICE
THE REGISTRATION
AND ISSUE OF
EDITORIAL: SEPTEMBER 5, 1963

The method is based on the knowledge that aminoalkyl silicon compounds or metal complexes these compounds can be applied to natural and artificial structures made of cellulose and the noun dyes on it have an improved overall stability, remarkable Give wash resistance and insolubility.

Numerous dye fixatives are already known. For example, formaldehyde, urea and Melamine polymers of formaldehyde, cationic plasticizers and heavy metal salts have a reduction the loss of color of most fabrics dyed with direct dyes. The wash resistance direct dyeing and color printing on rayon is generally carried out by metal salts, such as zinc acetate, or improved by cationic plasticizers or cationic resin-copper complexes. Cationic resin complexes, such as the polyanthrenes, can be used for viscose fabrics dyed with direct dyes Give wash resistance.

The most common industrially used agents for improving color fastness are fixing agents of the formaldehyde type, metal salts such as copper and chromium salts, resin-copper complexes such as copper coordinated condensates of diethylenetriamine, triethylenetetramine or tetraethylenepentamine with dicyandiamine. The known diazotization and coupling processes are used for dyes containing amino groups for follow-up treatment.

Since the lightfastness of textile dyeings is based on photochemical processes, to a large extent depend on the dye molecule, post-treatment methods to improve color fastness may apply no improvement in light fastness can be expected. Some of the known dye fixatives for substantive colors even reduce the normal lightfastness of the dye molecules. Other Color fixatives also cause noticeable changes in the hue or intensity of the dyed fabrics.

For a diazotization or coupling treatment to improve the color fastness is at least a free primary amino group in the dye molecule is required in order for it to react with aromatic Compounds containing activating groups can occur.

Post-treatments with copper salts mainly improve the lightfastness, during post-treatments with chromium salts increase the wash resistance. However, this will go through a considerable change in the original shade of the dyed fabrics. Formaldehyde process for fixing direct dyes

on colored or printed with it

cellulosic! material

Applicant: Union Carbide Corporation,

New York, N.Y. (V. St. A.)

Representative: Dr.-Ing. F. Wuesthoff, Dipl.-Ing. G. Pulse and Dipl.-Chem. Dr. rer. nat. E. Frhr. v. Pechmann, patent attorneys, Munich 9, Schweigerstr. 2

Claimed priority: V. St. v. America June 26, 1958

Domenick Donald Gagliardi, East Greenwich, R. I.

(V. St. Α.),
has been named as the inventor

Fixing agents also give the dyed fabrics a characteristic formaldehyde odor. the Amino resin fixatives produce an undesirable fishy odor and are also compatible with other, Chemicals used in textile treatment are poorly tolerated.

It has surprisingly been found that the aminoalkyl silicon compounds and their metal complexes are extremely effective dye fixatives, as do most others in textile treatment occurring chemicals are compatible and free of undesirable odors. You change the color tint not or only insignificantly and give the dyed or printed fabrics better Shelf life and greater abrasion resistance.

The process for fixing direct dyes on cellulose-containing printed matter! Material after the invention consists in that the dyed or printed material with a coating of a Aminoalkyl silicon compound containing at least one functional group of the formula

R '

NO

R "

-Si - X ₄ _ _c _6

contains, where R is a divalent hydrocarbon

309 670/251

3 4

group with at least 3 carbon atoms between. The dye fixatives can also consist of aqueous

the nitrogen and silicon atom, R 'and R "water-alkaline solutions are deposited,

material atoms or alkyl, aminoalkyl, cyanoalkyl, an aqueous mixture with a content of 40 to

Hydroxyalkyl, carboxyalkyl, carbalkoxyalkyl or 60 parts of water, 40 to 60 parts of an organic

Aryl residues or the monohydric group 5 alcohol, such as ethanol or isopropanol, and 5 percent by volume a monobasic acid such as acetic acid,

R - Si - X is an excellent means of loosening or dissolving

; dispersing the aminoalkyl silicon compound; it is

Z ₂ practically for every dyed or printed cellulose

lo-containing material suitable.

represent, X is alkoxy, the oxygen atom For a good stability of the colors of a nouns Siloxyrestes (-O- Si =), Y is a hydroxyl, on various cellulosic materials is the alkoxy, alkyl or aryl group, Z is an alkoxy, Concentration of the aminoalkylsilicon compounds, alkyl or aryl radical, c is 1 or 2, is not particularly important in the solutions. A comparison b equals 0 or 1 or 2 and (c + b) is no greater than 3 15 reduction from the initial value of 5 weight, or a compound produced from a metal complex of such a percentage to 1 weight percent. Reduction from 3.0 percent by weight to 0.6 percent by weight - The aminoalkyl silicon compounds can be reduced to percent of the silicon compound that was actually deposited by wet means following the usual dyeing and printing processes or from an aqueous 20. However, there was little or no sub-means as a finish applied to the dyed and dried fabrics, which differed in the washability of the fabrics in question. Most of the dye, end products. The concentration of the printing and finishing processes can be modified in such a way. The dye fixing agent can be selected so that 0.1 to, that each of the two aftertreatments can be carried out before more than 5.0 percent by weight of silicon compound. Generally it is 25 on the material that is deposited. With the more convenient, a wet process directly to most nouns dyes can already be joined by normal drying and printing. 0.1 to 2.0 percent by weight a good color fixation The difference between the application to be effected. The amount of dye fixing agent wet and the application from an aqueous one also depends on the particular hydrophilic or agent is that in the first case the fixing 3 ° hydrophobic nature of the cellulose-containing substance. Medium during the dyeing or printing process. A material treated in this way is then applied, but dried in one operation, which in many cases is followed by dyeing or printing in the air. The fixation can. Drying at elevated temperatures can be carried out with this procedure without intermediate effects, however, that the deposited silicon drying is applied to the substrate, the compound is even better bonded to the material while it is still moist from dyeing or printing.

is. Otherwise, the fixing agent is used as drying the aminoalkyl silicon compound

Final treatment on a base can even be done in seconds if the substance is the

brought, which has been dyed or printed beforehand and then withstand the required higher temperatures, has been dried. The dye fixation is here 40 is preferably at temperatures of 95 to 18O ⁰ C

a separate period from dyeing or printing and a drying period of a few minutes

dependent process step. to half an hour depending on the dyed material

The aminoalkyl silicon compounds are prepared beforehand. Drying can also be done under the

preferably applied by doing the dyed otherwise usual drying processes.

Material in an aqueous solution of the aminoalkyl 45 textiles and natural fibers on which

silicon compound dips. However, they can be used with success in the method according to the invention

also z. B. by spraying or by means of a padder, are z. B. cotton, linen, ramie, hemp, jute,

Instruct. One can check the solubility of aminoalkyl wood cellulose, paper, regenerated cellulose art

silicon compounds in aqueous solutions by silk, z. B. viscose and copper rayon,

Increase suitable additives or by introducing 5 ° The group necessary in the dye fixative can

appropriate groups into the aminoalkyl silicon molecule. Component of an aminoalkylalkoxysilane, an amino

Emulsions of the dye fixing agents can also be alkylpolysiloxane or a copolymer or

can be applied. a simple mixture of an aminoalkylpoly-

A more even distribution of the dye-fixing siloxane with one or more other siloxanes

by means of the colored or printed material 55. These connections do not have to be pure

obtained when wetting agents are added or form, crude hydrolyzates or

Solvents are used, which with the amino-aqueous or aqueous-alcoholic solutions of the

alkyl silicon compound does not react. Silicon compound can be used.

Suitable solvents for this are, for. B. Alcohols Aminoalkylalkoxy which can be used according to the invention

and ether alcohols such as ethanol, propanol, isosilanes are for example the following:

propanol, methoxyethanol and ethoxyethanol. For 0-methyl-y-aminopropyltriethoxysilane,

Increase in solubility have become monobasic. . _1x ..f.,.,

Acids such as formic acid, acetic acid, propionic acid, y-ammopropy triathoxysilane,

Lactic acid, gluconic acid and glycolic acids, as well as y-ammopropyltripropoxysilane,

Carboxylic acids, such as diglycolic acid, have proven their worth. S ₃ y-aminopropylmethyldiathoxysilane,

Mineral y-aminopropylethyl diethoxysilane,

acids and aromatic carbon aminopropylphenyl diethoxysilane as solvents,

Hydrogen, such as benzene, toluene and xylene, added ci-aminobutyltriethoxysilane,

(5-aminobutylmethyl diethoxysilane,

<5-aminobutylphenyl diethoxysilane,

y-aminoisobutylmethyl diethoxysilane,

y-aminobutyltriethoxysilane,

y-aminobutylmethyl diethoxysilane,

N - ^ - Carbäthoxyäthyl-y-aminopropyltriäthoxy-

silane,
Ny-aminopropyl-ö-ammobutylmethyl diethoxy-

silane,
Ny-aminopropyl-y-aminopropyltriathoxy-

silane,
N-zJ-Aminoathyl-y-aminopropyltrimethoxy-

silane,

N - ^ - cyanoethyl-aminobutyltriethoxysilane,
Ny-triethoxysilylpropyl-pyrrolidine,
Ny-triathoxysilylpropyl ^ S-dimethyl-

pyrrolidine,
N-phenyl-N-methyl-y-aminopropyltriethoxy-

silane,

N-phenyl-N-methyl-o-aminobutyltriethoxysilane,
N-methyl - ^ - methyl-y-aminopropyltriethoxy-

silane,

Bis (y-triethoxysilylpropyl) imine,
Bis (/ 5-methyltriethoxysilylpropyl) imine,
Ν, Ν-dimethyl-y-aminopropyltriethoxysilane,
N-naphthyl-N-methyl-y-aminopropyltriethoxysilane,
N- (Furfuryl) -y-aminopropyltriethoxysilane.

Aminoalkylalkoxysilanes and processes for their preparation are known. Silanes, the 2-amino nitrogen atoms can also contain by reaction of a diamine with the corresponding chloroalkylalkoxysilane getting produced.

The silane monomers that can be used form stable aqueous solutions with organic compounds. This is a particularly desirable property for sizing. In aqueous solution hydrolyze the alkoxy groups so slowly that the silane monomers are initially only soluble in water Aminoalkylpolysiloxanes are converted. Aqueous mixtures of such polysiloxanes with water-soluble ones organic compounds are sufficiently stable to be used in the textile industry for dyeing and finishing to be used satisfactorily.

The aminoalkylpolysiloxanes which can be used according to the invention can be linear, cyclic or crosslinked. The crosslinked aminoalkylpolysiloxanes are substituted by hydrolysis and condensation of trialkoxy Silanes are readily available and can contain small amounts of silicon-bonded hydroxyl groups or silicon atoms contain bonded alkoxy groups.

Crosslinked aminoalkylpolysiloxanes which practically no longer have any silicon-bonded alkoxy or hydroxyl groups can be produced by complete hydrolysis and condensation of an aminoalkyltrialkoxysilane. Polymers which still contain considerable amounts of alkoxy groups can also be prepared from the silanes used as starting material above by partial hydrolysis and complete condensation. Polymers with a considerable content of residual silicon-bonded hydroxyl groups can be obtained by practically complete hydrolysis and only partial condensation of the above-mentioned silanes. Polysiloxanes of the above type generally correspond to the following formula: R ' Za

N - R - Si - O

3-d

R "

R, R 'and R "therein have the above meaning, Z stands for hydroxyl or alkoxy groups and d is

ίο O to 2, preferably O to 1.

Such polymers are e.g. B. y-aminopropylsiloxane, (S-aminobutylpolysiloxane and related hydroxyl and hydrolysates containing alkoxy groups and condensates of these polymers.

Cyclic and linear aminoalkylpolysiloxanes are obtained by hydrolysis and condensation of dialkoxy-substituted Obtain silanes. They can be represented by the following formula:

"R 'Y

I i

N —R —Si —O -

R "

R, R 'and R ″ therein have the above meanings, Y is an alkyl or aryl radical, and η is an integer of at least 3. For cyclic polysiloxanes, η has average values of 3 to 7, for linear polysiloxanes higher values. Typical cyclic polymers are, for example, the cyclic tetramers of γ-aminopropylmethylpolysiloxane and <5-aminobutylmethylpolysiloxane.Linear polymers are, for example, γ- aminopropylmethylpolysiloxane, γ-aminopropylethylethylpolysiloxane, δ -aminobutylmethylpolysiloxane, in which one bis three alkyl, aryl, alkoxy or hydroxyl groups are bonded to the terminal silicon atoms. γ-aminopropylethylpolysiloxane endblocked by monoethoxy groups, γ-aminobutylmethylpolysiloxane endblocked by methyldiethoxysyl groups and a monoethoxydimethylsilyl group end-blocked y-aminopropylpolysiloxane by monoethoxydimethylsilyl groups are suitable Amine oalkylpolysiloxanes and silicon compounds which have alkoxy groups bonded to silicon, or by mixed hydrolysis and condensation of trialkylalkoxysilanes with aminoalkylalkyldiethoxysilanes or aminoalkylaryldiethoxysilanes. Polymers end-blocked with hydroxyl groups can also be obtained by heating linear or cyclic aminoalkylpolysiloxanes with water.

Mixed polysiloxanes which are suitable for the process according to the invention can contain siloxane units, which have one of the groupings explained above, as well as one or more other hydrocarbon-substituted Contain siloxane units of the following formula:

Γ W _e

W - SiO,

in which W and W 'are hydrocarbon radicals and e is an integer from 0 to 2.

These copolymers can by mixed hydrolysis and condensation of aminoalkylsilanes with

other hydrocarbon-substituted silanes or by an equilibrium reaction of a mixture from aminoalkylpolysiloxanes and other hydrocarbon-substituted silanes. Linear copolymers can also contain alkyl, aryl, hydroxyl and alkoxy radicals at the ends of the molecule exhibit.

The Aminoalkylsüiciumverbindungen can also in the form of their metal complexes, for example their Cobalt complexes, but preferably their copper and chromium complexes, are used. Copper complexes can e.g. B. by reaction of the silicon compounds with compounds such as copper chloride, acetate, sulfate, hydroxide or stearate will. These complexes can be added ready-made to the aftertreatment bath or they can be added in situ in the Post-treatment bath are formed.

The following examples illustrate the different non-complex Aminoalkylsüiciumverbindungen indicated by code numbers. The indicators go from Table I.

Table I.

Table I (continued)

Code number des
Fixative

Chemical name

35

45

y-aminopropyltriethoxysilane

ό-aminobutyltriethoxysilane

Copolymer of γ-aminopropyltriethoxysilane and phenyltriethoxysilane (30% solids content)

30% ethanol solution of γ-aminopropylpolysiloxane (Homopolymer; 30% solids content)

y-aminopropylmethyl diethoxysilane

Copolymer of γ-aminopropyltriethoxysilane and phenyltriethoxysilane (30% ethanol solution)

N-phenyl-N-methyl-y-aminopropyltriethoxysilane

Interpolymer silicone oil made from 95.2% trimethylsiloxy endblocked Dimethylsiloxane and 4.8% δ-aminobutylmethylsiloxy groups

Homopolymer of <5-aminobutylmethylpolysiloxane

Copolymer silicone oil made from 75% trimethylsiloxy end-blocked dimethylsiloxane and 25% o-aminobutylmethylsiloxy groups

Copolymer silicone oil made from γ-aminopropyltriethoxysilane and vinyltriethoxysilane (25% resin solids)

Copolymer silicone oil made from γ-aminopropyltriethoxysilane and amyltriethoxysilane (30% resin solids)

Cobalt chelate of y-aminopropyltriethoxysilane (17% in H ₂ O)

83.3% trimethylsiloxy endblocked copolymer silicone oil Dimethylsiloxane and 16.7% γ-aminopropylsiloxy groups

y-aminopropylpolysiloxane; the homopolymer of y-aminopropyltriethoxysilane (solids content 50% in ethanol)

Code number of the fixative

34 35

36

37 38 39 Chemical name

N-naphthyl-y-aminopropyltriethoxysilane Copolymer of 50% trimethylsiloxy end-blocked dimethylsiloxane and 50% <5-aminobutylmethylsiloxy groups Copolymer of 70% trimethylsiloxy end-blocked dimethylsiloxane and 30% N, N-bis-0? -Hydroxyethyl) -o-aminobutylmethylsiloxy groups

Copolymer of 27% trimethylsiloxy end-blocked dimethylsiloxane, 40% Diphenylsiloxy groups and 33% (5-aminobutylmethylsiloxy groups Copolymer of 68.5% trimethylsiloxy end-blocked dimethylsiloxane, 25% Diphenylsiloxy groups and 6.5% (5-aminobutylmethylsiloxy groups N-y-triethoxysilylpropylpyrrolidine

hydrochloride
N-j3-cyanoethyl- (5-aminobutyltriethoxy-

silane
RN-dimethyl-γ-aminopropyltriethoxysilane-hydroiodide

β-methyl-γ-aminopropyltriethoxysilane bis - (/ S-methyltriethoxysilylpropyl) -imine N-methyl-zS-methyl-y-aminopropyl-

triethoxysilane
N-yS-carbathoxyethyl-y-aminopropyltriethoxysilane

N-jS-Cyanoäthyl-ö-aminobutylmethylpolysüoxan (mainly cyclic compounds)
N - (/ S-furfuryl) -y-aminopropyltriethoxysilane

(5-aminobutylmethyldiethoxysilane o-aminobutylmethylpolysiloxane (crude product, comparable to 9; produced by hydrolysis of 30 (hydrolysis by nonsolvents) As 31, with the exception that δ-aminobutylmethylpolysiloxane, produced by solvent hydrolysis, contains incompletely condensed and therefore probably silicon-bonded ethoxy groups (Solid content in ethanol)
Aminomethyltriäthoxysilan N-ß-Aminoäthyl-γ-aminopropyltriäthoxysilan

Copolymer of 60% trimethylsiloxy end-blocked dimethylsiloxane and 40% N-iS-aminoethyl-y-aminoisobutylmethylsiloxy groups
N, N-bis - (/? - hydroxypropyl) -y-amino-

propylsiloxane
N, N-bis (j8-hydroxystearyl) -y-aminoisobutylmethyldiethoxysilane, N-octyl-y-aminoisobutylmethyldiethoxysilane

The reference refers to the dye names given in the following examples "C.I." on Color-Index, 2nd edition (1956), and the reference "Pr." To the prototype no. in technical Manual of the American Association of Textile Chemists and Colorists, 1958 edition.

example 1

Pieces of white, boiled, and bleached cotton cloth were put into a liquor that was 1 percent by weight Metromin RF Rubin 3BLL (Pr. 491), i.e. containing a direct dye, immersed at 82 ° C. The ratio of bath volume to the volume of the cloth was 40: 1. After 20 minutes, 15% Sodium chloride, based on the weight of the cloth, added to ensure complete transfer to achieve the color from the liquor on the cloth. After another 15 minutes the colored ones became Pieces of cloth removed and rinsed with water.

The dyed cotton towel pieces were placed in a series of solutions of equal parts water and isopropanol each containing 1 percent by weight of dye fixatives 1, 4, 8, 9 and 10 (Table I). Each of these solutions also contained 1% acetic acid. The solutions with the pieces of cloth were stirred for 15 minutes at 20 ° C, it removed the cloth pieces, rinsed with cold water and dried for 5 minutes at 121 ⁰ C. After drying, a piece of white cotton cloth was placed on each of the pieces of cloth treated in this way. These samples were then separately immersed in water at 71 ° C., stirred for 1 hour, then taken out, rinsed and dried. The amount of color that had passed from the dyed material to the white cloth and the color of the water in which the cloth pieces were immersed were compared with the corresponding results obtained from a dyed cloth piece that had not been post-treated with the dye fixing agent . In all cases the aminoalkyl silicon compound provided increased dye stability. The wash resistance of the cloth samples ranged from that of the untreated cloth pieces (worst quality) to those of cloth samples that had been treated with fixing agents 1, 4, 9 and 10 to that of cloth samples that had been treated with fixing agent 8 ( best quality).

Example 2

Five test pieces made of viscose rayon, which were previously placed in a reel skid with a direct red, turquoise, Navy blue, brown and copper red dyes were individually stained with the dye fixatives 1, 3, 4, 8, 9, 10, 11 and 12 are covered. A 5% solution was used for these treatments each of the dye fixatives in a water-isopropanol mixture 50:50 containing 5% acetic acid. The pieces of cloth were each individually in the foulard soaked with a fixative solution up to 65% absorption of moisture and then for 5 minutes dried at 160 ° C.

After the drying process, the washing resistance of the colors was determined using the method from Example 1 certainly. For comparison, a piece of cloth was also used for each of the dyed fabrics that had not been done before treated with dye fixative. At the results in the following table the worst wash resistance appears at the beginning of each column and the best at the end.

Turquoise dye Brown dye Copper red dye Red dye Navy blue dye untreated untreated untreated untreated untreated 11 4th 11 1 8th 9 3 4th 3 11 3 12th 3 11 4th 4th 11 9 9 3 12th 9 12th 12th 1 1 8th 1 4th 9 10 10 10 10 12th 8th 1 8th 8th 10

Example 3

Three copper complexes of dye fixative were prepared using the following amounts of Silicon compounds and copper salt were used:

Components complex
9-A complex
9-B complex
9-C Mole of dye fixing
by means of 9 1.0
1.0 1.0
0.5 0.5
1.0 Moles of CuCl ₂ · 2 H ₂ O ....

the mixtures were homogeneous. The mixtures were then diluted with water to a solids content of 1%. A part of this solution was applied as such to rayon or rayon dyed directly in navy blue. Then I ¹ I ₁ acetic acid was added to the remainder of the solution. It was then applied to a second set of samples of the same fabric. These two solutions had the following pH values:

60

The copper chloride was dissolved in water and then dye fixative 9 to one with stirring Total solids content of 20% in the water added. Heat developed, and so did the green copper salt solution turned blue. After several hours of stirring

complex Pjj without added acid Pjj after addition of acid 9-A
9-B
9-C 10.30
10.65
9.30 4.30
4.98
4.00

Without acid, all three complexes gave cloudy solutions, whereas with acid all solutions were clear and were blue.

309 670/251

In each case, the dyed cloth samples were treated in a padder up to 60% moisture absorption and 0.6% by weight of precipitation on the cloth. The pieces of cloth were then dried ^{at 149 ° C. for 10 minutes.} The color fixation examined by the above method was excellent. All three complexes gave the same effect as acidic solutions. The non-acidified samples from 9-A were slightly inferior. In addition, this complex had the most cloudy solution and the coarsest dispersion.

Example 4

Using the starting materials listed below, a number of chromium complexes of ¹ S was prepared.

while 10-A, 10-B and 10-C did not have the same effectiveness own. The commercially available fixative, however, proved to be extremely unsatisfactory, than it the tint of the fabric from the original scarlet red to a deep wine red with a blue tint changes. All other samples kept their original colors.

Table II

complex
description 1 Compilation 9-A ' 1 Moles of CrCl ₃ to 1 mole of fixative 9 9-B ' 1 Moles of CrCl ₃ to 2 moles of fixative 9 9-C 1 Moles of CrCl ₃ to 3 moles of fixative 9 10-A Moles of CrCl ₃ per equivalent of NH ₂ 1 in fixative 10 10-B Moles of CrCl ₃ per equivalent of 2 NH ₂ 1 in fixative 10 10-C Moles of CrCl ₃ per equivalent of 3 NH ₂ in fixative 10

Applied fixative Degree of going out
and staining *) none 4th 9 0 customary 0 9-A ' 0 9-B ' 0 9-C 0 10-A 4th 10-B 3 10-C 4th

*) Quality grade 4 = strong fading and coloration. Quality grade 3 = medium run out and rubs off. Quality grade 2 = easy going out and rubbing off. Quality grade 1 = slight loss of color and coloration. Quality grade O = no going out, no rubbing off.

Example 5

A. The wash resistance of directly dyed fabrics is determined by methods that use the

When using fixative 9, the typical stress during the application of the Chromium chloride dissolved in water and reproduced the amino substance. Some substances need, for example, an alkyl silicon compound added with stirring. It only developed resistance in cold water warmth. The solutions that show one while others are in hot water or hotter Having levels of 20% solids would need to be permanent under 35 soapy water. There hot soaps stirring cooled down. The complex fixatives 9-A ', generally meet the highest demands 9-B 'and 9-C were opaque dark green spots which were washable in the present Liquids. When diluted with water, hot soapy water was used as an example. In general all samples cloudy dispersions. When adding is the addition of fixative in the manufacture of Acetic acid formed clear dark green solutions. 40 fabrics increased when a greater wash resistance

This is required when using fixative 10. It therefore became the amount of fixing chromium chloride in water and the aminoalkyl silicon agents 9 and its metal complexes in the experiments compound dissolved in isopropanol and added to the chromium chloride solution. Developed in all cases

this example about the relatively low concentrations, as they are in the previous two

warmth. The complex dye fixative 10-A was to be applied and used in hot and 45 play

a dark green solution, whereas 10-B and 10-C formed dark green dispersions. All contained a solids content of 20% and all formed cloudy dispersions on dilution with water. When adding clear solutions resulted from acetic acid.

These metal complexes were used as a fixative for a scarlet red direct-dyed viscose gabardine cloth used. The usual finishing agent for such a wipe is a commercially available amine resin, the was also examined. The comparison tests 55 deal with:

cold water gave excellent results. The concentration of 1.0% is the same, as used industrially for an amine resin fixing agent, which is generally believed to be the best Overall resistance or authenticity of rayon fabrics causes.

In a first series of experiments, three directly dyed rayon fabrics were made with aqueous solutions of the following Connections or compilations be

were in the padder at 0.5%. Solid concentration in the solution carried out. As an additional control a cloth sample was treated with fixative 9.

The treatments were carried out as in the previous examples using aqueous solutions which contained 1% acetic acid, followed by drying and curing ^{at 149 ° C. for 10 minutes.} The experiments to determine the going out of color were made at 71 ⁰ C.

The results of these tests are shown in Table II. It follows that 9-A ', 9-B 'and 9-C are just as effective as fixing agents as 9 alone and the commercially available fixing agent, 1% fixative 9 + 1% acetic acid, 1% fixative 9-C (copper complex) + 1% acetic acid,

1% fixative 9-B '(chromium complex) + 1% acetic acid,

1% fixing agent 17 + 1% acetic acid, 1% commercial amine resin fixing agent, untreated.

These treatments were carried out in the same way as in the previous examples. After this Drying, a first series of samples was

examined by them, that 0.5% commercial soap flakes contained in water at 49 ⁰ C for 30 minutes long stirred, followed rinsed twice at 41 ⁰ C with water and ironed with an iron.

A second series of tests was carried out by applying 3% solids of the above compositions to the dyed fabric. These samples were washed in soap solutions at 60 ^° C., then rinsed with warm water and ironed.

A third series of tests was carried out with samples containing 3% solids of the above lists done by soaking them in a water solution containing 0.5% soap and 0.5% sodium carbonate contained, stirred for 45 minutes at 71 ° C. The grades of these samples according to the table II given scale are listed in Table III.

When designating the quality grades of the cloth samples, there were great difficulties because they were very different Tints had to be taken into account. In addition, the degree of going out could not be named as the original color of the cotton specimens from the subsequent exposure the soap solution has been at least partially removed. The designation with grades was made so that the amount of color removed from the specimens and the coloring of the white cotton specimen, as far as it was still visible on it, were determined. The numbers indicate that the fixing agents 9 and 17 have the same or better results than the commercial fixing agent deliver.

Table III

applied to cotton-rayon fabrics and then under various conditions with fixative 9 treated.

2% calcomin brilliant yellow cone. (CI. 365), 3% Calcodur 8 BL (C. I. 278),

2% Calcodur resin fast red 3 B (Pr. 491), 2% Calcodur resin fast blue 6 G cone. (Pr. 432),

3% Calcomin-Diazo-Black BHD (self-tinting) (Pr. 401),

2% Calcodur resin real gray 2 G, 2% Calcodur turquoise GL (Pr. 278).

The fixatives were used both alone and as metal complexes, in combination with thermosetting ones Finishing agents and, at reduced concentrations, with resin-free mixtures. These combinations When compiling the fixatives are listed below and have been used with all seven dyes made. Unless otherwise stated in the following experiments, was the textile material treated in a padder at 80% moisture absorption and dried at 149 ° C for 10 minutes.

Rayon fabrics

Applied
fixer

dye

Soap at 49 ° C

Loss of color in

To wash

Soap l alkali

at 6O ⁰ C at 71 ⁰ C

35 Treatment A:

30.0% urea formaldehyde resin, 1.5% fixative 9,
1.0% CuCl ₂ -2 H ₂ O,
1.0% acetic acid.

Treatment B:

1.5% fixative 9,
1.0% CuCl ₂ -2 H ₂ O,
1.0% acetic acid.

none
9-A
9-B '

customary
17th
9

none
9-A
9-B '

customary
17th
9

none
9-A
9-B '

customary
17th
9

turquoise

the same

the same

the same

the same

the same
Scarlet fever

the same

the same

the same

the same

the same
Brown

the same

the same

the same

the same

the same

4th 4th 2 2 2 1 2 2 1 2 1 1 4th 4th 3 1 3 2 2 3 1 1 0 1 4th 4th 0 0 0 0 0 0 0 0 0 0

Treatment C:

1.0% fixative 9,
1.0% acetic acid.

45 Treatment D:
Complete separation of the dye

3% fixative 9 }.

3% acetic acid based on the weight of the fabric;

Volume ratio of fabric to bath = 1:10; Heating the fleet of 20 ⁰ C to 60 ° C within 30 minutes; extracted; Dried at 121 ^° C. for 5 minutes.

Treatment F:
Not treated.

55 cotton

Example 6

The following seven direct dyes known to be difficult to fix have been made Treatment G:

20.0% urea-formaldehyde resin, 1.5% fixative 9,
1.0% CuCl ₂ -2 H ₂ O,
1.0% acetic acid.

Treatment H:

^e 5 10.0% dimethylolethylene urea, 1.5% fixing agent 9,
1.0% CrCl ₃ -6 H ₂ O,
1.0% acetic acid.

15th

Treatment I: 10.0% methylated methylolmelamine, 3.2% MgCl ₂ · 6 H ₂ O - catalyst, 1.5% fixative 9, 1.0% acetic acid.

Treatment J: Full separation of the dye fixing agent 3% 9 3% acetic acid J ^inscribed ° gene on the fabric weight;

Volume ratio of fabric to bath = 1:10; Heating the fleet of 20 ° C to 60 ⁰ C within 30 minutes; extracted; Dried at 121 ° C for 5 minutes.

Treatment K: Complete separation of the dye 1% fixative 9 1% acetic acid volume ratio of fabric to bath = 1:10; extracted; Dried at 121 ° C for 5 minutes.

Treatment L: Not treated. 16

Table V Soap Experiment - Cotton

Cloth dye (abbreviated)

Calcomo yellow ...

Calcodur Red

Calcodur resin red. Calcodur turquoise .. Calcodur resin blue Calcomin black Calcodur gray ...

2 of rubbing off and I. J 2 Going out 0 3 Degree 0 I ^H 1 4th 1 2 0 1 none y G O 2 0 3 4th 0 0 0 1 4th 1 1 1 4th 4th 0 0 2 4th 2 4th 1 4th 4th

based on the weight of the fabric; Table VI Hot Water Test - Rayon

Cloth dye (abbreviated)

Degree of coloration and fading

no! A | B.

Calcomo yellow ...

Calcodur Red

Calcodur resin red. Calcodur turquoise .. Calcodur resin blue Calcomin black

4th 0 4th 1 4th 0 4th 0 4th 0 4th 0 4th 0

1 0 0 1 3 3 0 0 0 0 0 0 0 0 0 0 2 2 0 0 0

Table VII Soap Trial - Rayon

Degree of coloration and fading

The fabrics were tested for color fastness by immersing them ^{in water for 1 hour at 71 °} C. (hot water tests) and the fabric together with a white cotton cloth in water containing 0.5% of a commercial soap flake product for 30 minutes at 60 ° C (soap experiment). The 30 Calcodur gray results according to the quality scale of Table II are listed in Tables IV, V, VI, and VII below.

The experiment in hot water (Table V) shows

that all treatments are the same for all dyes

Have effectiveness when it comes to cotton fabgekür

acts. Table VI shows similar results with none] A | B | C I D

dyed rayon fabrics, except that Treatments C, D, and E are on Calcodur Red only caused poor fixation and treatments C and D on calcomin black only very much were moderately effective.

The soap washing test, which was carried out under severe conditions, shows that the The effectiveness of the fixation treatments has great gradations, depending on the dye and the composition depend on the treatment solution. Calcodur red, calcomin yellow and calcomin black were found both on cotton (Table V) as The following direct dyes were found on cotton

also used on rayon (Table VII) as the most difficult 50 and rayon fabrics which afterwards with fixable. All colors have been treated by compound 9 fixatives:

Calcomo yellow ...

Calcodur Red

Calcodur resin red. Calcodur turquoise .. Calcodur resin blue Calcomin black Calcodur gray ...

B. C. 2 3 2 3 0 1 2 2 0 1 3 2 0 1

Example 7

sufficiently fixed when used in conjunction with the urea-formaldehyde resin finishing agent became.

Table IV

Hot water test - cotton

Cloth dye (abbreviated)

Calcomo yellow ... Calcodur red .... Calcodur resin red. Calcodur turquoise .. Calcodur resin blue Calcomin black Calcodur gray ...,

3rad of rubbing off unc ι! j 0 Going out 0 0 no G TT 1 0 4th 0 0 0 0 4th 0 0 0 0 4th 0 0 0 0 4th 0 0 0 0 4th 0 0 0 4th 0 0 3 0 0

Pontamine real yellow EFL, Pontamine real orange DL, Pontamine real brown BRL (Pr. 47), Pontamine Real Red 3 BLN (Pr. 491),

Pontamine Real Red 6 BL (Pr. 428),

Pontamine real violet 4 BL (Pr. 429),

K 60 Pontamine real blue ML,

Pontamine real blue 3 RLN, Pontamine real blue 3 GL (Pr. 432).

The following aqueous solutions were applied to the colored rayon samples

0 0 0 0 0 0 0 to treat it.

They were treated in a padder at 94% moisture absorption and then for 10 minutes at Dried at 149 ° C.

Treatment A:

30.0% urea formaldehyde resin, 1.5% fixative 9,
1.0% acetic acid,
1.0% CuCl ₂ -2 H ₂ O.

Treatment B:

30.0% urea-formaldehyde resin paste, 2.0% fixative,

1.0% acetic acid, 1.0% 2-amino-2-methyl-1-propanol hydrochloride.

Treatment C:

30.0% urea-formaldehyde resin paste, 2.0% commercial amine resin fixative, 1.0% 2-amino-2-methyl-1-propanol hydrochloride.

Treatment D:
No.

30th

The following aqueous solutions were used, with which the cotton samples were impregnated with 70% moisture absorption in a padder. This was followed by ^{drying at 149 °} C. for 10 minutes.

Treatment E:

1.5% fixative 9,
1.0% CuCl ₂ -2 H ₂ O,
1.0% acetic acid.

Treatment F:

2.0% fixative 9,
2.0% acetic acid.

Treatment G:

2.0% commercial amine resin fixative. Treatment H:

No.

40

The resistance of the color was determined according to the soap washing test, which is described in Example 6, established. The grades according to the scale in Example 4 are listed in Tables VIII and IX and indicate that the fixing agent 9 is completely in the effectiveness of the commercially available fixing agent is equivalent.

Table VIII Rayon

55

6o

Table IX
cotton

Cloth dye
(abbreviated) Degree
no of the at
Output
A. to dye
jhens
B. and
C. Yellow EFL 4th 0 0 0 Orange DL 4th
4th 0
1 1
2 0
1 Brown BRL 4th 0 0 0 Red 3 BLN 4th 1 1 1 Red 6 BL 4th 0 0 0 Violet 4 BL 4th 0 0 0 Blue ML 4th 0 0 0 Blue 3 RLN 4th 0 0 0 Blue 6 GL

Cloth dye
(abbreviated) Degree
no of the Ab
Output
E. to dye
shens
F. and
G Yellow EFL 4th
4th
4th 1
2
1 1
2
2 1
2
1 Orange DL 4th 1 1 1 Brown BRL 4th 2 2 2 Red 3 BLN 4th 0 0 0 Red 6 BL 4th 1 1 1 Violet 4 BL 4th 1 0 1 Blue ML 4th 0 0 1 Blue 3 RLN Blue 6 GL

If fixing agents of the types 35, 36, 37, 38 and 39 are applied to directly dyed fabrics in the manner described in Example 2, good Wash resistance and resistance to going out can be determined. Others can too Aminoalkyl silicon compounds can be used as dye fixing agents, e.g. B. N-jS-aminoethyl-y-aminopropyltrimethoxysilane Contained in various degrees of purity.

35

Claims (4)

PATENT CLAIMS: 1. Process for fixing direct dyes on cellulose-containing materials that have been dyed or printed with them! Material, characterized in that the dyed or printed material is coated with an aminoalkylsilicon compound containing at least one functional group of the formula R ' NO R " - Si — X ₄ _ _c _ _ft where R is a divalent hydrocarbon group having at least 3 carbon atoms between the nitrogen and silicon atom, R 'and R "hydrogen atoms or alkyl, aminoalkyl, Cyanoalkyl, hydroxylalkyl, carboxyalkyl, carbalkoxyalkyl or aryl radicals or the monovalent radicals group R-Si- X represent, X is an alkoxy or the oxygen atom of a siloxy radical (—O - Si =), Y is a hydroxyl, alkoxy, alkyl or aryl group, Z is an alkoxy, alkyl or aryl radical, c is 1 or 2, b is equal to 0 or 1 or 2 and (c + b) is not greater than 3, or is made up of a metal complex of such a compound. 309 670/251 19 20 2. The method according to claim 1, characterized in an optionally acidic aqueous and / or draws that one complexes up a copper or chromium alcoholic solution or suspension the silicon compound is used. wearing. 3. The method according to claim 1 or 2, there- 4. The method according to claim 1 to 3, characterized characterized in that the aminoalkyl 5 is characterized in that the material is an silicon compound or their complex is heated from closing. © 309 670/251 8.63