JPS6021986A - Improvement in fastness of dye or fluorescent brightener on base material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION 1) Industrial Field of Application The present invention relates to a post-treatment method for improving the fastness of dyes and light brighteners on substrates containing hydroxy, amino and thiol groups. .

2) Prior Art The following subject matter is known from British Patent Application No. 2099007 and corresponding US Pat. No. 4,439,203 (the disclosures of which are incorporated herein by reference). That is, the fastness of dyes and fluorescent brighteners, in particular direct dyes and reactive dyes, on hydroxy group-containing substrates can be improved by combining monofunctional or polyfunctional primary or secondary amines with cyanamide, dicyandiamide (DCDA), reaction products A) with guanidine or pyguasonine (herein included up to 50 mol % of cyanami-l-', DCDA, guasonine or biquanidine or with socarponic acids or mono- or no-esters thereof; The product A) is worked up with an initial condensate obtained by reacting the products A) containing reactive hydrogen atoms bonded to the nitrogen system and the shrimp halohydrins or their precursors B), followed by a crosslinking step. It can be improved by doing.

When neutralized with an alkali, such as that disclosed in the above-mentioned British patent application, and optionally acidified in the presence of a water-soluble polymer, this forms a stable dispersion and an incipient condensate. It was found that the stability of

The following facts were also discovered. That is, post-treatment with the initial condensate, whether for neutralization or acidification, is effective against substrates containing amino or thiol groups,
In particular it improves the fastness of dyes on wool and sets.

3) Means and effects for overcoming the problem The present invention thus provides a method for improving the fastness of dyes or fluorescent brighteners on substrates comprising fibers containing hydroxyl, amine or thiol groups. This method may be used to prepare the reaction product AX with a monofunctional or polyfunctional primary or secondary amine didine or biguanidine, in which up to 50 moles of cyanamide, DCDA, guanidine or biguanidine are reacted with their dicarboxylic acid. ? by reacting the products A) with nitrogen-bonded reactive hydrogen atoms) and shrimp herrohydrins or their precursors B) and then characterized in that the initial condensate obtained by acidifying the reaction mixture is applied onto a dyed, printed or brightened substrate and then subsequently or simultaneously with the application to the substrate a crosslinking step is carried out. shall be.

The term "initial condensate" shall mean a reaction product that is water-soluble, remains in a shrunk, non-dulled state, and is capable of further crosslinking.

Component A) is preferably cyanamide, nocyandiamide (DCDA) or guanidine, more preferably DCD
It is a reaction product of A and polyalkylene/polyamine.

Preferably, the polyamine is of formula I.

RRN-(-z -x+V-z -NRRI, where each R is independently hydrogen or unsubstituted or hydroxy, C
1-10 alkyl group monosubstituted with 1-4 alkoxy or cyano, n is a number from 0 to 100, 2 or each 2 is independently B) C1-4 when o;
is alkylene or hydroxyalkylene, and furthermore, Xl or each X is independently n) 1, -0-
, -8- or -NR- (R has the meaning defined above)
, provided that the amine of formula 1 has at least one reactive -Nu- or -NH2 group.

More preferably, each 8 is hydrogen, 11 is O-4, X is NH or -NCH3-, and each 2 or each 2 is independently n
>0, it is C1-4 alkylene.

Particularly preferred compounds are diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 2-aminoethyl-3-aminoglobylamine, diethylenetriamine and N,N-bis-(3-aminoethyl)methylamine.

Component A is known, for example British patent 657753,
US Patent No. 2,649,354 and UK Publication Application No. 207,000
It can be manufactured according to the method described in 6A. It is suitable to react the amine in free base or salt form with the other starting materials under anhydrous conditions at elevated temperature, optionally in the presence of a non-aqueous solvent. Preferably the reaction is carried out in the presence of a solvent.
It is carried out at a temperature of 160° C., and for many combinations of reagents, ammonia is released. The reagent is preferably reactive -NH or -NI (0.1 of cyanamide, DCDA, guanidine or biguanidine per mole of two groups).
It is preferably reacted at a molar ratio of ~1 mole, and further DCDA
When reacting with a polyalkydene polyamine, the molar ratio of the reactants is more preferably from 2:1 to 1:2, especially about 1:1:
1 is preferred. The reaction product can be in free base form or can be converted wholly or partially into salt form by adding an acid, preferably sulfuric acid.

The product (A) is a mostly colorless viscous liquid or solid, which is basic and water-soluble in either the free base or salt form, and is also a reactive compound bound to nitrogen. Contains hydrogen atoms.

Up to 50 molt, preferably up to 20 molt of DCDA or other reagent to be combined with the amine is added to the dical? These acids can also be di-substituted with their 1- or 2-esters. Suitable acids may include adipic acid, oxalic acid and terephthalic acid, for example in the form of their dimethyl esters. It is carried out at a temperature of room temperature to 100°C, preferably 40°C or less. Preferred reagents are epichlorohydrin and dichlorohydrin, CI
CH2, CHOH, CH2Cl, more preferably epichlorohydrin. Ingredients for shrimp halohydrin'
The molar ratio of A) is preferably 1:0.1-0.5, more preferably 1:0.1-0.4, particularly preferably 1:0
．． It is 1 to 0.29.

Where component A) is a preferred l:1 molar reaction product of DCDA and amino/DCD to shrimp halohydrin
These molar ratios of A are much higher (ie less shrimp is used) than those exemplified in UK Patent Application 2099007. The initial pH of the reaction mixture is adjusted to between 1 and 2 by adding an acid, preferably sulfuric acid.
It is preferable to adjust it to 9.

To prepare the precondensate in the form of a stable dispersion, the reaction product is optionally soaked in a water-soluble polymer, such as polyvinyl alcohol, etc. Acidification in the presence of lyacrylamide or hydroxyethylcellulose. The water-soluble polymer can be added to the reaction mixture before acidification or can also be present during the reaction with A) and B). The second alternative method is preferred but should use a water-soluble polymer that is not preferentially attacked by shrimp halohydrin under the reaction conditions used.

Acidification can be carried out by adding inorganic or organic acids, preferably sulfuric acid or fumaric acid, in order to obtain a final pH of 2 to 5, preferably 4 to 4.5. The acidified product is then in the form of a dispersion rather than a solution, which has good chemical stability and long shelf life. The presence of water-soluble polymers is desirable to ensure the physical stability of the dispersion against sedimentation.

If the acidification is carried out with sulfuric acid, the low stability of the sulfate salt results in a stable dispersion without the need to add a water-soluble polymer.

The improved chemical stability of the products according to the invention is due to the use of the products of the invention as well as the corresponding products manufactured according to the method described in UK patent application 2099007 (in each case before storage and at 40°C). Q is demonstrated by carrying out post-processing tests on dyed cotton fabrics (using fresh samples after two weeks of storage). It has been found that the effectiveness of the product of the invention is not affected by this treatment. On the other hand, the product of UK Patent Application No. 2,099,007 is glued and insoluble in thick solutions, whereas dilute solutions lose considerable effectiveness.

The substrate is preferably cellulose, regenerated cellulose or natural polyamide, especially cotton, rayon, wool or silk alone or blended with synthetic fibres. The substrate can be dyed, printed or fluorescently bleached by conventional methods, such as dyeing or photobleaching by exhaustion, followed by heat fixation or cold fixation, or by reactive fixation. In the case of dyes, alkali fixation can be used. The method according to the invention is particularly stable towards reactive and direct dyes when it is applied to cellulosic substrates, and the white metal complex direct dyes, especially the same complex dyes, are preferred. Natural? For lyamides, acidic and metal complex dyes, especially chromium and cobalt complex dyes, are preferred.

The process according to the invention is carried out on a substrate that has been dyed or printed, including any necessary fixing steps. The substrate may be dry or may remain wet, but must not be so wet that it cannot be picked up further. The post-treatment material is applied to the substrate by aqueous medium or short exhaustion, blowing, spraying, foaming, blowing, or other conventional application methods. A preferred method of application is by exhaustion at room temperature to 50°C.

In the exhaust method, when using a long bath ratio (>io:i), the initial condensate in the dye liquor is preferably 0.2
5-311/l, more preferably 0.5-1.5.1i
l/1, whereas for short exhaustion methods amounts of up to 30 g/l are required. (All weights are based on the dry weight of the active ingredient.) Based on the dry weight of the substrate, the amount of precondensate used is preferably 1 to 3% by weight M%, more preferably about 2.5% by weight. 5% by weight of O. The crosslinking step can also be carried out under alkaline conditions in an exhaustion bath, or after applying the exhaustion method under neutral or acidic conditions, or after applying the carbonation method. It can be carried out in a continuous heat curing process. The base material can be dried at, for example, 70 to 120°C, and the final tag can be dried at 1
Crosslinking can be carried out at 30 to 180°C for 30 seconds to 8 minutes.

Particularly preferred direct dyes for use in the process of the invention for dyeing cotton fabrics are: 20. I. Direct Red 80183184.92,95,201
7゜211.218: C, 1, Direct Yellow 39.50.98, 1
06.129: C, 1, Tirek FJ Kan Oret 47
,66.95:C,1,Direct Blue 71.7
7.7'1.80, 85.90, 94°98.217.
251: c, r, direct green; / 27, 31.65+
67°c, r, direct brown l0L111,1
13,1] Ci, 220: C, 1, Direct Black 62,117.118: and particularly preferred reactive dyes are C, 1, Reactive Blue 23 and C, 1, 1, Reactive Blue 79 and 6.

The wash aA fastness of dyes and prints with direct dyes is often insufficient. Most of the dye bound to the cellulose fiber surface is removed from the fiber during repeated washing, and the dye bleed into the washing solution is partially reabsorbed onto the undyed cellulose material. Many attempts have been made to overcome these drawbacks. For example, by complexing the fibers with metal salts, forming dyes on the fibers, treating the dyes and/or fibers with formaldehyde, impregnating them with synthetic resins and post-treatment with cationic auxiliaries, etc. It is. The use of cationic post-processing aids has been found to be particularly effective.

A drawback of all previously used methods is that the results are irregular, although the robustness is indeed improved. Even in the case of cationic post-treatment, the auxiliary agent is removed from the fiber by repeated washing, especially under alkaline conditions and at high temperatures of 50 DEG to 100 DEG C. Loss of the cationic auxiliary causes the dyeing to once again lose its improved wet fastness properties.

It was desired to solve the wet fastness problem by using reactive dyes that form chemical bonds to the fibers. However, the disadvantages of using reactive dyes are as follows. That is, dyes chemically bonded to the fibers have excellent fastness, but after dyeing, the fabric must be thoroughly washed to remove residual rice-fixed dyes that have poor washing fastness @ dried cellulose according to the present invention (by dealing with profiteering)
Improved wet fastness properties, particularly wash fastnesses, are obtained, including washing under alkaline conditions at temperatures of 40 to 90°C, especially at temperatures of 60°C or higher. For example, it can easily withstand repeated washing at 60° C. for 30 minutes using a washing solution containing 5/l/l soap and 29/l soda at a bath ratio of l:50.

When dyeing with reactive dyes, the wash fastness of unfixed dyes can reach almost the same level as that of fixed dyes, thereby eliminating the need to remove unfixed dyes.

For dyeing wool, acidic or metallized dyes are used in the customary manner, followed by post-treatment under mild alkaline conditions. Particularly suitable dyes include, for example: 20.1. acid yellow 1
27 C・■・ Acid Orange 67 C, 1, Acid Red 412, 336, 339, 3
99C,1, Acid Blue 126.296° The wool substrate may or may not be chlorinated.

The treatment of dyed wool substrates according to the invention imparts a certain degree of shrink processability and further improves the wet fastness of the dyeing.

Although alkaline and acidic precondensates can be used for the treatment of both wool and silk, it is preferred to use stable dispersions of precondensates obtained by acidification as explained above.

The following examples illustrate the invention. In the examples, all parts and parts are by weight and temperatures are in °C.

Examples 1 to 4: Preparation example 1 of initial condensate 103 parts of diethylene triamine/and 84 parts of DCDA
is heated to 110°C. At this temperature, an exothermic reaction occurs and further ammonia is generated. The temperature was raised to 150°C and then held at 160°C for 6 hours to complete the reaction, which resulted in the evolution of 34 parts of cyanmonia. Finally, the reaction mixture is cooled to room temperature and powdered.

125 parts of the solid product are dispersed in 80 parts of water containing 0.75 parts of polyvinyl alcohol (Poval 204) and then neutralized to pH 7-7.5 using 96.25 parts of 28% hydrochloric acid at a temperature below 50°. do. The mixture is then raised to 90° C. and further stirred until all solids are dissolved. 250 times this solution was cooled to room temperature, and then 12.5 parts of epichlorohydrin was gradually added while stirring at room temperature.
Make sure the temperature does not exceed 40℃. Stirring is continued for 3 hours, during which time the temperature falls to room temperature, after which 12.5 parts of 85% formic acid are added to obtain a pH of 4-4.5. A milky dispersion is obtained, which is used as a post-treatment agent for the dyeing of cotton wool or silk.Example 2,3 Epichlorohydrin 12.5 m (0.2 mol 17 mol DC)
Example 1 is repeated using epichlorohydrin 6.251B or 25 parts (0,1 and 0.4 mol 1 liter DCDA) instead of DA).

Example 4 Repeat the contents of the first section of the procedure in Example 1. The solid product obtained is dissolved in ice water and neutralized using 50 g of sulfuric acid to obtain a yellow solution with a pH of 7.5-7.8 containing about 55% by weight.

Add 100 parts of this solution to 9 parts of shrimp chlorophyll and 10 parts. Add the fluff over a period of 1 hour at room temperature. . The temperature rises to 35°C and stirring is continued overnight. The final pH of the product was adjusted to between 4 and 4 by adding about 9.5 parts of 50% sulfuric acid.
Adjust to 5. The resulting dispersion of the sulfate salt of the reaction product is stirred until homogeneous. The product is a stable dispersion, which can be used as a post-treatment agent for the dyeing of cotton, wool or silk.

Examples 5 and 6: Post-processing example 5 for direct dyeing of cotton fabric Color Index Direct Blue 2513 Mft
% dyed cotton substrates are treated with a post-treatment liquid at a bath ratio of 20:1. This liquid contains 6% by weight of the dispersion obtained in Example 1, based on the dry weight of the substrate, and 59/l of sodium sulfate (approximately 2.6% by weight active solids, based on the dry weight of the substrate).

Raise the bath from room temperature to 40°C over 5 to 10 minutes.
Hold at 0°C for 5 minutes. Add 4 ml/ll of 30% caustic soda solution to this bath and then keep the bath at 40 °C for a further 25 minutes. Finally, wash the base material with water and then
Dry with. Dyeings with excellent wet fastness properties are obtained.

Example 6 The procedure is repeated as in Example 1, except that no caustic soda is added to the after-treatment bath. After 30 minutes at 40℃, the substrate was
Dry for 5 minutes at 0°C. get similar results.

Examples 7 to 10: Post-treatment of metal complex dyeing of wool and silk with pH 6.5 and 3% ammonium sulphate (based on substrate)
A wool substrate is dyed with t5% of Color Index Acid Red 399 in a bath containing O. (based on weight) using a post-treatment bath containing a bath ratio of 30:
Treat the dry substrate in step 1. 4. Leave the bath for 5-10 minutes.
Raise to 0° and hold at 40°C for 30 minutes. After washing and drying, a dyed product with good wet fastness properties is obtained.

Example 8 A lightly chlorinated wool substrate is dyed with 3.0% of Color Index Acid Red 399 in a bath having a pH of 6.5 and containing 3% am/monium sulphate (based on the substrate). do.

After washing with water, the dried substrate is treated with a post-treatment bath containing 4.0% (based on the dry weight of the profiteer) of the dispersion of Side 4 in a bath ratio of 30:l. After 5 minutes, 6.0% (on a dry weight basis of profiteer) of the soda family is added and the process is then continued for an additional 25 minutes. The temperature of the post-treatment bath is maintained at 30° during treatment and the final pH of the bath is 9.8. After washing with water and drying, a dyed product with good wet fastness is obtained.

White Example 9 Repeat Example 8 using 2.4% Color Index 1 Acid Pull 296. Get good results as well.

Example 10 A copper substrate is dyed using 4.0% Color Index Acid Red 399 in a bath containing 1.0% acetic acid and 10.0% Glauber's Salt (all values are based on the weight of the substrate). ).

After washing with water, the dried substrate is treated with a post-treatment bath containing 4.0% of the dispersion of Example 4 at a bath ratio of 30:1.

After 5 minutes, add 6.0% of the soda family and then add an additional 25% of the soda family.
Continue processing for minutes. The treatment bath was maintained at 30°C during the treatment,
Final pH is 10.1.

After washing and drying, a dyeing with very good wet fastness properties is obtained.

Example 11: Post-treatment of acid dyeing of wool A wool substrate is dyed using the following combinations of acid dyes (all profiteering M, quantity basis): 3.0% acetic acid at pH 5.0 (substrate basis) ) in a bath containing CI of 4.0.
Acid Red 3360.6% CI Acid Blue 126° After washing with water, the dry substrate was mixed with the 2.0% dispersion of Example 6.
(based on the base material) using a post-treatment bath containing 30:1 bath ratio. After 5 minutes, 3.0% of the soda family (based on the weight of the substrate) is added and the process is continued for an additional 25 minutes. The temperature of the post-treatment bath is maintained at 30°C and the final pH of the bath is 9.9. After washing with water and drying, a dyed product having good wet fastness properties, especially sweat fastness properties, is obtained.

After washing with water and drying, Example 12: Post-treatment of reactive dyes on cotton fabric A cotton substrate is dyed in a conventional manner using 6% (based on the dry weight of the substrate) of C,1, Reactive Blue 9 and then dyed. Wash the substrate in cold water. After washing with water, the first part of the substrate was left without further treatment and the second part was treated with 4% dispersion of Example 4.
(base material basis) at 40°C for 30 minutes and then washed with water, while the third part was treated with 4% dispersion of Example 4 at 40°C for 30 minutes.
After treatment for 5 minutes, 29/ml of sodium hydroxide is added to the bath and the sample is treated at 40° C. for a further 15 minutes and then washed with water. Dry all three sutures/pulls and then apply 1. to the multi-fiber yarn or fabric. S.O.NI
Test using the IL3 wash test. Contamination on cotton attached fabrics is very low compared to treated materials as well as on untreated dyed substrates.

patent applicant Sanodo Akche/r Zelshaft patent application agent Patent attorney Akira Aoki Patent attorney Kazuyuki Nishidate Patent attorney Yukio Uchida Patent attorney Akira Yamaguchi Patent Attorney Masaya Nishiyama

Claims (1)

[Claims] 1. A method for improving the fastness of a dye or a fluorescent brightener on a substrate comprising fibers containing hydroxyl groups, amine groups or thiol groups, the method comprising: Reaction products A) of primary or secondary amines with cyanamide, dicyandiamide (DCDA), guanidine or biguanidine (where cyanamide, DCDA1 guanidine or biguanidine)
Up to 50 mol % can be substituted with those nocarboxylic acids or mono- or no-esters, said product A)
Initial sardine alloy gold, dyed and glint, obtained by reacting Vt (containing all reactive hydrogen atoms bonded to nitrogen) and shrimp halohydrin or their precursors Vt B) and then waverizing the reaction mixture. The method is characterized in that the crosslinking step is carried out simultaneously with the coating or application to the substrate. 2. The method according to claim 1, wherein the reaction products of A) and B) are acidified to -I2-5. 3. The method according to claim 1 or 2, wherein the reaction products of A) and B) are acidified with sulfuric acid. 4. The method according to claim 1, wherein the reaction products of A) and B) are acidified in the presence of a water-soluble polymer. 5. The method according to claim 4, wherein the water-soluble I remer is polyvinyl alcohol, polyacrylamide or hydroxyethyl cellulose. 6. - Reaction products A) of functional or polyfunctional primary or secondary amines with cyanamide, dicyandiamide (DCDA), guanidine or biguanonine, in which up to 50 mol % of the cyanamide, DCDA, guanidine or biguanidine These socals can be substituted with acid or mono- or no esters, and the product A
) contains a reactive hydrogen atom bonded to nitrogen) and shrimp halohydrins or their precursors B) and are obtained by acidifying the reaction mixture. 7. The dispersion according to claim 6, having a pH of 2 to 5. 8. The dispersion according to claim 6 or 7, which is acidified using sulfuric acid. 9. Reacting the above A) and B) and then acidifying the reaction product in the presence of a water bathable polymer The dispersion according to claim 6, which is obtained by: 10. The water-soluble polymer is polyvinyl alcohol,
The aqueous solution according to claim 9, which is polyacrylamide or human xyethylcellulose. 11. - Reaction product A of a functional or polyfunctional primary or secondary amine with cyanamide, dicyandiamide (D(:DA ), guanidine or biguanidine), where 50 mol of cyanamide, DCDA, guanidine or biguanidine up to these radicals can be replaced by phosphoric acids or mono- or di-esters, the product A) containing a reactive hydrogen atom bonded to the nitrogen) and amino lohydrins or their precursors. B)
1. A method for stabilizing an incipient condensate obtained by reacting with and then acidifying the reaction mixture, the method comprising the step of acidifying the reaction product. 12. The method of claim 11, comprising the step of acidifying the reaction products of A) and B) in the presence of a water-soluble polymer. 13. substantially equimolar amounts of polyalkylene, r? Reacting the reaction product A) of IJ amine with DCDA and amino lohydrin B) in a molar ratio of component A to shrimp halohydrin of 1:01 to 1:05 based on the number of moles of DCDA in NA). The initial condensate obtained by 14. A method for improving the fastness of a dye or a fluorescent brightener on a substrate comprising fibers containing hydroxyl groups, amino groups or thiol groups, comprising a monofunctional or polyfunctional first or second Reaction products A) of amines with cyanamide, dicyandiamide (DCDA), guanidine or biguanonine (where cyanamide, DCDA, guazonine or habiguanidine
up to 0 mol % can be substituted with their tucarpic acid or mono- or di-esters, the nuclear product A) containing a reactive hydrogen atom bonded to the nitrogen) and epi-lohydrins or their precursors. The initial condensate obtained by reacting with substance B) is dyed,
A process as described above, characterized in that it is applied onto a printed or whitened substrate and then a crosslinking step is carried out subsequently or simultaneously with the application to the substrate. 15. The method according to claim 14, wherein the dye is a metal-containing or acidic dye and the substrate is wool or silk. 16. The initial condensate is the reaction product t- of A) and B)
16. The method according to claim 14 or 15, which is a stable aqueous suspension obtained by i.