UA71785A - Method for disperse coloring and wightening of polyamide materials - Google Patents

Abstract

Method for disperse dyeing and whitening of polyamide materials where as colorant there is used a water-dissoluble compound, this is directly in the process of dyeing transformed to disperse colorant.

Description

Description of the invention

The invention relates to the field of dyeing, including fluorescent dyeing and bleaching of polyamide materials - fibers, fabrics, etc.

For dyeing polyamides, acid, basic, active and dispersed dyes are used, but polyamide materials are difficult to dye due to high crystallinity, hydrophobicity and a small number of polar functional groups in the composition of their macromolecules (B.N. Melnikov, G.I. Vinogradova. Application of dyes. Moscow : Chemistry, 1986, pp. 27-43). This explains the limited number of known dyes for polyamides. 70 Dyes for fluorescent dyeing of polyamides and fluorescent dyeing methods are even less known due to such additional requirements for fluorescent dyes as the need to provide bright fluorescence, increase chemical resistance and light resistance. That is, the requirements for fluorescent coloring are much higher than for ordinary ones.

Known fluorescent dyeing of nylon fabrics with active dyes of formula 1 (Ass. USSR 75 Mo326208, СО9К1/02, СО9857/00): 20.5 5 and o Pe) 1 2 where K is an alkyl, substituted or unsubstituted aryl substituent.

Dyeing is carried out due to the presence of a reactive group, which can either directly react with the polymer, forming a covalent bond with it, or react in the form of activated form 2. The method of dyeing with active dye 1 is that the dye (395 by weight of the fabric) is rubbed with a 195% aqueous solution of a nonionic surfactant (surfactant), add sodium bicarbonate solution to (0 module of the bath 1:80, heat to 402, load kapron fabric and slowly (over 40 minutes) heat the solution to boiling and boil 1.5-2 hours, after which the solution is cooled to 80 C, the fabric is pulled out, it is washed first with a solution of nonionic surfactant (g/l) for 1 hour at boiling, then with warm and - cold water and dried.

The advantages of this method of dyeing with active dyes in comparison with disperse dyeing include the high resistance of dyed materials to wet processing due to the strong covalent bond between dye molecules and polymer molecules. Polyamide materials dyed with these dyes have high color indicators and resistance to various physical and chemical influences.

The main disadvantages of the method are a long dyeing time, uneven coloring, as well as over time "loss of activity of the reactive group of the active dye, for example, due to oxidation, hydrolysis, etc., which leads to a decrease in coloring characteristics during long-term storage. - c Disperse dyeing of polyamide materials consists in the fact that the polyamide material is first boiled in an aqueous solution of a disperse dye, and then cooled (B.N. Melnikov, G.I. Vinogradova. Application of "" dyes. Moscow: Chemistry, 1986, pp. 156, 160). At the same time, the dispersed dye, which has limited solubility in water, enters the polymer and is fixed in it. If the dye is not water-soluble, then coloring will be impossible, because the solid dispersion will not be able to get inside the polymer. But if the dye well - and dissolves in water, then the coloring will be ineffective or non-permanent, because the water-soluble dye will be very easily "washed out" from the polymer into the solution. Thus, the disperse dye must have a limited solubility in water, and the degree of its solubility affects the coloring properties A decrease in water solubility significantly slows down dyeing and can even completely prevent dyeing, and an increase in water solubility of 50% leads to a decrease in the durability of dyed polyamide materials for wet processing, for example, washing, therefore, ordinary water-soluble dyes, unlike dispersed dyes, are not suitable for dyeing polyamides. Thus, the development of disperse dyes for polyamides, which would be both resistant to wet processing and quickly and efficiently dye the polymer in bright colors, is a very difficult task.

A dispersed method of fluorescent coloring of polyamide fibers with quaternary salts of the formula C is known (Patent C5 Mo198050.209869/00): p? F and them /

NM

(Nm is M--k 60 o

Where K is methyl, phenyl or paratolyl. because such salts have limited solubility in water, which makes it possible to use them as disperse dyes. Methods of dyeing polyamide materials with C dyes are not given in the specified patent, so it should be assumed that the authors of this patent use the usual method of dispersion dyeing from an aqueous solution. No characteristics of dyed materials, such as color time, color brightness and resistance to washing, are given either. Therefore, we synthesized dye C according to the methods specified in the patent and performed all the necessary studies to compare its characteristics with those obtained for our proposed invention. Thus, it was established that dyeing polyamide fabrics with dye Z both in water and in the presence of sodium bicarbonate gives bright colors, but when dyeing with acetic acid solutions (the usual method of disperse dyeing), the color is very weak. The disadvantage of this method is also the long boiling time (1.5-2 hours) required for dyeing, and the very weak resistance of fabrics to washing, regardless of the dyeing time (table 1, 2).

The method of dispersed fluorescent dyeing with dyes C was chosen as the prototype as the closest to our proposed method, and fluorescent dyes C are the closest structural analogs of those dyes that can be used according to our proposed invention.

The basis of this invention is the task of developing a dispersed dyeing method, including fluorescent dyeing and bleaching, which would make it possible to quickly and efficiently dye polyamide materials with bright colors that are resistant to wet processing.

The solution to the problem is provided by the fact that in the method of disperse dyeing and bleaching of polyamide materials, according to the invention, a water-soluble compound is used as a dye, which is directly converted into a disperse dye during the dyeing process.

All known disperse dyes do not change their solubility in water during the dyeing process, i.e. the chemical formula of the dye molecule, with which the polymer is colored, is the same as at the beginning of dyeing. The essence of the proposed invention is that a water-soluble dye, compared to ordinary dispersed dyes, quickly enters the polymer, after which it is chemically converted into an insoluble or slightly soluble compound, which makes it possible to permanently "fix" it in the polymer and obtain colors resistant to wet processing . "

The use of the proposed method for fluorescent dyeing allows you to give polyamide materials bright colors with a glow from the ultraviolet to the red region of the spectrum. The best results were obtained when dyeing with water-soluble dyes of the general formula 4:

SNu ri 7 no. | co

And in the 2nd century.

M "-

Zore EB and - 4 where В/-85 are hydrogen atoms or any organic or organometallic radical, but at least one of the "substituents В!-ВЕ7 contains a chromophoric fragment that gives a certain color and/or fluorescence;

X is any anion. o) c Chemical reactions that allow turning water-soluble organic compounds into insoluble ones can be, for example, reactions of cleavage of sulfogroups, conversion of water-soluble salts of carboxylic or "sulfonic acids into insoluble salts, etc. These can also be reactions of the hydrolysis of quaternary ammonium salts with the general formula 5 (Vorozhtsov N.N. Fundamentals of the synthesis of intermediate products and dyes. Moscow: GNTI

Chemical literature, 1955, p. 484):

Sh- ia - t- Mb not m - o 50 in 5 sl where K!-87 are hydrogen atoms, or any organic or organometallic radical, but at least one of the substituents B!-БЕ7 contains a chromophoric fragment that gives certain color and/or fluorescence.

Hydrolysis can be carried out directly with water, which is a solvent for dyeing, or, more effectively, with the addition of alkali. in. Salts of type 5, as a rule, dissolve very well in water, but during hydrolysis, one of the В-Е7 radicals is quickly detached and transformed into insoluble or poorly soluble amines in water 6: eat Re bo lower ho? Pdrolv, t --z and 5 B 65 The chromophoric fragment can either remain connected to the nitrogen atom, as in the above scheme, or vice versa, be split off, as in the following case 7:

M.Sc. Mem

Us o a a kN hu zh h-s -- y y s

M hydrolysis ra

MI ---- IR

Not Ts 5 and n

WITH

(8) Fr

Two substituents in formula 5 can form a cyclic or polycyclic system, as, for example, in formula 9. Cyclic compounds of type 9 are stable in water, but when heated in an alkaline environment, the substituent B? and are transformed into insoluble or slightly water-soluble compounds of the general formula 10 75 (Raivepkeg I.O., ei ai. Temgapeygop, 2000, M.56, Mo.37, p.7319-7323; Lyubenko O.N. et al. ChHS, 2003, Mo4,

P.594-602; Patsenker L. D. et al. KhGS, 2003, Mo4, pp. 608-617). The possibility of using the hydrolysis reaction of quaternary salts for dyeing is not obvious. Only special experiments and a careful selection of reaction conditions made it possible to develop specific techniques for dyeing polyamide materials. it's in it! 20 eyes. y r ve ge ear hydrolysis not ge

IR NU and Shchy

Shk Z R eZ 25

From 10 "

The chemical structure of any of the substituents 1-2? and counterion X is not of fundamental importance for the essence of the invention.

But it is clear that in order for compounds of type 9 or 10 to be dyes or fluorescent dyes, at least one of the K!-K7 substituents must contain a chromophoric or fluorophoric moiety. These fragments of 30 can be, for example, derivatives of naphthalic acids, 2,5-diaryl-1,3-oxazoles, 2,5-diaryl-1,3,4-oxadiazoles, etc. (compounds 11-16):

Snu a , SNU r , ns -schi SI ne -i si - 35 « schi o ( in c) m y GU s u s

Ich m-n and F. hu t . of them 50 (8) (8) not with 11 12 . i snu a i se NN Хх 18 Nas v soosan si 7 s sn, u - ts E iCh-- M re a

V i «/ we 50 so o sn sl 13 14 ne ee , savoasSane 55 | M --M -che uh o un;

R Nis (iyito ke s y

I still don't have IR and 60

K ne M-x x sn, 65 16

Compounds used for dyeing according to the proposed method may contain more than one fragment of type 9. Thus, the following formulas 17 and 18 contain two reactive water-soluble fragments connected through the chromophoric system: sn ns , z ne -di and also c s (7 -k 5 with os

M. M. and U

Not SNU 17

SNU (c) ns don't want to; - mo i. Te 5. SI ( M » si

M | Our SNU 18

The EP substitute, which is split off during the dyeing process, can be any. So, for example, in the following compounds K"-CH3, P-H (11) and B? - СоНв, БР-СНу» (19):

SN, , not - 25. 5 si ( I « - и и -- still M

IS) and Sat 11 - Sun -

Not - and - and - p s o so Well 7,

M

Mane -7 h shi s o :z» 19

To obtain a wide range of colors, mixtures of the proposed water-soluble dyes or these dyes in a mixture with ordinary disperse dyes can be used. -And Table 1 shows the estimated data on the quality of kapron coloring at different times of dyeing according to the stated method in comparison with the analog and the prototype. - Table 2 shows the estimated data of resistance to different washing conditions of polyamide fabrics dyed according to the proposed method, analogue and prototype.

The proposed method of dispersion dyeing is illustrated by the following examples. Example 1. 0.003 g of 9,9,11-trimethyl-4,6-dioxo-5-phenyl-5,6,8,9,10,11-hexahydro-4H-isoquino|(4,5-dp) quinosolin-9-yl chloride 11 (390 by the weight of the fabric) is dissolved in 5 ml of a 195% solution of surface-active substance OP-10. The solution is heated to 402C, a sample of kapron fabric is covered, sodium bicarbonate solution (5-10g/l) is added to the bath module 1:80, the bath temperature is slowly brought to a boil and boiled for 30 minutes. The coloring solution is cooled to 802C, the sample is removed, washed in a solution of OP-10 (g/l) for 1 hour at boiling, then with warm and cold water and dried. The fabric is dyed in a bright yellow color, 7.7 au luminescence 54 Ohm.

Example 2. Dyeing of polyamide fabric is carried out according to example 1, but the dye is 8,10,10-trimethyl-4,6b-dioxo-5-phenyl-5,6,8,9,10,11-hexahydro-4H-isoquino| 5,4-u|quinosoline-10-u chloride 12. 60 Bright yellow colors are obtained. AH tdu lLYUyumM. - 535 NM.

Example C. Dyeing is carried out according to example 1, but the dye is 12-ethyloxycarbonyl-2,2,4,11-tetramethyl-8-oxo-2,3,4,8-tetrahydro-1H-pyrazolo|1",5": 2,3|isoquino|(4,5-dn)quinosol yn-2-y chloride 13. A red color is obtained. Atdu lum. - BZ0 nm. 65 Example 4. Bleaching is carried out according to example 1, but instead of a dye, an optical brightener is used -

1,3,3-trimethyl-6-I(5-(1,3,3-trimethyl-1,2,3,4-tetrahydroquinozolin-3-ium-6-yl)-1,3,4-oxadiazol- 2-yl|-1,2,3,4-tet rahydroquinozolin-3-ium dichloride 17. Bleached tissue samples with blue luminescence are obtained.

Atah lum. - 415 nm.

Example 5. Dyeing is carried out according to example 1, but the dye is 11-zyl-9,9,10-trimethyl-4,6b-dioxo-5-phenyl-5,6,8,9,10,11-hexahydro-4H- with isoquino|(4,5-9p)quinosoline-9-chloride 19, Samples of kapron fabric of yellow color with yellow luminescence are obtained. Htah LumM. - 540 nm.

Example 6. Kapron dyeing is carried out according to example 1, but the dye is a water-soluble compound 7, which in the process of dyeing turns into a water-insoluble dye 8. Samples of kapron fabric 70 are obtained in yellow color and with yellow luminescence.

Example 7. Dyeing is carried out according to example 1, but the dye is a water-soluble compound 14. A yellow color is obtained. X tah LUyumM. - 535 NM.

Example 8. Dyeing is carried out according to example 1, but the dyes are a mixture of water-soluble compounds 11 and 13 75 in a ratio of 1:1. They get an orange-red color. X tach lum. - B15 nm.

Example 9. Dyeing is carried out according to example 1, but the dyes are a mixture of water-soluble compounds 11 and 13 in a ratio of 2:11. Get an orange color. хХ тах люмМ. - 580 nm.

Example 10. Determination of resistance of dyed polyamide fabric to washing. Three grams of canine measuring TOx4cm are sewn together. The first fabric is undyed nylon, the second is dyed nylon, the third is viscose. The obtained sample is boiled for 30 minutes in a solution that contains 0.595 ordinary soap and 0.295 sodium carbonate. Bath module 1:50. The sample is washed with water, stitched and analyzed according to the scale of gray standards.

As can be seen from the text of the description and the tables, the proposed method of dispersion dyeing of polyamide materials in comparison with the prototype allows: - to reduce the dyeing time (up to 10 minutes); "- prepare large volumes of dyeing liquid and achieve a high speed of dyeing even in large volumes of dyeing solution; - to obtain dyed materials with high color uniformity, high resistance to wet processing and washing; - increase the resistance of dyed polyamide fabrics to various washing conditions; (2,0) - to give polyamide materials bright colors with a glow from the ultraviolet to the red region of the spectrum when using a method for fluorescent dyeing.

The proposed coloring method does not require special equipment, so it is completely ready for practical use. them

Dyeing method Dye Evaluation of the quality of caproch dyeing depending on the dyeing period 7) « ю Z

SO dsivnystobzaanaloyumimido pine 010000000200000000000000000005456000 ;" with sh and so sl

R

Claims (2)

Formula of the invention 60; h: o, p. I. 1. The method of disperse dyeing and bleaching of polyamide materials, which differs in that a water-soluble compound is used as a dye, which is directly converted into a disperse dye during the dyeing process. 2. The method according to claim 1, which differs in that the water-soluble compounds are quaternary salts of the general formula: snu in , Na -0 ra ho 9 m these foods Ez where B/-85 are hydrogen atoms or any organic or organometallic radical, but at least one of the 70 substituents B'-B7 contains a chromophore fragment that gives a certain color and/or fluorescence; X is any anion. Official bulletin "Industrial Property". Book 1 "Inventions, useful models, topographies of integrated microcircuits", 2004, M 12, 15.12.2004. State Department of Intellectual Property of the Ministry of Education and Science of Ukraine. « IS) so i- «- i - shi s ;" -And - -And at 50 sl 60 b5