JPS6128525A - Water-soluble cationic polymer electrolyte, manufacture and use - 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 [Field of Industrial Application] The present invention provides a method for finishing or finishing fiber materials for improving the dyeability of cellulose fibers, increasing their color fastness, and completing dyeing with reactive dyes. The present invention relates to a water-soluble cationically active polymer electrolyte useful in cleaning processes, a method for producing the same, and a method for finishing or cleaning fibrous materials containing cellulose fibers that have been dyed or printed using the same.

[Conventional technology]

A conventionally known treatment agent for improving the dyeability of cellulose fibers uses quaternary ammonium compounds obtained from tertiary amines and shrimp chlorohydrin as a reactive group for the tertiary amines. It was based on

Good results have been obtained using quaternary ammonium compounds obtained from heterocyclic compounds containing two nitrogen atoms and having two reactive groups. The two reactive groups mentioned above can self-bond to a high degree on the cellulose fibers and at the same time can cross-link the cellulose chains.

The above quaternary ammonium compound has the following formula (1): [However, in the above formula, Y represents a group of the following formula, r represents an integer of 1, 21 or 3, and k represents 1 or 2.
X represents an anionic residue of a strong organic or inorganic acid; M represents a heterocyclic residue derived from a heterocycle having two nitrogen atoms. be.

These compounds can also be used to improve the color fastness of direct dyes. The effect of these compounds on dyeings with other anionic dyes is only moderate. Therefore, these compounds do not exhibit a high Atb effect on dyed products using reactive dyes.

After dyeing or printing, it is necessary to remove from the textile material any dyestuffs that are not sufficiently fixed to it, as well as any chemical auxiliaries that have been adsorbed, and also to In contrast, it is necessary to reduce its washing removability, and for this purpose it is necessary, for example, to form a complex of the dye with a macromolecular compound having a charge opposite to that of the dye molecule.

In the finishing process of textile materials, especially after dyeing and printing, cleaning the textile materials is a process that takes a long time and consumes a large amount of water and energy.

When cellulosic fiber materials are dyed or printed with reactive dyes, washing is a particularly important and complex process. When dyeing fabrics with this group of dyes, it is well known that only a small portion of the dye reacts with the cellulose fibers.

A relatively large proportion of the dye is hydrolyzed and therefore needs to be removed. The color fastness of the dye or print depends primarily on the complete washing away of the hydrolyzed dye from the material.

Solving the above problems of reactive dye cleaning has traditionally been done by
And it is still being researched in various directions.

First of all, with respect to the dye reaction system and conditions described above, we seek ways to ensure that the dye is fixed on the fibers in the highest possible yield and that the amount of dye that has to be removed by washing is as small as possible. Must.

Another strategy, which is already being used in part by selecting the state of the dye, is to make the hydrolyzed dye as washable as possible. Another possibility is to establish a useful cleaning method, both in terms of technique and equipment.

An interesting technique is the use of suspensions of adsorbents. However, the problem with this method is that it is relatively expensive and, apart from that, suitable plant equipment to allow full utilization of the adsorbent has not been fully achieved and successful. There is.

In addition, various cationically active treatment agents are often used at the end of the washing process, the purpose of which is to sequester residual dyes that have not been washed away. However, this method is the least recommended of the above-mentioned possible methods, since it reduces the light fastness of many dyes.

[Problems to be solved by the invention]

The problem to be solved by the present invention is to make the removal of hydrolyzed components of reactive dyes more effective after dyeing or printing of cellulose fiber materials, and to increase the color fastness of anionic dyes such as direct dyes. An object of the present invention is to provide a water-soluble cationically active polymer electrolyte, a method for producing the same, and a finishing or cleaning treatment method using this compound.

[Means for solving the problems and their effects] A group of water-soluble cationically active polymer electrolytes of the present invention for solving the above problems has the following repeating unit of the general formula (2): OHOH... (2) [However, in the above formula, r is 1, 2. or represents an integer of 3, k is 1 or 2
n represents an integer from 2 to 10t, X represents an anion residue of an inorganic or organic strong acid, and is 1, 2, 3, .
or an integer of 4, M is a heterocyclic residue of the following structural formula: [wherein R is a hydrogen atom, or 1
represents an alkyl group having ~4 carbon atoms], and R and R2 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a formula (2) above. Represents the same repetition unit as . ].

The method of the present invention for producing a water-soluble cationically active polymer electrolyte having the repeating unit of the general formula (2) above includes a compound of the following general formula (1): (y yl -y ) 1@'L zrC)
,,,,,,' (1) [However, in the above formula, k represents an integer of l or 2, and r represents 1, 2, . or an integer of 3, M is a heterocyclic residue of the following structural formula: [wherein R is a hydrogen atom, or 1 to
represents an alkyl group having 4 carbon atoms]. [However, in the above formula, n represents an integer from 2 to 10t, and S is 1, 2,
3. or an integer of 4, and R3 and R4 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms] at a temperature of 10°C to 100°C. It involves carrying out a polymerization reaction.

When the reaction molar ratio of the compound of the above formula (1) and the amine compound of the above formula (3) is within the range of 1:0.5 to 1,
The resulting polyelectrolytes have particularly useful properties.

Furthermore, the method of finishing or washing a dyed or printed cellulose fiber-containing fibrous material of the present invention has a repeating unit of the general formula (2).

Water-soluble cationically active polyelectrolyte from 0.1 to 507
The method comprises treating a dyed and/or printed cellulose fiber-containing fibrous material with an aqueous solution containing an amount of 7/11 at a temperature of 10°C to 100°C.

In the production method of the present invention, the polyfunctional amine compound of general formula (3) is used in an amount of 0.1 to 2 moles per 1 mole of the compound of general formula (1).

The molar ratio of the compound of general formula (su and (3)) is 1:0.5~
The reaction product of 1.0 has particularly useful properties.

As the polyfunctional amine of general formula (3), it is preferable to use substances used in epoxy resin production chemistry and substances used in the production of complex-forming substances.

Such amines include, for example, ethylenediamine, diethylenetriamine, and triethylenetetraamine.

A method for producing a compound having a repeating unit of general formula (1) has already been disclosed and patented.

As a rule, first a salt with a strong acid and with a heterocyclic compound having two nitrogen atoms is prepared, and then an aqueous solution of this salt is quaternized. At this time, 2 moles of shrimp chlorohydrin/per 1 mole of this salt are used. After the quaternization is completed, the manufacturing method of the present invention is carried out.

Then, the polyfunctional amine of general formula (3) or its aqueous solution is gradually added to the quaternized compound. Both of these reactions are exothermic and are carried out at temperatures from 10°C to 100°C, preferably from 40°C to 60°C.

After the above reaction is completed, the product obtained can be used as a processing agent without any further manipulation.

In the production process according to the invention, the concentration of active substance in the reaction mixture is provided by the necessary adjustment.

40% of the substance of the present invention. It seems convenient to use one having an aqueous solution containing a concentration of between 1 and 60 cm. Products with higher concentrations have excessively high viscosities, which make process control difficult.

For the compound of general formula (1), an aqueous solution containing the active substance with a content of 70% to 85% is prepared, whereby the concentration of the substance according to the invention in the final product is brought to the above-mentioned state. maintain. Furthermore, it is convenient for the synthesis to use the polyfunctional amine of general formula (3) in the form of an aqueous solution having a concentration of 40 to 50 moles.

The reaction product of the process according to the invention is a yellow-brown viscous liquid containing active substance in a content of 401 to 60%.
It also has a specific gravity of 1.5 to 1.5 g, cm, which is the same as that of water.
They are miscible in all proportions.

Examples of various starting materials and molar ratios between reactions that can be used in the present invention are shown in Table 1.

The chemical formulas of the repeating units of the polyelectrolytes obtained from these starting compounds are shown in Table 2.

The compounds of this invention have many properties that are useful in finishing techniques. In alkaline media, the compounds of the invention can react with alcoholic --OH groups in cellulose macromolecules and thereby form crosslinks between these groups. By bonding the quaternary nitrogen atom-containing group of the compound of the present invention, the dyeability with anionic dyes is substantially improved in the same way as when the compound of general formula (1) is used.

However, unlike the compound of general formula (1), the compound of the present invention significantly improves the fixing effect of anionic dyes, especially direct dyes. However, a completely surprising and exceptional effect of the compounds of the invention is expressed in finishing operations after dyeing and printing with reactive dyes.

The finishing and cleaning method according to the invention is characterized by an extremely good cleaning effect. That is, this method can be carried out without the use of special equipment and has no adverse effect on the light fastness of sb, dyed products and printed products. Utilization of the cationically active polyelectrolyte of the present invention significantly shortens the cleaning process1, which saves water, power, and labor.

In the aqueous solution of the cationically active polyelectrolyte of the invention, a vigorous desorption of the dye takes place and also the formation of a complex between the dye and the polyelectrolyte of the invention. This complex does not bind to or be adsorbed to cellulose fibers.

By the finishing washing method of the present invention, the washed dye will not bleed into the white background even in printed materials or textile materials in which white areas, light colored areas, and dark colored areas are arranged alternately. can avoid. The final washing method of the present invention can be used not only in industrial technology, but also in domestic washing of textile materials with low washfastness.

Furthermore, the finishing cleaning method of the present invention can also be used to repair textile materials contaminated by leaching of unfixed reactive dyes.

Depending on the type of machinery used, the amount of cationically active polyelectrolyte according to the invention added to the aqueous treatment bath is from 0.1 to 209. It is within the fl range. The fiber material is then finished or washed in this treatment bath at a temperature of 15° C. to 100° C. for a period of 10 seconds to 60 minutes. This finishing and cleaning effect improve as the treatment bath temperature increases. Most preferably, the temperature of the bath varies within the range of 80°C to 100°C.

The effect of the cationically active polymer-solites according to the invention having groups of general formulas (1) and (3) on dyeings with direct dyes is different from their effect on dyeings with reactive dyes. In the case of direct dyes, the polyelectrolytes of the invention act similarly to known fixatives derived from dicyandiamide, for example. Therefore, the polymer electrolyte of the present invention is
Improves the color fastness of dyed products. However, unlike known compounds, the polyelectrolytes of the invention do not reduce the light fastness of dyeings.

The cationically active electrolytes of the present invention are capable of binding metal cations due to the effective arrangement of the -M groups and 10 groups therein. Dyings stabilized by cationically active electrolytes can therefore be treated with aqueous solutions of salts of suitable metals. Both the wet fastness and the light fastness of the dyeings are thereby improved. Co2
■Mg 2■.

Zn2Φ, Cu2■, Fe2■, Co2■ and Ni2
Water-soluble salts (2) can be recommended as convenient for this purpose. The aqueous solution for the above treatment is 0.1 to 2
It contains a divalent or trivalent cation of 011.1. These salts may be used simultaneously with the cationically active polyelectrolyte of the present invention or separately and sequentially.

〔Example〕

The water-soluble cationically active polymer electrolyte of the present invention, the method for producing the same, and the method for finishing and cleaning fibrous materials using the same will be specifically described in the following examples.

Example 1 1.1.3-bis(3-
318 fI of an 83% aqueous solution of chloro-2-hydroxypropyl)imidazolinium sulfate was injected. The temperature was set at 25° C. and within 60 minutes, a 120p aqueous solution of 50 thiethylenediamine was added to the flask with continuous stirring. The temperature of the reaction mixture began to rise spontaneously with the addition of the aqueous ethylenediamine solution. The temperature of the reaction mixture was maintained within the range of 65°C to 70°C using cooling means and by addition of aqueous ethylenediamine solution. The reaction mixture was allowed to react for an additional 30 minutes after all of the ethylenediamine had been added. After cooling, the reaction mixture becomes a yellowish brown liquid with a specific gravity of 1.43 ji/an.
It was miscible with water in any proportion.

Example 2 A 71% aqueous solution of 1,4-di(3-chloro-2-hydroxypropyl)-1-methylpiperazinium hydrochloride 4509 was added to the same glass apparatus (flask) as described in Example 1. Injected. Briefly, 50 g of 9120 g of ethylenediamine were added in the same manner as described in Example 1. The resulting reaction mixture was a yellow-brown viscous liquid with a specific gravity of 1.351//crs.

In the same method as above, in place of the 1,4-di(3-'lrolow-2-hydroxyglobil)-1-methyl-piperazinium hydrochloride of 450II, 1,3 of 490I was added.
-bis(3-chloro-2-hydroxypropyl)pyrimidinediylium acetate (78% aqueous solution), 432g 1,4-bis(3-chloro-2-hydroxypropyl)pyrimidinediylium sulfate (84% aqueous solution)
, or 240 g of 1,3-bis(2,3-edexyglobil)
Using imidazolinium hydrochloride (75% aqueous solution), the corresponding cationically active water-soluble polymer electrolytes could be obtained.

Example 3 An aqueous solution of 1,3-bis(3-chloro-2-hydroxypropyl)imidazolinium sulfate (active substance) of 140 k, p is added to an enamelled reactor equipped with a stirrer, a temperature needle and a reflux condenser. content of 83%) was injected. To this, at a temperature of 25° C., a 50% aqueous solution of diethylenetriamine was added. This addition operation is
The temperature of the reaction mixture was controlled not to exceed 70°C.

A total of 80 mm of a 50 mm solution of diethylenetriamine is added, after which the reaction mixture is heated for a further 45 mm at a temperature of 70 °C.
It was allowed to react for a minute and then cooled down. The viscous brown liquid obtained had a specific gravity of 1.47 g/l.

In the same method as above, 110 kg of hexamethylene diamine (50 g aqueous solution) and 70 kg of N,N'-dimethylethylenediamine (50 g
The compound of the method of the present invention could be produced using 116 kg of triethylenetetramine (50% aqueous solution).

Example 4 Mercerized cotton thread was dyed with direct dye Orange C, 1,
To 39! ! It was dyed to a concentration of 72% and treated in a treatment solution containing the compound prepared in Example 1 at a concentration of 11713 at a temperature of 30° C. in a bath ratio of 1:20.

After this treatment, the dyed material was centrifugally dehydrated and dried. The dyeings obtained showed very good fastness to water, sweat and washing (40° C.).

Example 5 Undyed cotton threads identical to those used in Example 4 were treated with the compound prepared in Example 1 at a concentration of 51//l and
The samples were treated in a treatment solution containing sodium hydroxide at a concentration of 21//II for 30 minutes at a temperature of 50° C. and with a mixing ratio of 1:20. After washing and neutralization, the yarn was dyed as in Example 4. The dyeings obtained showed very good wash, sweat and launder (95°C) IL fastnesses, the level of fastness being higher than that obtained with the finish according to the method of Example 4.

Example 6 A cotton fabric was subjected to a conventional scouring and bleaching process and pretreated using dye wince. Furthermore, compound A2 in Table 2 is
At a concentration of 15 Vl, sodium hydroxide was also added at 6 g/
55 at a bath ratio of 1:20 in a treatment solution containing a concentration of
The treatment was carried out for 50 minutes at a treatment temperature of .degree.

After washing, the cotton fabrics were dyed in the usual manner using the reactive dye Blue 0, 1.4. Unlike regular cotton cloth, this cotton cloth was dyed at twice the normal concentration.

Example 7 Blend of polyester fibers and cellulose fibers (67
A woven fabric made from 33% of 100% polyester was impregnated with an aqueous treatment solution containing the following ingredients in No. 4 Y goo.

Disperse Dye Blue C, 1,7310, S'/phrase Reactive Dye Sol-C, L5 3I Sodium Alginate
2117It After drying this at 100℃ 1
Perform thermal treatment (dry heat treatment) at 95°C for 50 seconds,
Next, this woven fabric was impregnated with an aqueous treatment solution containing the following components.

Compound A I 6011/11 of Table 2 Sodium hydroxide 20y
The fabric was rolled up and aged at room temperature for 10 hours with continuous rotation. During this aging process, the compound of the present invention sufficiently fixed the crosslinking bonds between the reactive dye and the cellulose fibers, thereby providing a wrinkle-resistant finish that did not require ironing.

Example 8 Six colors of printing bases each containing the following reactive dyes) (A
)-F)・) was used to print a cotton fabric.

A) Reactive dye Yellow C,1,3 B) Reactive dye Orange C,1,5 C) Reactive dye C,1,24D) Reactive dye Sol-〇,1.5 E) Reactive dye Dyes Green C, 1,8 F) Reactive Dyes Black C, R, S This printing paste contained a thickener, an alkali, and a reduction inhibitor in a conventional manner.

After printing and steam fixation, the printed fabric was washed using a cloth spreading washer having 8 sections each containing the following treatment solutions.

1 Cold water 2 Warm water (50°C) 6 Warm water (80°C) 7 Warm water (50°C) 8 Cold water The unfixed dye is completely removed by passing the printed fabric through the above washing machine once at a speed of 70 m/min. I was able to do that. The printed fabric showed excellent water and washing fastness. Moreover, no influence of the above treatment on sunlight fastness was observed.

The following is a margin Example 9 A cotton yarn wound around X-sgur was put into a dyeing machine in a conventional manner and dyed using the following dye.

Reactive dye Orange C, 1, 42, 0-chi Reactive dye Red C, 1, 23, 5-chi Reactive dye Blue C
, 1, 40, 2 dyed systems were rinsed in cold water for 5 minutes and then in warm water (50°C) for an additional 5 minutes. Next 1c This yarn was treated with an aqueous treatment solution containing 21/l of the cationically active polyelectrolyte compound A2 listed in Table 2.

The treatment temperature at that time was 90° C. and the treatment time was 10 minutes. This treatment was followed by a 5 minute wash with warm water (50°C) and a short rinse with cold water. The fastness of the resulting extremely deep dyed product was as follows. However, when ordinary finishing treatments were applied, the fastness was as shown below.

Example 10: A knitted fabric made from a mixture of cotton and short rayon fibers was reactively dyed in a water-jet dyeing machine using a conventional method, and dyed by Do C, 1, 2, 94.5%. stained to a concentration of

After dyeing, the fabric was washed with cold water (25-25°C) for 5 minutes, warm water (60°C) for another 5 minutes, and then treated with cationic active polyelectrolyte compound A3 listed in Table 2 at 29/l.
The sample was treated at 90C for 10 minutes in a treatment solution containing an amount of .

The wet stiffness of the dyed fabric obtained was superior to that obtained by the conventional method.

Example 11 Direct dye Blue C, 1,78 yoshiji with 2 towf.

A cotton fabric dyed with GAR was washed with cold water and then treated in a treatment solution containing the compound A1 listed in Table 2 in an amount of 59/l in a dissolution ratio of 1:5.

The fabric treated in this way had excellent washability and good washing fastness.

Example 12 A cotton fabric dyed and fixed in the same manner as described in Example 4 was treated with a treatment solution containing 2.59/l of crystalline sulfuric acid steel (If) and 1.0ψ of glacial acetic acid. The mixture was treated in a bath ratio of 1:5 at a temperature of 60° C. for 20 minutes.

The washing and sunlight fastness of dyed fabrics obtained by this treatment are
It has further improved.

Margin below

Claims (1)

[Claims] 1. Repeating unit of the following general formula (2): ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) [However, in the above formula, r represents an integer of 1, 2, or 3. , k represents an integer of 1 or 2, n represents an integer of 2 to 10, X represents an anion residue of an inorganic or organic strong acid, s represents an integer of 1, 2, 3, or 4. Represents an integer, M is the following structural formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼▲ There are mathematical formulas, chemical formulas, tables, etc. ▼▲ There are mathematical formulas, chemical formulas, tables, etc. ▼▲ There are mathematical formulas, chemical formulas, tables, etc. ▼or ▲mathematical formula, chemical formula,
There are tables, etc. ▼ Heterocyclic residue [wherein R is a hydrogen atom, or 1-
represents an alkyl group having 4 carbon atoms], and R^1 and R^2 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or
It represents the same repeating unit as the above formula (2). ] A water-soluble cationically active polymer electrolyte containing. 2. Compound of the following general formula (1): [Y-M-Y]＾k■k/rX^r■・・・・・・・・・
・(1) [However, Y in the above formula represents a ▲ group that has a mathematical formula, chemical formula, table, etc., or a ▼ group that has a mathematical formula, chemical formula, table, etc., and k represents an integer of 1 or 2. r represents an integer of 1, 2, or 3, M is the following structural formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼▲ There are mathematical formulas, chemical formulas, tables, etc. ▼▲ There are mathematical formulas, chemical formulas, tables, etc. ▼▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼ Heterocyclic residue [However, in the formula, R is a hydrogen atom, or 1-
represents an alkyl group having 4 carbon atoms], and X represents an anion residue of an inorganic or organic strong acid], and 0.1 to 2
Polyfunctional amine of the following general formula (3) up to moles: ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼・・・・・・(3) [However, in the above formula, n is an integer from 2 to 10 s represents an integer of 1, 2, 3, or 4, and R^3 and R^4 each independently have a hydrogen atom or 1 to 4 carbon atoms. Representing an alkyl group] A repeating unit of the following general formula (2), which involves a polymerization reaction at a temperature of 10°C to 100°C: ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(2) [However, in the above formula, r, k, n, X, s and M are the same as defined above, and R^1 and R^2 each independently represent a hydrogen atom, 1 to an alkyl group having 4 carbon atoms, or
It represents the same repeating unit as the above formula (2). ] A method for producing a water-soluble cationically active polymer electrolyte having the following. 3. The polyfunctional amine of general formula (2) is a group consisting of alkylene diamine, dialkylene triamine, and trialkylene tetramine (provided that the alkylene group in each of the above compounds has 2 to 6 carbon atoms). 4. Repeating unit of the following general formula (2): ▲There are numerical formulas, chemical formulas, tables, etc.▼・・・・・・(2) [However, In the above formula, r represents an integer of 1, 2, or 3, k represents an integer of 1 or 2, n represents an integer from 2 to 10, and X is an anion of an inorganic or organic strong acid. Represents a residue, s represents an integer of 1, 2, 3, or 4, and M is the following structural formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼▲There are mathematical formulas, chemical formulas, tables, etc.▼▲Mathematical formulas , chemical formulas, tables, etc. ▼▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ Mathematical formulas, chemical formulas,
There are tables etc. ▼ Heterocyclic residue [wherein R is a hydrogen atom or 1
represents an alkyl group having ~4 carbon atoms], and R^1 and R^2 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or
It represents the same repeating unit as the above formula (2). ] of 0.1 to 50
Dyeing and/or with an aqueous solution containing in an amount of g/l
Dyeing, comprising treating the printed cellulose fiber-containing fibrous material at a temperature of 10°C to 100°C;
Or, a method of finishing or washing a textile material containing printed cellulose fibers.