JPS609980A - Dyeability enhancer of fiber - 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 The present invention relates to a dyeability improver for fibers, and more specifically, it improves the dye exhaustion efficiency of fibers by treating them prior to dyeing, and improves workability, economy, and efficiency in the subsequent dyeing process. This invention relates to a dyeability improver that increases the versatility of dyes.

Conventionally, natural cellulosic fibers such as cotton and hemp, and regenerated cellulosic fibers such as rayon, polynosic rayon, and cupola can be dyed with various anionic dyes, but the dyes and fibers form covalent bonds, resulting in color tone. It has become mainstream to use reactive dyes, which have a clear color and excellent color fastness, and direct dyes, which are dyed through physicochemical adsorption and whose color fastness can be easily improved by post-dyeing fix treatment. There is. However, the affinity of cellulose fibers with reactive dyes, direct dyes, etc. is not that high (and therefore, when actually dyeing, salts such as glauber's salt are added to increase the affinity between the fiber and the dye. There are problems such as the need to carry out dyeing, increase the dye concentration in the dye bath, and dyeing treatment at high temperatures for a long time.Also, when dyeing cellulose fibers with reactive dyes, the dye-fiber There is a problem in that the addition of an alkali is necessary to carry out the bonding reaction between the two, which complicates the process.Furthermore, even if a large amount of auxiliary agents such as salts and alkalis are used, The molecules of the dye used are not dyed onto the fibers, and a large amount of dye remains in the dyeing residue and is discarded, resulting in problems such as the dye not being used effectively and the need for a wastewater treatment process. Furthermore, fibers with 10H groups on the fiber surface, such as cellulose fibers and polyvinyl alcohol fibers, cannot be dyed with acid dyes because the OH groups are stable in acidic baths. The problem is that it is not possible to impart a unique and excellent color tone to textile products.

As a solution to these problems, a treatment method using a compound represented by the general formula (1) or 55-65478).

0 In formulas (1) and (1), Rld and f have 1 to 2 carbon atoms
Indicates each organic group of alkyl, alkenyl, alkylaryl, human tetraxyalkyl, amidoalkyl, polyethenoxy and ester alkyl having 2 straight or side chains,
X represents a halogen atom, and Y represents an anion. However, as a result of the inventors' studies on these compounds, it was found that the dyeability was improved only slightly, and they were far from being suitable for practical use.

Therefore, the inventors of the present invention have conducted intensive research to solve the above-mentioned problems that occur when dyeing fibers, and have found that if fibers are treated with a specific compound, reactive dyes, direct dyes, acid dyes, etc. The present invention has been completed by discovering that all of the above-mentioned problems can be solved in dyeing with anionic dyes such as dyes.

In formula (1), R, R2, R, and R4 are each hydrogen, an alkyl group having 1 to 18 carbon atoms, a Schifftetraalkyl group,
An aryl group or an aralkyl group having 7 to 18 carbon atoms,
n is an integer of 2 or more, m is an integer of 1 or more, and each of M and A2 is hydrogen, -
The present invention provides a fiber dyeability improver comprising a compound represented by ou2aHon2x (x is an OH acid residue).

The compound represented by the general formula (1) according to the present invention can be produced by various known methods.

For example, in the formula (IJ R (formula (1)), RJIRRm and n are
2j 5a 4j It is the same as . ) A polyalkylene borea or a salt thereof represented by the formula (S0H2-CjHOH2X (1) \1 (X represents)'-tetragene atom, preferably chlorine or bromine atom) is an epoxy compound represented by the formula A manufacturing method such as quaternization can be used. Typical examples of compounds represented by the formula (phantom) are N, N, H', di/-tetramethylhexamethylenecyamine, tetramethylethylenediamine, tetraethylp, pyrenediamine, pentamethyldiethylenetriamine, hexamethyl Triethylenetetraamine, Tetraethyl, Samethylenediamine, Tetraethyldiethylenetriamine, Dimethylhexamethylenediamine, Dimethylpyrenediamine, Diethylhexamethylenediamine, Diphenylhexamethylene Schiff 2
Examples include dicyclotetrahexylhexamethylenediamine, dimethyldioctylhexamethylenediamine, and dimethyldioctylhexamethylenediamine.

The effect of the dyeability improver of the present invention can be seen even when it is applied to textile materials as it is, but to obtain a more pronounced effect, it is necessary to treat textile materials in the presence of an alkali or after treatment with an alkali. Preferably, it is processed into a fibrous material.

If necessary, the fiber material may be treated with an alkali and then further treated in the presence of an alkali, or the fiber material and the dyeability improver of the present invention may be treated with an alkali in advance. Either treatment may be performed after the treatment. As alkali, NaOH, KOH,
Na2Co, 2005. CnH2)2CjO5°(NH4)2Co or other alkaline substances can be used.

In the treatment of the fiber material with the dyeability improver of the present invention, the compound represented by the formula (υ) is 0.001 to 1000%, preferably 0.01 to 5
The amount of the compound is preferably 0.00%, and within that range, the amount of the compound is determined depending on the degree of cationization. If the amount of the compound is too small, it will not be effective, and beyond a certain point, no improvement in effectiveness will be observed, so there is no point in using too much of the compound, and it will instead become a supplement. The amount of alkali used is preferably 0.1 to 30 times, preferably 0.5 to 20 times, the amount of alkali required to ring-close the compound represented by formula (1).

The method for treating the fiber material may be either a dipping method or a dip-nip method; in the former case, for example, a sieving-washing-drying step, and in the latter case, for example, a dip-nip-drying process (although heat is preferable). (Can also be applied with dry heat) - Water washing - Drying process. Although the water washing step is not necessarily necessary, it is preferably carried out in order to remove excess alkali and the like. The treatment temperature may be any value as long as it is 5 to 200C, and the deep burial time is appropriately selected depending on the treatment temperature.

When the fiber material subjected to such treatment is dyed with anionic dyes such as reactive dyes, direct dyes, and acid dyes, dyeing is carried out using an aqueous dye solution of a predetermined concentration and an appropriately selected bath ratio. A simple aqueous solution of the dye alone is sufficient for dyeing, but if necessary, various dyeing aids may be used in combination without interfering with the dyeing. The temperature may be any temperature between 0 and 100C, but dyeing will be sufficient even if the temperature is not particularly high, so from the point of view of energy saving etc., it is best to carry out the process at around room temperature.
is more preferable, and the dyeing time is appropriately selected depending on the temperature. After dyeing, annealing is performed if necessary.

In the case of textile printing, usually a color paste mixed with a dye and a paste agent and adjusted to an appropriate viscosity is printed on the textile material, dried, and then subjected to pI and saturation soaping with relatively moist steam to obtain the printed textile material. ing.

When using the dyeability improver of the present invention, the dyeability improver of the present invention is mixed with an alkali and a glue agent to the fiber material to adjust the viscosity, and then treated in the same manner as normal textile printing. The treated fiber material is dyed using a dyeing method or the like. By this operation, the cationized parts absorb the dye, and the non-cationized parts do not adsorb the dye, so that the pattern used in the preliminary treatment can be dyed and printed.

In this dyeing as well, since the dye exhaustion efficiency of the fiber material is improved, the amount of dye used can be reduced and the coloring of the dyeing residue can also be reduced. It also has the advantage that, for example, it is possible to dye with acid dyes, which are generally considered unsuitable in the case of cellulose fibers.

By treating the dyeability improver of the present invention to give cationic properties to fiber materials having -OH groups on the fiber surface, such as cellulose fibers and polyvinyl alcohol-based fibers, it is not normally applicable to dyeing the fiber materials. Since it becomes possible to use acid dyes, which have been thought to be possible, it becomes possible to give the fiber material the color characteristic of acid dyes. In addition, the addition of glauber's salt, alkali, etc., which was indispensable when dyeing CEL-PS fibers with reactive dyes and direct dyes, is no longer necessary in the dyeing method using the dyeability improver of the present invention, and the workability is significantly improved. In addition, the dye exhaustion efficiency of the fibers is significantly improved compared to conventional dyeing methods, and the dye concentration is higher, reducing the amount of dye used.The dye concentration of dyeing waste liquid is also lower, making wastewater treatment easier. Therefore, the cost for wastewater treatment can be reduced, and when using the dyeability improver of the present invention, dyeing can be done at a much lower temperature and in a shorter time than with conventional methods, which can save energy and has many excellent features. is demonstrated.

The dyeability improver of the present invention is suitable for fibers having hydroxyl groups on the fiber surface, such as natural cellulose fibers such as cotton and hemp, recycled 4E cellulose fibers such as rayon, polynosic rayon, and cupola, and polyvinyl alcohol fibers such as vinylon. It has also been shown to be effective against acetate fibers such as diacetate and triacetate, wool, and animal fibers such as Al2, cashmere, mohair, and silk. use, composite use of these fibers, these fibers and polyester,
It can be used in combination with other fibers such as nylon or acrylic, and can be used in various forms such as fibers (raw cotton, yarn), yarn, cheese, textiles, woven fabrics, knitted fabrics, non-woven fabrics, as well as clothing and bedclothes. It does not matter whether it is a final textile product such as a packaged product or the like.

As described above, by using the dyeability improver of the present invention, it is not necessary to add various auxiliary agents such as mirabilite or soda ash when dyeing cellulose fibers with reactive dyes or direct dyes. (The dyeing itself can be done at a low temperature such as room temperature, so there is no need to raise the temperature to high temperatures.The dye exhaustion efficiency of the fiber material is greatly improved by cationization, so there is no need to unnecessarily increase the dye concentration in the dye bath.) Therefore, compared to the conventional dyeing waste liquid, which only contains a small amount of dye, the dyeing waste liquid becomes extremely clean, and the amount of waste water treatment required is greatly reduced. It is now possible to dye cellulose fibers with acidic dyes, giving cellulosic fibers the colors unique to acid dyes, or it can be applied to various fibers other than the cellulosic fibers mentioned above. The thermal history of the fibers during dyeing is extremely small compared to conventional products, so there is less damage to the fibers and dyed products with a good texture can be obtained. characteristics are demonstrated.

Next, the present invention will be explained in further detail with reference to synthesis examples and examples, but the present invention is not necessarily limited to the following synthesis examples and examples.

Synthesis Example 1 Tetramethylhexamethylenediamine represented by the following formula is 1
2 mol of hydrochloric acid (1st class reagent) is added dropwise to a 4 mol Turow flask and stirred at 50-60C for 1 hour. While keeping this neutralized product at about 50 C and stirring well, 2.4 mol of epichlorohydrin is gradually added. After adding epichlorohydrin to the entire container, aging was performed for about 2 hours to obtain the desired product.

Analysis of this compound confirmed that it was 100% quaternized. The compound obtained by this synthesis was a 50% aqueous solution having the structural formula shown below.

Synthesis Example 2 1 mole of tetramethylethylenediamine represented by the following formula 4
2 mol of hydrochloric acid (1st class reagent) is added dropwise to a Tulo flask and stirred at 50-60C for 1 hour. Approximately 50% of this neutralized product
C. While stirring well, 2.4 mol of epichlorohydrin was gradually added. After adding epichlorohydrin to the entire tray, ripening was performed for about 2 hours to obtain the desired product. Analysis of this compound confirmed that it was 100% quaternized. The compound obtained by this synthesis was a 50% aqueous solution having the structural formula shown below.

Synthesis Example 5 1 mol of tetramethylpropylenediamine represented by the following formula is placed in a 4-ton flask, and 2 mol of hydrochloric acid (primary reagent) is added dropwise thereto, followed by stirring at 50 to 60 C for 1 hour. Approximately 5% of this neutralized product
00 (gt) Gradually add 2.4 mol of epichlorohydrin while itching. After adding all the epichlorohydrin, ripening was performed for about 2 hours to obtain the desired product.

Analysis of this compound confirmed that it was 100% quaternized. The compound obtained by this synthesis was a 50% aqueous solution having the structural formula shown below.

1 mol of pentamethyldiethylenetriamine represented by Synthesis Example 4 was placed in a 4-ton flask, 3 mol of hydrochloric acid (1st grade reagent) was added dropwise, and the mixture was stirred at 50 to 60C for 1 hour. This neutralized product was kept warm at about 50 C and 3.6 mol of epichlorohydrin was gradually added while stirring well. After adding the entire amount of epichlorohydrin, ripening was performed for about 2 hours to obtain the desired product.

Analysis of this compound confirmed that it was 100% quaternized. The compound obtained by this synthesis was a 50% water bath solution having the structural formula as shown below.

H Example 1 a) Pretreatment 5 g of scoured cotton stockinette and an aqueous solution of the compound of Synthesis Example 1 2.5 #1 caustic soda in a dyeing pot (capacity 1ii 200 cc) for high-temperature and high-pressure tester D-4C manufactured by Chuo Rikaki Seisakusho. 0.5, F was prepared at a bath ratio of 1:20, and the rotation speed was 5°r, p, m at a temperature of 80G in a high-temperature, high-pressure tester.
Processed for 0 minutes. Further, the compounds obtained in Synthesis Examples 2 to 4 and comparative Tf11 (H5 H30H d degree 50%) were also subjected to similar treatments.

Next, these cloths were washed with water and dried at 80C for 30 minutes.
Dry for a minute.

b) Kayaci for cotton stockinette pretreated by dyeing a)
on Re (IA-5B (reactive dye manufactured by Nippon Kayaku C Co., Ltd.)) at a dye concentration of 2% owf' and a bath ratio of 1:2.
0, temperature 2001 hours 30 minutes, then anionic soaping agent 2! i/-1a17) Soaped with an aqueous solution at a bath ratio of 1:20.80c for 10 minutes, washed with water, and dried.

As a control, scoured cotton knitted fabric was dyed using the same dye under various conditions shown below, and then similarly soaped, washed with water, and dried.

Dyeing condition dyeing Bath ratio temperature time awn Nitrogen soda ash staining (1) 2% owf 1:20 20C30 minutes 01
71 01711(2) II # I 70e990
20g (3) pg z 80 50 0 0g (4)
zz z #70'Blue)90 201(5)5 l #
, 7 g (160 to 20 g) was added gradually over the first 10 minutes, then after 30 minutes, soda ash was added and dyeing was continued for another 30 minutes.

The color of the thus obtained dyed cloth was measured using an 8M color computer model 5M-3 manufactured by Suga Test Instruments Co., Ltd., and the color density (0'') was determined and shown in Table 2.

0'' is calculated by the following formula.

0 = 21.72X10°°t", a072""C; Munsell color system C (chroma) 1/ = 77 cell color system VCBA degree] taaH'=
0.01 +0.001 ΔH5pΔH5, = 10
Hue on the Munsell color wheel divided into 0 equal parts 5. Number of steps from the OP position It is said that the commonly used expressions for "color lineness", such as line color, medium color, or light color, are expressed as M2R when expressed in C" value [Reference material: Based on Sei Osamu, Akiko Nakamura: Journal of the Japan Textile Society, Vol. 36, No. 2] Tables 1 and 2 show the results of friction dyeing fastness and sweat dyeing fastness measured based on JIS LO849 and JIS LO84B. The evaluation results of the condition and texture of the dye bath residue are also shown together (the measurement method for the items of Kona et al. is the same in Example 2 and thereafter).

Note 1) Color fastness is measured using dyed fabric and standard white cloth sewn together, treated according to the Japanese Industrial Standards below, and the contamination grade of the standard white cloth is determined according to Japanese Industrial Standard JIS L-08.
05 pollution gray scale (1 for the most contaminated
Comparisons were made on a 9-point scale, with a grade 5 indicating no contamination at all. Note that those with a C9 value of 2 or less were omitted because they were very light in color.

Washing resistance conditions: Method according to JIS L-0844 Sweat resistance conditions: Method according to JIS L-0848 2) When using refined cotton knitted fabric as a control Judgment: 10 Softer than the control 10 Slightly softer than the control ± Same as the control Softness - Slightly harder than the control m - Those that are harder than the control and do not use Glauber's salt and soda ash are not only stained at 20°C (staining (1)) but also stained at 80'C (staining (3))
Even in this case, there is almost no dyeing. When dyeing with Glauber's salt and soda ash, there is almost no dyeing at 20'C (dying (2)), and dyeing occurs only at 80°C (dying (4)), but the color density is at a low level. Starting with the system using a large amount of dye (dyeing (5)), we reach the systems using the dyeability improver of the present invention in Synthesis Examples 1 to 4. Further, in all of the dyeings (violet) to (5), the dyeing residual liquids are highly colored and turbid. An improvement in color density is also observed in the comparative product, but the degree of improvement is small and the coloring of the dyeing residue is also significant. In contrast, the methods using the dyeability improver of the present invention all have high color density, the dyeing residue is almost transparent, making wastewater treatment easy, and the dyeing fastness is also good. There is.

Furthermore, the product of the present invention can provide excellent softening effects.

Example 2 The cotton knitted fabric used in Example 1 was squeezed to 100% ow using a mangle roll using a mixed solution of 200 g of a 30% aqueous solution of the compound of Synthesis Example 1 and 20Ii of caustic soda.
The sample was treated by the 2-dip-2-nip method as f and dried at 120° C. for 5 minutes using a Binten Ku dryer. This was then washed with water and dried in a dryer at 80°C for 60 minutes.

Next, 51 samples were cut out from this cotton knitted fabric and Example 1
Dyeing by the same method as in Example 1 using the dye used in
Next, it was washed with water and dried. Table 3 shows the 0*, friction dyeing fastness, perspiration dyeing fastness, and state of dyeing residue of the obtained dyed fabric.

As is clear from the results in Table 6, sufficient color density was obtained in this case as well, the dyeing residue was almost transparent, and the color fastness was also good.

Example 3 The cotton knitted fabric used in Example 1 was treated with the compound of Synthesis Example 1 and caustic soda for 2 dips and 2 nips in the same manner as in Example 2, and then heated at 120°C using an HT steamer.
Processed for 7 minutes.

Next, this was washed with water and dried in a dryer at 80°C for 30 minutes.

Next, a 5g sample was cut out from this cotton knitted fabric and Example 1
Dyeing by the same method as in Example 1 using the dye used in
Then, it was washed pink, washed with water, and dried. Table 4 shows the C*, friction dyeing fastness, perspiration dyeing fastness, and condition of dyeing residue of the obtained dyed fabric.

As is clear from the results in Table 4, sufficient color density was obtained in this case as well, the dyeing residue was almost transparent, and the color fastness was also good.

Example 4 In Example 2, the dyeing temperature was 10'C and 40'C.

Dyed fabrics were obtained in the same manner except that the temperatures were 60°C and 100°C. 0′ of the obtained dyed fabric, friction dyeing fastness,
Table 5 shows the sweat color fastness and the state of the residual dye.

As is clear from the results in Table 5, sufficient color density was obtained in all cases, the dyeing residue was almost transparent, and the color fastness was also good.

Example 5 5 g of refined rayon fabric, an aqueous solution of the compound of Synthesis Example 2, and caustic soda were placed in the dyeing pot used in Example 1 at a bath ratio of 1:20 and placed in the high temperature and high pressure tester used in Example 1. Rotation speed 5 Or, p, m, temperature 4 at 60℃
Processed for 0 minutes.

The aqueous solution of the compound of Synthesis Example 2/caustic soda used was pretreatment fil O, 3,9/0.06 g, pretreatment (2
) 1.01110.2 g, pretreatment (315,0#/
1.0 #, preprocessing (411o, o 11/2.
0&, pretreatment (combination of 5120, 0, 9/4.09) (with respect to the fiber-type lid, the lids of the compound of Synthesis Example 2 were 3% owf, 10% owf', 50% owf,
(equivalent to 100% owf, 200% owf). These cloths were then washed with water and dried in a drying chamber at 80° C. for 30 minutes.

Next, Kayacion Bl was applied to these rayon fabrics.
Using ue A-5R (reactive dye manufactured by Nippon Joyaku Co., Ltd.), the dye concentration was 2.5% owf, the bath ratio was 1:20, and the temperature was 25°C.
The dyeing was carried out under conditions of , 30 minutes. As a control, a rayon fabric that had not been pretreated was also dyed in the same manner. Then, in the same manner as in Example 1, it was dyed pink, washed with water, and dried. c* of the obtained dyed fabric, friction dyeing fastness,
Table 6 shows the sweat color fastness and the state of the residual dye.

As is clear from the results in Table 6, almost no dyeing occurred in the case without pretreatment (the dyeing residual liquid was also heavily colored, but with the method of the present invention, a high color density was obtained, and the dyeing residual liquid was also thick). It is almost transparent or slightly colored and has good color fastness.

Example 6 A dye concentration of 2% owf was applied to a cotton knitted cloth pretreated with the compound of Synthesis Example 1 obtained in Example 1.

Dyeing was carried out under the conditions of a bath ratio of 1:20, a temperature of 20° C., and a time of 30 minutes. As a dye (11Kayarus 5upraB
lue BCf, (direct dye manufactured by Nippon Joyaku Co., Ltd.), (
2) Mitsui Aoid Fast Re
L (Antacid dye manufactured by Mitsui Toatsu Chemical Co., Ltd.) was used. In addition, as a control, cotton knitted fabric that had not been pretreated was also dyed in the same manner. Table 7 shows the C*, friction dyeing fastness, perspiration dyeing fastness, and state of dyeing residue of the obtained dyed fabric.

As is clear from the results in Table 7, no dyeing was observed in the samples without pretreatment, but the samples according to the present invention had sufficient color density and good color fastness.

Example 7 201 parts of caustic soda was added to 100 parts of the aqueous solution of the compound of Synthesis Example 1.
1 and subjected to a ring-closing reaction, the vinylon, acetate, and wool fabrics were subjected to a pretreatment similar to a) pretreatment in Example 1. However, at this time, Xunsi soda was not used.

Next, the pretreated vinylon, acetate, and wool fabrics were dyed using the dyes used in Example 1 in the same manner as in Example 1.

Table 8 shows the C*, friction dyeing fastness, sweat dyeing fastness, and state of dyeing residue of the obtained dyed fabric.

As is clear from the results in Table 8, when there is no pretreatment, there is almost no dyeing and the dyeing residue is heavily colored, but with the method of the present invention, it is sufficient to dye any fibers such as vinylon, acetate, and wool. The color density is high, there is little coloring of the residual dye, and the color fastness is good.

Example 8 Refined cotton broadcloth was hand printed with two types of pastes having the following compositions.

Paste 1 Paste 2 Compound of Synthesis Example 1 12.5# 53.5.9 Caustic soda 2.519 6.5.9 Water 485. 9 460 11 The fabric was then dried at about 80°C and treated with moist hot air at 150°C for 5 minutes in an HT steamer.

After pretreatment, the cotton broadcloth was dyed according to the method of Example 1 using the dye used in Example 1. C* of the obtained dyed cloth
Table 9 shows the friction dyeing fastness, sweat dyeing fastness, and the state of the dyeing residue.

As is clear from the results in Table 9, a sufficiently high color density was obtained in this case as well, and there was little coloring of the residual dye, and the color fastness was also good.

Applicant's agent Kaoru Furuya 1, Indication of the case Japanese Patent Application No. 119574/1983 2, Name of the invention Fiber dyeability improver 3, Person making the amendment Relationship to the case Patent applicant (091) Kao Soap Co., Ltd. 4. Agent Nakai Building, 1-3 Nihonbashi Yokoyama-cho, Chuo-ku, Tokyo Column 6: Detailed explanation of the invention in the specification (6) Contents of the amendment 1
6. sJ to l"14.6J and paste 2 row r14.
Corrected 6J to [16 and 5J respectively (1) Paste line 10 in the column of dyeing residual liquid in Table 9 on page 56 “Hatondo Toru F!A
Set J to "Slightly colored" and paste line 20 "Slightly colored" to "
#1: Almost transparent”

Claims (1)

[Scope of Claims] (In the formula (IJ, R4, R2, R3 and R4 are each hydrogen, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group,
An aryl group or an aralkyl group having 7 to 18 carbon atoms,
n is an integer of 2 or more, Peng is an integer of 1 or more, M and A2 are each hydrogen, unless both are hydrogen,
-〇H20HOH2XH Y is an acid residue. ) An agent for improving dyeability of IJl and fibers, consisting of a compound represented by: