JPS585318B2 - Polyester / Cellulose Container - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for dyeing polyester/cellulose blend fibers.

More specifically, polyester/cellulose blend fibers are dyed using an O/W type emulsion dyeing bath containing a disperse dye and a water-soluble reactive dye having an anionic group. The present invention relates to a one-bath continuous dyeing method in which dyeing is carried out using a water-soluble reactive dye, which is then fixed, and the unfixed dye is washed and removed.

Conventionally, a method is known in which polyester/cellulose blend fibers are continuously dyed in one bath using a water-based dyeing solution containing a disperse dye and a water-soluble reactive dye having an anionic group. There are various problems.

(1) Depending on the alkali used to fix the reactive dye,
Disperse dyes are easily destroyed during high temperature heat treatment.

(2) In order to completely remove unfixed reactive dyes, a large amount of washing water is required, 100 to 150 times the weight of the fibers.

(3) In polyester/cellulose blend fibers,
Soaping is usually used as a method to remove unfixed disperse dyes and unfixed reactive dyes, but unfixed disperse dyes contaminate cellulose fibers during washing, resulting in the lack of sharpness, which is a characteristic of reactive dyes. make you lose.

On the other hand, for several years, solvent dyeing has attracted much attention in the dyeing industry from the perspective of pollution prevention due to the problems of dyeing wastewater treatment, the problem of water resource depletion, and the advantages of organic solvents, and research on solvent dyeing of polyester fiber alone has been conducted. Numerous reports have been published, confirming the advantages of shortening dyeing time, improving dye utilization, and saving heat energy.

However, for cellulose fibers, completely non-aqueous dyeing has been abandoned because it is thought that the action of water is essential to swell the amorphous region of the cellulose and cause the reactive dye to enter by thermal spraying.

Based on these facts, regarding solvent dyeing of polyester/cellulose blend fibers, dyeing from an emulsion system or a solution system consisting of water and an organic solvent is considered to be conceptually possible, but the actual dyeing process has not yet been established. The current situation is that this has not been done.

Furthermore, even if an emulsion dye bath is used as the dye bath, a large amount of washing water is still required to remove unfixed reactive dye in the washing process, and the advantages of solvent dyeing cannot be utilized to the fullest.

In view of the above circumstances, the present inventors have aimed to provide a dyeing method that solves the problems of the aqueous-bath continuous dyeing method, the problems of the solvent dyeing method, and the problems of the emulsion-based bath continuous dyeing method. As a result of various studies, we have found that polyester/
The inventors discovered that cellulose-mixed fibers can be dyed with scales in an industrially advantageous manner, leading to the completion of the present invention.

That is, the present invention provides a one-bath continuous dyeing method for polyester/cellulose mixed fibers using a disperse dye and a water-soluble reactive dye having an anionic group, including (a) a disperse dye having an anionic group; Padding is carried out using a 0/W type dyeing bath consisting of a water-soluble reactive dye, water, a sparingly water-soluble organic solvent, an anionic surfactant, and a nonionic surfactant in an amount of 2 to 15 times the weight of water. Dyeing step (b) A fixing step in which the dyed product obtained in this step is subjected to an intermediate drying treatment and then treated with steam at 140 to 200°C to fix the dye, (C
) Next, by processing in a washing bath consisting of an acidic aqueous phase, an organic solvent that is sparingly soluble in water, and an oil phase consisting of an organic amine that is easily soluble in this organic solvent, unfixed particles that did not stick to the fibers are removed. A method for dyeing polyester/cellulose blend fibers, comprising a washing step of washing and removing disperse dyes and water-soluble reactive dyes having unfixed anionic groups.

Next, the present invention will be explained in more detail.

The cellulosic fibers in the polyester/cellulose blend fibers used in the present invention include natural fibers such as cotton and linen, and semi-synthetic fibers such as viscose silk and copper ammonium silk.

Further, examples of the polyester fiber include regular polyester and modified polyester.

Disperse dyes used in the dyeing process of the present invention are water-based disperse dyes produced by using a water bath dispersant such as a formaldehyde condensate of naphthalene sulfonic acid, or sulfosuccinic acid disperse dyes. Examples include oil-dispersed disperse dyes manufactured using oil-soluble dispersants such as esters.

Examples of the disperse dye raw material include azo type disperse dyes, anthraquinone type disperse dyes, quinophthalone type disperse dyes, perinone type disperse dyes, and the like.

Examples of water-soluble reactive dyes having an anionic group include those having one or more 18O3Na or one or more -COONa in the molecule, such as monochlorotriazine dyes and methylsulfonylchloromethylpyrimidine dyes. , methoxymonochlorotriazine type dyes, trichloropyrimidine type dyes, and vinylsulfone type dyes.

Two or more of these dyes may be used in combination.

The organic solvent used in the dyeing bath must be sparingly soluble in water, and examples of the sparingly soluble organic solvent in water include aromatic hydrocarbons such as toluene and xylene, 1,1.2-
Trichloroethane, 1,1゜1-trichloroethane, 1
, 1,1,2-tetrachloroethane, 1,1,2.2-
Examples include halogenated hydrocarbons such as tetrachloroethane, 1,2.2-trifluorotrichloroethane, pentachloropropane, trichloroethylene, tetrachlorethylene, dichlorohexane, and dichlorobenzene.

Two or more of these may be used in combination. Among these, those having a boiling point of 80 to 160°C are particularly preferred, and for example, tetrachlorethylene and trichlorethylene are preferred.

The amount of the organic solvent that is sparingly soluble in water needs to be 2 to 15 times the weight of water, particularly preferably 2 to 10 times the weight of water.

Examples of anionic surfactants used in the dyeing process include carboxylic acid-based surfactants such as metal salts of carboxylic acids, sulfuric acid-based agents such as sodium dodecylbenzenesulfonate, sulfuric ester-based agents such as lauryl alcohol sulfate, and phosphorus esters. Examples include acid ester-based surfactants that are easily soluble in water, and phosphoric ester-based surfactants are particularly preferred.

Two or more of these may be used in combination.

Further, the amount of anionic surfactant used is preferably about 0.0005 to 0.03 times the weight of the organic solvent.

In addition, as a nonionic surfactant, it is easily soluble in water, and H
Those with a LB of about 14 to 20 are particularly effective, such as alkyl allyl ether types such as polyoxyethylene nonylphenyl ether, alkyl ether types such as polyoxyethylene lauryl ether, and alkyl ester types such as holoxyethylene stearate. , polyoxyethylene sorbitan fatty acid ester type, and pluronic type and tetronic type, which have polypropylene oxide as a lipophilic group and polyethylene oxide as a hydrophilic group.

Further, two or more of these surfactants may be used in combination, and a mixture with a pluronic type surfactant is particularly suitable.

These nonionic surfactants are required in an equivalent molar amount or more relative to the anionic surfactant, and are usually 0.0 molar or more relative to the organic solvent.
It is preferable to use it at a ratio of about 0.0005 to 0.06 times by weight.

The emulsion dyeing bath used in the present invention is prepared by applying a commonly used emulsion preparation method, using the above-mentioned disperse dye, a water-soluble reactive dye having an anionic group, water, It can be prepared by stirring a difficult-to-bath organic solvent, an anionic surfactant, and a nonionic surfactant in ~15 times the weight of water using a homogenizer or the like.

The emulsion dye bath prepared in this way is 0/W
In the mold, the external continuous phase is an aqueous phase.

Further, the dyeing method can be carried out by padding under the same conditions and operations as a normal water-based dyeing method.

Note that it is preferable to add sodium bicarbonate, sodium trichloroacetate, etc. to the dyeing bath.

The dyed product obtained in the dyeing process is then subjected to a fixing process in which the dye is fixed to the fibers.

The fixing process consists of intermediate drying the dyed product obtained in the dyeing process and then treating it with steam at 140 to 200°C (hereinafter this process is referred to as H, T, S, treatment).
.

The intermediate drying treatment is preferably carried out at 100 to 120° C. for about 1 to 3 minutes using, for example, a pin tenter type thermosol machine.

H, T, S, processing using a high temperature steamer at 140-200
It is preferable to carry out the reaction at a temperature of 1 to 10 minutes.

Particularly preferably, the temperature is 160 to 180°C for 3 to 7 minutes.

After fixing the dye to the fibers in the fixing process, the dyed product is washed to remove unfixed disperse dyes that were not fixed to the fibers and unfixed water-soluble reactive dyes having anionic groups in the washing process. .

The washing process consists of treating the dyed product obtained in the fixing process in a washing bath consisting of an acidic aqueous phase, an organic solvent that is sparingly soluble in water, and an oil phase consisting of an organic amine that is easily soluble in this organic solvent. .

The acidic aqueous phase must always be maintained at a slightly acidic pH of less than 7, preferably at a pH of 5-6, during washing of the dyed articles.

In order to make the aqueous phase acidic, inorganic acids such as sulfuric acid, hydrochloric acid and perchloric acid, and organic acids such as P-toluenesulfonic acid, acetic acid and trifluoroacetic acid can be used.

The amount of water used is usually about 0.3 to 10 times the weight of the dyed product, preferably about 1 to 3 times the weight.

In addition, organic solvents that are sparingly soluble in water have a boiling point of 40°C to 1°C.
Preferably, the temperature is 60°C.

For example, aromatic hydrocarbons such as toluene and xylene, halogens such as trichloroethane, tetrachloroethane, pentachloropropane, dichlorobenzene, dichlorohexane, perfluoro-n-hexane, and 1,2.2-trifluorotrichloroethane. Carbonized hydrocarbons are preferred, especially 1.
1,2.2-tetrachloroethane, 1,1゜2-trichloroethane, 1,1,1-4lychloroethane, 1,1,
1.2-tetrachloroethane, trichlorethylene, and tetrachlorethylene are preferred.

Two or more of these may be used in combination. The amount used is at least 3 times the weight of the dyed material, preferably 10 to 4 times the weight of the dyed product.
0 times the weight.

As the organic amine that is easily soluble in the organic solvent, an organic amine that is sparingly soluble in water is used.

For example, 1-(3-ethylpentyl)-4-ethyloctylamine, octadecylamine, N-benzyl-1-(
Synthesized from 3-ethylpentyl)-4-ethyloctylamine, di(tridecyl)amine, trilaurylamine, butyllaurylamine, tribenzylamine, a linear aldehyde with a carbon number of 9,11°13.15, and ammonia. A mixture of primary, secondary and tertiary amines is used;
Particularly suitable are alkylamines such as Premen JM-T, Amberlite LA-1, Amberlite LA-2 (both Premen and Amberlite are manufactured by Rohm & Barth).

Furthermore, two or more of the above organic amines may be used in combination.

The amount of the organic amine used may be a stoichiometric amount based on the unfixed reactive dye, and is usually 0.000% relative to the organic solvent.
It is about 1 to 10% by weight, preferably about 0.01 to 0.1% by weight.

Further, the washing temperature is preferably in the range of 80 to 120°C.

Furthermore, during cleaning, add score roll #90 to the cleaning bath as appropriate.
A cleaning surfactant such as 0 (manufactured by Kao Soap Co., Ltd.) may be added.

Note that after washing the dyed product, the organic solvent can be recovered by distillation and reused.

In order to carry out the above-mentioned washing continuously, several types of washing baths can be used in parallel.

Next, the cleaning principle of the cleaning process will be explained with reference to the accompanying drawings.

In the figure, F is the dyed product, W is the acidic aqueous phase, S is the oil phase, the shaded area indicates the location where the non-dyeing dye is present, and the pot indicates the movement of the non-dyeing dye.

Set to a predetermined cleaning temperature and confirm that the pH of the aqueous phase W of the cleaning bath is less than 7, as shown in P-1.
A dyed polyester/cellulose blend containing a water-soluble reactive dye having an anionic group in an undyed state and a disperse dye in an undyed state (hatched) is placed in a washing bath.

Then, as shown in P-2, the undyed reactive dye once dissolved in the water phase further migrates to the oil phase S as a result of interaction with the organic amine in the oil phase.

On the other hand, most of the undyed disperse dye dissolves in the oil phase due to the difference in solubility in water and organic bath agents, and as shown in P-3, the undyed reactive dye and disperse dye are almost completely dissolved. It falls off from the dye and dissolves in the organic phase.

Thereafter, as shown in P-4, the undyed dye can be washed and removed by taking out the washed dyed material from the bath.

According to the present invention described in detail above, there are the following advantages compared to conventional water-based dyeing methods.

(1) Migration resistance of disperse dyes during intermediate drying is improved.

(2) Intermediate drying time is reduced to about 1/2.

(3) The utilization rate of disperse dye increases by about 10 to 20%.

(4) The amount of washing water used is reduced to about 1/15 to 1/30.

(5) The specific heat of the organic bath agent used for cleaning is 1/1 that of water.
Since it is about 4 to 115, the heating energy is 1/4 to 1
It can be reduced to about 15%.

(6) Cleaning time is shortened to about 1/1.5 to 1/2.

(7) Cotton staining caused by disperse dyes can be extremely reduced.

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to the following examples unless it exceeds the gist thereof.

Example 1 A polyester/cotton blend was continuously dipped in a 0/W type emulsion dye bath having the composition shown in Table 1 below using a commonly used padding machine and mangle, and the drawing rate was 110.
%, using a pin tenter type thermosol machine, 100
℃ x 90 seconds, then using a high temperature steamer,
170°C x 7 minutes or 180°C x 5 minutes (H, T, S,
) to fix the dye.

Next, the dyed product was placed in a washing bath having the composition shown in Table 2 with a washing temperature of 87°C, and the pH of the aqueous phase of the washing bath was adjusted to around 5 to 6 using concentrated sulfuric acid. The dyeing process was performed for 3 minutes with vigorous shaking using a shaking dyeing machine.

Furthermore, the dyed material was transferred to a freshly prepared washing bath and treated for 3 minutes.

Repeat this operation once more, and finally apply 50% to the dyed material.
It was rinsed for 1 minute in an 87°C rinsing bath consisting of 20 times the weight of water and 20 times the weight of tetrachlorethylene.

The obtained dyed product was dyed in a bright orange color.

Note 1: Phosphate ester surfactant manufactured by Toho Chemical Co., Ltd. Note 2; Nonionic surfactant manufactured by Nippon Nyuka Co., Ltd. Note 3; Pluronic type nonionic surfactant manufactured by Nihon Yushi Co., Ltd. Note 4; Polyester/cotton dye manufactured by Bayer Co., Ltd. Mixture of disperse dye and reactive dye) To prepare an emulsion dyeing bath, first add 650% tetrachlorethylene, .

20ml of water, 3.0g of each surfactant, however, GAFAC
LO-529, which had been adjusted to pH 10 with alkaline water, was sequentially added and shaken to prepare an O/W type emulsion stock solution.

Next, add the reactive dye, water-based disperse dye, and urea in order to another container, dissolve the reactive dye with 140 ml of hot water, and after uniformly dispersing the disperse dye, add the emulsion stock solution prepared in advance. All of the ingredients were added thereto and thoroughly stirred with a homogenizer. Immediately before dyeing, 15 g of sodium bicarbonate was added and thoroughly stirred with a homogenizer to completely dissolve the alkali, thereby preparing an 0/W emulsion dye bath.

The dye utilization rate in this example was as shown in Table 3 below.

The disperse dye utilization rate was measured by an extraction method using chlorobenzene, and the reactive dye utilization rate was measured by a hydrochloric acid dissolution method.

For comparison, H, T, and S in the above example.

When the usual thermosol method was carried out at 200 ° C for 1 minute instead of the treatment (Comparative Example 1), when the following water-based dyeing bath was used for H, T, S, treatment (Comparative Examples 2 and 3), The dye utilization rate when a normal thermosol method was carried out at 200° C. for 1 minute using the following aqueous dyeing bath (Comparative Example 4) is also shown.

Water-based dyeing bath T, T, Pr1nting Orange G
30g urea 100g
Aqueous solution 1 containing 15 g of baking soda and 1 g of sodium alginate
000m1 As is clear from Table 3, the utilization rate of disperse dye of the present invention is 1 to 1.5% higher than that of the aqueous method regardless of the fixing conditions.
It was 50% better.

Furthermore, it was used in the present invention.

The H, T, S method had the following advantages over the thermosol method.

■ Increased dispersion and reactive dye utilization.

Thermal discoloration of the zero-reactive dye is small, so the hue of the dyed product is clear.

■ The degree of thermal decomposition of the surfactant is small, so it is unlikely to adversely affect the hue of dyed products.

For comparison, the cleaning results in this example and the water-based method (
The cleaning results of Comparative Example 5) are shown in Table 4.

As the aqueous method, the fibers were dyed using the dyes shown in Table 1, and as the washing method, the commonly used open soap method was applied.

As is clear from Table 4, compared to the water-based method, the method of the present invention reduces the amount of washing water used to about 1/14, and also reduces the washing time to 1/1.
It was shortened to 7.

Moreover, various fastness properties were equivalent to those of the water-based method.

The wet rubbing fastness was tested according to JIS LO849-1967, the water fastness was tested according to the JIS LO846-1967B method, the washing fastness was tested according to the JIS LO844-197OA-2 method, and the light fastness was tested according to JIS L1044-1959.

Comparative Example 7 A polyester/cotton blend was continuously dyed using a W10 type emulsion dye bath having the composition shown in Table 5 below.

As a method for preparing a W10 type emulsion dyebath, first, surfactant 21 is dissolved in 650 g of tetrachlorethylene.

Add reactive dye, disperse dye, and urea to another container and add hot water
01rLl to dissolve the reactive dye and uniformly disperse the disperse dye.

After cooling, 15 g of sodium bicarbonate was further dissolved in the bath, and these were gradually added to the tetrachloroethylene solution to prepare a W10 type emulsion dye bath.

This was used in a dyebath to dye a polyester/cotton blend in the same manner as in Example 1.

After dyeing, the dyed fabric was treated with a normal water-based washing method, but compared to water-based dyed products, the cotton side was hardly dyed, and the emulsion dye bath started to break down after about 30 minutes, resulting in W1
Type 0 emulsion dyeing was industrially impractical.

Comparative Example 8 Using an O/W emulsion dye bath shown in Table 6 below and an aqueous dye bath shown in Table 7 below, one-sided dyeing was carried out on the polyester side for a polyester/cotton blend.

The experimental method involved soaking a polyester/cotton blend fabric in each dye bath, squeezing it with a mangle, and then dyeing it with a pin tenter type Suichimosol machine PT-2 model tester (manufactured by Tsujii Dye Machinery Co., Ltd.).
Intermediate drying was performed at 00°C for 3 minutes.

During intermediate drying, only the upper fan of the upper and lower operating fans was operated to artificially force migration.

After intermediate drying, both fans of the thermosol machine were operated to perform treatment at 200° C. for 1 minute.

Finally, the Nippon Denshoku Kogyo Co., Ltd.'s Fluorescent Colorimeter Colorimeter N with Memory Device
Determine the lightness (L value) of the front and back sides of the fiber using the 5F type in D-,
The migration properties were compared.

The results obtained are shown in Table 8.

7 The upper row shows the value after intermediate drying, and the lower row shows the value after thermosoling at 200°C for 1 minute Note 9: Disperse dye manufactured by Mitsubishi Kasei As is clear from Table 8, migration resistance is improved by using the 0/W type emulsion dye bath. compared to 2
It's more than twice as good.

This is a huge advantage when continuously dyeing polyester/cellulose blends.

Example 2 Using a 0/W type emulsion dye bath having the composition shown in Table 9 below, a polyester/cotton blend fabric was continuously immersed in the dye bath, squeezed to a squeezing rate of 105%, and heated to 102°C using a pin tenter type thermosol machine. After intermediate drying for 90 seconds, it was treated at 180° C. for 6 minutes using a high-temperature steamer.

The dyed product was placed in a washing bath with a washing temperature of 93°C and the composition shown in Table 10, and after adjusting with acetic acid so that the pH of the aqueous phase of the washing bath was around 5 to 6, it was placed in a shaking dyeing machine. The mixture was shaken vigorously for 3 minutes.

The dyed material was transferred to a freshly prepared washing bath and treated for 3 minutes.

This operation was performed once more.

Finally, it was lightly rinsed with tetrachloroethane at 90°C.

The obtained dyed product was dyed in vivid blue.

Note 10; Mitsubishi Chemical Industries Dianic Sprue B G-
The raw material of FS was dispersed in tetrachloroethylene using dioctyl succinate as a dispersant, and the dye concentration was adjusted to be equivalent to 37 g of a commercially available aqueous disperse dye (powder).

Note: Note 12: All reactive dyes manufactured by Ciba-Geigi.

To prepare an emulsion dyeing bath, first prepare an emulsion stock solution in the same manner as in Example 1, add the disperse dye in oil to this, and stir with a homogenizer.
Disperse in the O phase (tetrachlorethylene phase) of the W-type emulsion.

Next, add reactive dye and urea in order to another container, and add hot water to 140 ml.
After dissolving the reactive dye in m1, add all of the emulsion stock solution (containing disperse dye) prepared in advance to this, stir well with a homogenizer, and add 15 g of sodium bicarbonate immediately before dyeing, and mix with a homogenizer. An emulsion dye bath was prepared by thoroughly stirring to completely dissolve the alkali.

The utilization rate of the disperse dye in this example was 84%.

For comparison, when dyeing was carried out using the disperse dyes and reactive dyes listed in Table 9 by a normal water-based method, the utilization rate of the disperse dyes was 61%.

For comparison, the cleaning results in this example and the water-based method (
The cleaning results of Comparative Example 9) are shown in Table 11.

Note 13: Amount used per dyed product 11 As is clear from the amount of clothing used, the method of the present invention reduces the amount of washing water used to 1/25 compared to the water-based method, and the washing time is also 171.5 times.
was shortened to

Furthermore, various fastness properties were equivalent to those obtained using the water-based method.

Comparative Example 10 During washing in Example 2, white cotton cloth (undyed cloth) of the same weight was allowed to coexist with the dyed article to examine the cotton staining property of the disperse dye.

Similarly, when washing water-based dyed products with an open soaper, a white cotton cloth was used to compare the staining properties of disperse dyes on cotton.

The cotton staining property was compared using the JIS LO805-1965 gray scale for staining.

The results are shown in Table 12.

[Brief explanation of drawings]

The drawing is an explanatory diagram for explaining the principle of cleaning in the present invention, P-1 shows the state of the cleaning bath at the start of cleaning,
p-2 indicates a state in which non-dyed dye migrates to the oil phase, and P-2
3 shows the state in which the non-dyed dye has migrated to the oil phase, and P-4 shows the state of the washing bath after washing is completed.

Claims (1)

[Scope of Claims] 1. In a method for continuously dyeing polyester/cellulose blend fibers using a disperse dye and a water-soluble reactive dye having an anionic group, (a) a disperse dye and an anionic group-containing water-soluble reactive dye are used. Water-soluble reactive dye with water, 2 to 2 to water
A dyeing step of padding using an O/W type emulsion dyeing bath consisting of a poorly soluble organic solvent, an anionic surfactant, and a nonionic surfactant in 15 times the weight of water; (b) the dyed product obtained in this step; After intermediate drying treatment, 140-20
A fixing step in which the dye is fixed by treatment with steam at 0°C; (c) Next, an acidic aqueous phase, an organic solvent that is sparingly soluble in water, and an organic solvent that is resistant to water by easily bathing in this organic solvent; a washing step of washing away disperse dyes that did not adhere to the fibers and water-soluble reactive dyes having anionic groups by processing in a washing bath consisting of an oil phase consisting of an amine; Types of staining methods.