JPS5917230B2 - Dyeing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for dyeing cellulose fibers or structures containing the same.

Conventionally, many attempts have been made to dye cellulose fibers favorably using dyes such as disperse dyes that do not inherently have dyeing properties on cellulose fibers.

These attempts have increased in number with the development of sublimation transfer printing methods that mainly use disperse dyes, such as the Japanese Patent Publication No. 47-40593, which used special disperse dyes and swelling agents, and the use of resin in dry transfer printing methods. Special Publication Showa 47-5173 by processing method
4, a cross-linking agent, and a swelling agent in combination with JP-A-50-12389.
, JP-A-50-38213, JP-A-50-90788,
Dispersion is mainly achieved by fiber processing methods such as Japanese Patent Publication No. 50-29552, or by chemically modifying cellulose fibers, which normally have no affinity for disperse dyes, using agents such as acetylating agents and benzoylating agents. JP-A-50-18778 and JP-A-51-991 which aim to have affinity for dyes
85 etc. are known.

However, although these methods using the above-mentioned fiber treatment agents are possible using relatively simple equipment, they lack clarity in color development and have poor color fastness, especially wet fastness. .

On the other hand, conventionally known methods of chemically modifying cellulose have poor workability due to the irritation and odor of the chemicals themselves, and the process is complicated and requires expensive equipment. I have no choice but to do so.

For example, acid chlorides such as benzoyl chloride have the disadvantage that they have a pungent odor under normal conditions and are easily hydrolyzed when stored in the air for a long time, so they cannot be used in batch-type or similar processes. There is no other choice but to carry out the reaction using a method of oxidation, and the process is also complicated, as the alkali agent must be treated in a separate bath.

In order to solve these problems, the inventors treated cellulose fibers or a mixed structure containing cellulose fibers with a mixed solution containing microcapsules of at least one of an acid chloride and an alkaline agent, and then subjected them to steam treatment or We devised a method of chemically modifying the material through dry heat treatment, and then dyeing it with disperse dyes, oil-soluble dyes, mordants, basic dyes, vat dyes, etc.

The present invention will be explained in detail below.

A method using an alkali catalyst has been known as one of the methods for chemically modifying cellulose fibers using acid chlorides.

That is, a reaction is caused after cellulose fibers are treated with an alkali agent and an acid chloride in an arbitrary order, and (1)
There are two known methods: applying an alkaline agent to cellulose fibers and then treating them with an acid chloride; or (2) treating the cellulose fibers with an acid chloride in advance and then treating them with an alkali agent. This is a multi-bath treatment process with two or more stages of treatment.

When using such a method, if the drying conditions after the alkaline treatment are insufficient in method (1),
When the alkaline agent and water are mixed into the next acid chloride solution, even the acid chloride that does not participate in the reaction is likely to be hydrolyzed.
In method (2), which tends to lead to waste of reagents, the hydrophilic cellulose fibers are treated with the hydrophobic acid chloride and then treated with the alkaline agent aqueous solution. Separation is likely to occur and uneven reforming is likely to occur.

Moreover, since both methods involve multi-bath treatment, when an industrial continuous reforming process is considered, treatment machine units corresponding to the treatment steps are required, which increases the cost in terms of equipment.

Therefore, in a method of chemically modifying cellulose fiber structures and mixed structures of cellulose fibers and synthetic fibers to make them dyeable with disperse dyes using acid chlorides and alkaline agents, among acid chlorides and alkali agents, Such structures are treated with a mixed solution in which at least one of them is microencapsulated, and then chemically modified by steaming or dry heat treatment, followed by dispersion dyes, oil-soluble dyes, mordants, and basic dyes. The inventor has invented that by dyeing with a dye or the like, the above problem can be solved and a good dyed product can be obtained very easily.

That is, acid chlorides are usually hydrophobic and tend to undergo hydrolysis in the presence of alkaline agents.

Therefore, in order to make such acid chlorides coexist stably in an aqueous alkali solution under normal conditions, they are microencapsulated and then dispersed in an aqueous alkali solution, which is uniformly treated on a fabric, and then subjected to steam treatment. Alternatively, cellulose fibers can be chemically modified very easily by dry heat treatment.

In other words, microencapsulated acid chlorides are stable under normal conditions and do not cause any change even when coexisting with an alkaline agent, but the capsules rupture only when subjected to steam or dry heat treatment. The coexisting alkaline agent acts as a catalyst, and the esterification reaction of cellulose by the acid chloride proceeds.

Here, the steaming treatment conditions include normal pressure saturated steam or superheated steam at 100 to 180°C, or 100 to 140°C
Good results can be obtained by treating with high-temperature, high-pressure saturated steam for 30 seconds to 20 minutes, and relatively good results can be obtained by baking at 60°C to 180°C for 30 seconds to 20 minutes. You can get good results.

According to the experimental results of the inventors, better results were obtained with steam heat treatment than with dry heat treatment.

The reason for this is that in steam heat treatment, when cellulose fibers are chemically modified by acid chloride in the presence of an alkaline agent, the reaction proceeds while the swollen state of cellulose is maintained by the steam heat, compared to dry heat treatment. Therefore, it is judged that it will bring extremely effective results.

Such a concept is not introduced in the above-mentioned known documents and is one of the features of the present invention that should be noted.

According to this method, unlike the conventional multi-bath treatment method, chemical modification can be easily carried out by performing a single bath treatment, improving quality stability and simplifying the process. It is of great industrial significance.

Furthermore, as mentioned above, acid chlorides such as benzoyl chloride have a pungent odor under normal conditions and are difficult to handle; however, by microcapsulating them, these problems can be solved.

Here, as a method for microencapsulating hydrophobic acid chlorides, for example, U, S, P, -1957-28004
Publication No. 57, Special Publication No. 36-13412, Special Publication No. 3
It is sufficient to follow the method described in Publication No. 8-22817, etc. If the acid chloride is normally liquid, it is microencapsulated as it is, and if it is usually solid, it is inert to the acid chloride and What is necessary is to dissolve it in a solvent that dissolves it well and microcapsule it.

A detailed explanation of microencapsulation is omitted since it is known from the above-mentioned publications.

On the other hand, the following is also possible with the present invention.

That is, instead of microcapsulating acid chloride, an aqueous alkaline solution is microcapsulated, this is dispersed in a hydrophobic solution containing acid chloride, this is uniformly treated on a fabric, and further steam treatment or dry heat treatment is performed. to perform chemical modification treatment.

As a method for microcapsulating the alkaline agent aqueous solution, the method described in Japanese Patent Publication No. 13703/1983 may be used.

However, according to experiments conducted by the inventors, it is better to microcapsule the acid chloride and disperse it in the acid chloride aqueous solution and then process it into fabric. The method of dispersing and processing into a fabric gave better results in terms of ease of handling and reaction efficiency.

When the thus obtained modified fabric was dry-printed using commercially available transfer paper using sublimable disperse dyes, the dyeability of the disperse dyes was good, and the dyeability was high and the color fastness was good. I was able to obtain some beautiful prints.

Acid chlorides that can be used in the present invention include sulfones whose general formula has the following structure, such as P-toluenesulfonyl chloride, benzenesulfonyl chloride, 0-nitrobenzenesulfonyl chloride, m-nitrobenzenesulfonyl chloride, and P-nitrobenzenesulfonyl chloride. Acid chlorides can be used.

(X means H, -NO2, or CH3) The alkaline agents used in the present invention include alkali metals or alkaline earth metals such as lithium, sodium, potassium, beryllium magnesium, calcium, barium, and strontium. Hydroxide etc. can be used.

Moreover, this method can also be used in combination with other conventional methods.

For example, the modified fabric obtained by the above method can be dyed with resins that are dyeable with disperse dyes, oil-soluble dyes, mordant dyes, basic dyes, vat dyes, etc., such as amino alkyd resins, polyamides, urethanes, vinyl chloride, acetic acid. By treating with vinyl, polyester, acrylic, acetal, polyvinyl alcohol, vinylidene chloride, vinyl acecool, styrene, polycarbonate, epoxy resin, etc., and then performing dry transfer printing, it is possible to further increase density, hue color, depth, etc. can.

In addition, the modified fabric can be dimethylol urea, dimethylol propylene urea, dimethylol dihydroxyethylene urea, dimethylol uron, trimethylol melamine, trimethoxymethyl melamine, hexamethoxymethyl melamine, dimethylol methyl triazone, dimethylol ethyl triazone. , dimethylol hydroxyethyl triazone, dimethylol methyl carbamate, dimethylol ethyl carbamate, dimethylol hydroxyethyl carbamate, N-methylol acrylamide, methylol glyoxal monourea, methylol glyoxal diurea, formaldehyde, tetraoxane, glitaraldehyde, dieboxide, divinyl sulfone , 4-methoxy-5-dimethyldimethylolpropyleneurea, tetramethylolacetylene diurea, etc., and crosslinking catalysts, such as organic acids such as acetic acid and maleic acid, and ammonium salts such as ammonium chloride, ammonium sulfate, and ammonium hydrogen phosphate. , ethanolamine hydrochloride, amines such as 2-amino-2-methylpropertool hydrochloride, magnesium chloride, zinc nitrate, zinc chloride, magnesium nitrate, zinc fluoroboride, aluminum chloride, magnesium phosphate, etc. to crosslink the crosslinking agent. By doing so, it is possible to improve the texture, and for example, it is possible to freely adjust the finish, such as a hard finish or a soft finish.

Cellulose fibers applied to the present invention include natural cellulose fibers such as cotton, regenerated cellulose fibers such as viscose rayon, and mixtures of these fibers and synthetic fibers such as polyester are also applicable. Of course, thread-like materials other than fabrics are also possible.

In addition, dyes that can be used in this method include disperse dyes, oil-soluble dyes, mordant dyes, basic dyes, vat dyes, etc., which may or may not have sublimation properties, and are printed by direct printing or transfer printing. be able to.

In particular, when a sublimable dye is used, a dry transfer printing method is possible.

The present invention will be further explained in detail below using the drawings.

That is, FIG. 1 shows a schematic diagram of a modifier used in the present invention, in which a cellulose fiber structure and a mixed structure of cellulose fibers and synthetic fibers, that is, raw fabric 1, are passed through a lead roll R1 and treated with a modifier. That is, at least one of the acid chloride and the alkaline agent is introduced into a mixed solution tank 2 in which microcapsules are formed, and then squeezed with a squeezing roll 3 so that the amount of treatment becomes uniform, and dried with a dryer (pin tenter oven) 4. Dry it.

Next, the treated raw fabric 1 is introduced into a continuous loop steamer 5 via a lead roll R2 for the purpose of further steam treatment, and then sequentially into a water washing (or hot water) bath 6, a soaping bath 7, and a washing bath 8. The chemically modified fabric 10 is obtained by introducing the chemically modified fabric 10 into a drying dryer (pin tenter oven) 9.

This will be explained below using examples.

Example 1 (1) Using P-toluenesulfonyl chloride as the e-chloride, dissolve 40 parts by weight in toluene and microcapsulate the solution to obtain a P-toluenesulfonyl chloride toluene solution that accounts for 70% of the total weight of the microcapsules. Microcapsules containing the following were obtained.

(2) Next, 50% by weight of the microcapsules obtained in (1) are mixed into 5 parts by weight of an aqueous sodium hydroxide solution, stirred in a star sea, and dispersed uniformly in the treatment liquid. The molar ratio of the active ingredients of sodium hydroxide and P-toluenesulfonyl chloride was approximately 0.85.

(3) Next, mercerized polyester/cotton =
One side of a 65/35 blended broad fabric was roll coated using the treatment solution obtained in (2), and 1 coat was applied to the fabric.
00 parts by weight of the treatment solution was applied.

Next, this cloth was dried by staying in a pin tenter oven at 60°C for 40 seconds, then steamed for 3 minutes in normal pressure saturated steam at 100°C, and then washed with water, soaped with Marrecel soap, and washed with water. and then dried to obtain a modified fabric.

(4) Next, gravure printing was performed on 60 g/m'' single-sided starch-coated paper using ink having the composition below to obtain a transfer paper.

<Ink> (5) Layer the transfer paper (4) on the modified cloth (3) at a temperature of 195°C and a pressure of 300 g/a? t, time 4
When transfer printing was carried out by applying heat and pressure for 0 seconds, a printed fabric with a red density between the polyester portion and the cotton portion was obtained, and the fastness was also good.

Example 2 (1) A modified fabric was obtained as in Example 1.

Next, the modified fabric was immersed in a solution of the following formulation (a), then squeezed to a squeezing rate of well over 80, pre-dried at 100°C for 12 minutes, and then baked at 150°C for 3 minutes.

(b) Prescription (2) Next, a transfer paper was prepared as in (Example 1).

(3) The modified cloth (1) was overlaid with the transfer paper (2), and the temperature was 195°C, the pressure was 300 g/cmt, and the time was 4.
When the transfer was performed by heating and applying pressure for 0 seconds, it was possible to obtain a printed fabric with red density, coloring, and depth between the polyester portion and the cotton portion.

When the washing fastness was measured, it was grade 5 according to method (A-2), indicating that the printed fabric was fast.

In addition, when the color density of the transferred printed fabrics with and without resin treatment was measured using a Macbeth reflection densitometer, the former was 1.20 and the latter was 1.28, indicating a clear increase in density.

Example 3 Instead of steaming for 3 minutes in saturated steam at 100°C under normal pressure in Example 1, baking was performed in a dry heat oven at 130°C for 3 minutes, resulting in a chemically modified fabric similar to Example 1. However, the color density of the transfer-printed chicks was 1.20 in Example 1 using a Macbeth reflection densitometer, whereas in this example it was 1.05, indicating that the effect of the modification was due to the steam heat. It turned out to be better.

Example 4 (1) A sodium hydroxide aqueous solution was microencapsulated to obtain microcapsules containing sodium hydroxide at a ratio of 30 to the total weight of the microcapsules.

(2) Next, 25% by weight of the microcapsules obtained in (1) are mixed into a toluene solution containing 20 parts by weight of P I'luenesulfonyl chloride, stirred with a starmer, and uniformly dispersed for treatment. The molar ratio of the active ingredient of sodium hydroxide and P-1 luenesulfonyl chloride in the liquid was about 1.8.

(3) Next, mercerized polyester/cotton
Example 2 on one side of a 65/35 blend camp link fabric
Similarly, roll coating was performed using the treatment liquid obtained in (2), and 100 parts by weight of the treatment liquid was applied to the fabric.

Next, this cloth was air-dried in a pin tenter oven at 25°C, then steamed for 3 minutes in normal pressure saturated steam at 100°C, washed with water, soaped, washed with water, and then dried and modified. A cloth was obtained, and transfer printing was performed in the same manner as in Example 2, resulting in a beautiful printed cloth.

Example 5 (1) Dissolve 40 parts by weight of 0-nitrobenzenesulfonyl chloride in toluene and microcapsule the solution to form microcapsules containing 0-nitrobenzenesulfonyl chloride/toluene solution at 70% of the total weight of the microcapsules. Obtained.

(2) Next, 50 parts by weight of the microcapsules obtained in (1) are mixed into 5 parts by weight of an aqueous sodium hydroxide solution, stirred with a starmer, and dispersed uniformly. The molar ratio of the active ingredients of sulfur oxide and O-nitrobenzenesulfonyl chloride (sulfur hydroxide 10-nitrobenzenesulfonyl chloride) is approximately 1.0.
And so.

(3) Next, mercerized polyester/cotton
Using the apparatus shown in FIG. 1, 100 parts by weight (100% 0 Wf) of the treatment liquid obtained in step (2) was applied to a 65/35 blended broad cloth.

This cloth was then placed in a pin tenter oven at 60°C for 50 minutes.
After staying there for a second and drying, it was further steamed for 3 minutes in normal pressure saturated steam at 100° C., washed with water, soaped, washed with water, and then dried to obtain a modified fabric.

(4) Then, using dry transfer printing paper manufactured by Toppan Printing Company using disperse dyes, the temperature was 195℃ and the pressure was 200g/cyr.
When transfer printing was carried out under the conditions of Y and time of 35 seconds, a beautiful printed cloth was obtained and the fastness was also good.

Example 6 (1) Benzenesulfonyl chloride was microencapsulated to obtain microcapsules containing 5ob benzenesulfonyl chloride of the total weight of the microcapsules.

(2) Next, 30 parts by weight of the microcapsules obtained in (1) are mixed into 5 parts by weight of sodium hydroxide aqueous solution, stirred with a starmer, and dispersed uniformly. The molar ratio of the active ingredients of sodium oxide and benzenesulfonyl chloride was approximately 1.03.

(3) Next, mercerized polyester/cotton
Using the apparatus shown in Figure 1, the treatment solution obtained in step (2) was uniformly applied to a 65/35 blended broad cloth at 100% ow, and then continuously heated in a pin tenter oven at 60°C for 5 minutes.
After drying for 0 seconds, it was further steamed for 3 minutes in normal pressure saturated steam at 100°C, and further washed with water and soaped to obtain a modified fabric in the same manner.

(4) Thereafter, dry transfer printing was performed in the same manner as in Example 5, and a beautiful pattern was obtained.

[Brief explanation of the drawing]

The drawings show one embodiment of the present invention, and FIG. 1 shows a schematic diagram of a reforming device used in the dyeing method of the present invention. 1... raw fabric, 2... modifier treated bathtub, 3
... Squeezing roll, 4, 9 ... Drying dryer (pin tenter oven), 5 ... Continuous loop steamer, 6 ... Washing with water (or washing with hot water) Bathtub, 7...soaping bathtub, 8...washing bathtub, 10...chemically modified cloth, R1°R2...
...Lead roll.

Claims (1)

[Scope of Claims] 1. A cellulose fiber structure and a mixed structure of cellulose fibers and synthetic fibers are treated with a liquid mixture in which at least one of an acid chloride and an alkaline agent having the following structure is microencapsulated, and then subjected to steam treatment. Or perform dry heat treatment and chemical modification, then disperse dyes, oil-soluble dyes, mordants,
A dyeing method characterized by dyeing with basic dyes, vat dyes, etc. (phrase 2 in which X means H, -No2. or -CH3) Claim 1 states that the dyeing is dry transfer printing using a heat transferable dye such as sublimation, vaporization, or melt transfer dye. 3. After chemically modifying cellulose fiber structures and mixed structures of cellulose fibers and synthetic fibers, dyeability is further imparted to disperse dyes, oil-soluble dyes, mordant dyes, basic dyes, vat dyes, etc. The method according to claims 1 to 2, wherein the cellulose fiber structure and the mixed structure of cellulose fiber and synthetic fiber are chemically modified, and then further crosslinked with a fiber crosslinking agent. The method according to any of claims 1 to 3, wherein the method is treated with a catalyst.