JPS6059939B2 - disperse dye composition - Google Patents

Description

[Detailed description of the invention] The present invention relates to disperse dye compositions.

Specifically, it relates to a disperse dye composition that can be used for printing and thermosol dyeing of synthetic fibers such as polyester fibers and triacetate fibers, or blended fibers of these synthetic fibers and natural fibers, such as blended fibers of polyester fibers and cellulose fibers. It is something. Conventionally, disperse dye compositions have been produced by adding a fairly large amount of an anionic dispersant, such as sulfonate salts of phenol-formalin low condensates, to the dye base material, and then micronizing the dye base, usually in water. .

Although such disperse dye compositions maintain very good dispersibility, they have various drawbacks due to the addition of a large amount of anionic dispersant. Normally, when printing,
A color paste for printing is prepared by mixing the above-mentioned disperse dye composition with a printing paste made of a water-soluble polymer material such as starch, polyoxymethylcellulose, or locust bean gum, and then this colored paste is mixed with a polyester. Printing is performed on fibers or blended fibers of polyester fibers and cellulose fibers.
Subsequently, high temperature and high pressure steam fixation method (hereinafter abbreviated as HPS method), high temperature normal pressure steam fixation method (hereinafter referred to as ET
It is abbreviated as S. ), or dry heat fixation method (hereinafter referred to as Cure
Abbreviated as law. ) The dyes are fixed in the fibers by various methods such as In particular, with the rationalization of staining due to recent advances in staining methods, HTS
With the widespread adoption of the Cure method and the Cure method, it has become possible to streamline the process through continuous textile printing.

However, when conventional disperse dye compositions are used in the above-mentioned continuous printing, the dye particles are significantly stabilized within the printing paste layer due to the large amount of anionic dispersant added thereto, and the During the fixing process, the diffusion of dye particles within the glue layer is significantly inhibited.

As a result, there is a limit to the fixation rate of dyes on synthetic fibers such as polyester fibers, resulting in insufficient surface coloring density and difficulty in developing vivid colors. In particular, the deep dyeing properties in deep color dyeing are very poor, and the current situation is that there are various problems from the economic point of view. In order to improve this shortcoming,
For example, it is conceivable to achieve deep dyeing by increasing the amount of dye used, but this is unsatisfactory in many respects, such as severe contamination of hot water due to unfixed dye during the washing process and the burden of wastewater treatment. Also known is a method of printing by adding a so-called carrier, a compound capable of swelling polyester such as chlorobenzene or methylnaphthalene, to a color paste for printing.

This method promotes the diffusion of disperse dye inside the fiber, so
Although it is possible to improve the fixation rate of dyes and increase the surface color density, there are unsatisfactory aspects such as a decrease in light fastness and deterioration of the texture of the fibers. There is also a method of adding a surfactant as an auxiliary agent to the color paste for printing to make the disperse dye into a monomolecular, that is, a method of printing by adding a so-called deep dyeing agent, which is a compound that can speed up dye solubilization. It has been known.

This method promotes the diffusion of disperse dyes within the glue, improving the dye fixation rate and increasing the surface concentration. There are problems such as decreased sharpness during coating, poor coating strength that causes stains, and deterioration of the adhesive. In the case of thermosol dyeing, a disperse dye is generally mixed with an aqueous solution of a water-soluble polymer such as sodium alginate or a copolymer of maleic anhydride and vinyl acetate to prepare a bud bath. Polyester fibers or blended fibers of polyester fibers and cellulose fibers are immersed in the water, squeezed, pre-dried, and then processed using the HTS method or Cur'
A method of fixing the dye into the fiber by a fixing method such as the e-method is adopted.

However, when conventional disperse dye compositions are used in thermosol dyeing, the fixation rate of the dye is low due to the strong interaction between the dye particles and the anionic dispersant, similar to the behavior described above in the case of textile printing. Difficult to dye dark colors. In that case, if a large amount of dye is used for deep color dyeing, unfixed dye will flow out into the waste water, causing a problem of pollution. Furthermore, in order to improve the level dyeing property, a! Large amounts of water-soluble polymer substances such as sodium ruginate, so-called anti-migration agents, are added, but because they have poor compatibility with dyes, secondary aggregation of dye particles tends to occur, making it difficult to see specks. be. The present inventors have fully grasped the above-mentioned situation, and have applied the HTS method and Cure method particularly in textile printing, as well as the HTS method and Cure method in thermosol dyeing. To obtain a disperse dye composition for textile printing and thermosol dyeing, which has a significantly high dye fixation rate and a surface coloring density that is significantly better than expected from the fixation rate, and is free from the above-mentioned defects. We conducted intensive research with the aim of

In conventional disperse dye compositions, the amount of anionic dispersant used is extremely reduced or completely eliminated, and instead, a specific polyvinyl alcohol having protective colloid dispersion ability is added to the dye base material. .05~2. The present invention was achieved based on the finding that printing and thermosol dyeing of fibers such as polyester can be carried out extremely well by using a disperse dye composition prepared by adding twice the amount. That is, the gist of the present invention is to provide water-insoluble or slightly water-soluble dyes and JO. The average degree of polymerization of O5 to 2.0 times by weight is 300 to 2000 and the degree of saponification is 97 to 7.
A disperse dye composition characterized in that it contains 5 mol% of polyvinyl alcohol.

Hereinafter, to explain the present invention in detail, the water-insoluble or poorly water-soluble dyes used in the composition of the present invention include various well-known water-insoluble or poorly water-soluble anthraquinones, azo dyes, and quinophthalones. Any of the conventional nonionic dyes such as the dyestuffs and the like can be used.

The composition of the present invention contains polyvinyl alcohol having an average degree of polymerization of 300 to 2000 and a degree of saponification of 97 to 75 mol% as an essential component. Such polyvinyl alcohols are highly compatible in dye compositions. The polyvinyl alcohol used in the composition of the present invention is generally represented by the following formula. (In the formula, m and n do not represent the number (number of moles) of each unit in the polymer.

Therefore, m+n represents the average degree of polymerization, m/m+n×1
00 represents the degree of saponification. ) Such polyvinyl alcohols can be selected from, for example, those commercially available from Nippon Gohsenol Co., Ltd. under the registered trademark 0 Gohsenol, such as 1 Gohsenol Type A, 1 Gohsenol Type G, and 1 Gohsenol K. This applies to products marketed under the trademark "Katayo". In obtaining the composition of the present invention, the average degree of polymerization of polyvinyl alcohol is from 300 to
2000 and a saponification degree of 97 to 75 mol% can be used, but especially those with an average polymerization degree of 500 to 1500 and a saponification degree of 90 to 75 mol% can be used.
Best results are obtained using 78 mole percent polyvinyl alcohol.

These polyvinyl alcohols need to be blended at a ratio of 0.05 to 2.0 times by weight, preferably 0.2 to 1.7 times by weight, relative to the water-insoluble or poorly water-soluble dyestuff. . In addition to the above-mentioned polyvinyl alcohol, the composition of the present invention may further contain an organic solvent, a dispersant, an emulsifier, an emulsion stabilizer, a foam suppressor, an antifoaming agent, a viscosity modifier, an anti-drying agent, etc., as necessary. good.

The compositions of the present invention are prepared in the same manner as conventional dye compositions.

For example, a water-insoluble or poorly water-soluble dye base material is finely ground, and water and polyvinyl alcohol are dispersed therein as necessary, usually 0.5 to 2 times the weight of the dye, preferably 1 to 10 times the weight. A paste is prepared by adding agents and emulsifiers, and if necessary, dispersion aids, viscosity modifiers, anti-drying agents, anti-foaming agents, etc.
0.0 with a grinder or paint conditioner.
It is produced by pulverizing and dispersing particles of 0.01 to 10 μm, preferably 0.01 to 1 μm. In this way, a paste-like disperse dye composition can be obtained. A colored paste for textile printing can be obtained by adding the composition of the present invention to a base printing paste made of ordinary natural or synthetic water-soluble polymeric substances or an emulsion base paste composed of an emulsified mineral turpentine.

A dye bud bath can also be obtained by adding a migration inhibitor such as aqueous sodium alginate. Examples of fibers that can be printed or thermosol dyed using the composition of the present invention include polyethylene. Examples include various hydrophobic synthetic or semi-synthetic fibers such as lenterephthalate fibers and polyoxybenzoate fibers, as well as blended fibers of these synthetic fibers and natural fibers such as cellulose fibers. Especially effective when applied to polyester fibers. The fruit is remarkable. The composition of the present invention is extremely useful in terms of economy, operability, etc. since it is possible to produce a product with a high concentration of dye, and the composition of the present invention can be stored in a stable dispersion state for a long period of time. The printing dyeing paste or thermosol bud bath prepared using this method is stable for a long period of time.

When printing or thermosol dyeing polyester fibers or blended fibers of polyester fibers and cellulose fibers using these printing pastes or thermosol bud baths, they exhibit extremely high dye fixation rates and surface color development. concentration is obtained. EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof.

In addition, 1 part in the examples indicates 1 part by weight.

Example 1 To 15 parts of azo disperse dye raw material powder represented by the following formula, 5 parts of polyvinyl alcohol having an average degree of polymerization of 600 and a saponification degree of 91 to 94 mol%, and an average degree of polymerization of 1700.
5 parts of polyvinyl alcohol with a degree of saponification of 87 to 89 mol%, 1 part of ethylene glycol, a silicone antifoaming agent (
Manufactured by Asahi Chemical Co., Ltd., trademark AsahiSillcOrleAF-
66) Disperse dye composition (color paste) with very low viscosity and long-term stability, by adding 0.5 parts and 73.5 parts of water and grinding in a sand grinder at room temperature to give a dye particle size of 1 to 10 microns. I got it.

Using this color paste, a colored paste was prepared according to the following recipe and used for printing.

However, the above-mentioned base glue was prepared and provided according to the following formulation.

The printing conditions were as follows: After screen printing the above color paste on polyester silk satin cloth, intermediate drying (80℃ x 3 minutes),
It was dried and fixed (200° C. for 2 minutes), then subjected to reduction soaping and then washed with water to obtain a beautiful, uniform, clear, dark yellow print.

In addition, when the intermediate dry cloth after printing was treated with a high temperature normal pressure steam fixing method (170°C x 7 minutes) and a high temperature high pressure steaming fixing method (130°C x 3 powders) instead of the dry heat treatment, Excellent printing results were also obtained.

The printing results are shown in Table 1. Example 2 Three parts of polyvinyl alcohol having an average degree of polymerization of 1400 and a degree of saponification of 87 to 89 mol% were added to (to) parts of the raw dye powder used in Example 1, and a commercially available Pluronic antifoaming agent (Toho Chemical Co., Ltd.) was added. A color paste was prepared using the same recipe as in Example 1 by adding 0.5 parts of Pronal 502 (trade name) and 81.5 parts of water, and was made into a color paste using a highly fluid, long-term stable, high-concentration disperse dye. A composition (color paste) was obtained.

This was subjected to color pasting and printing in the same manner as in Example 1 to obtain a uniform, clear, beautiful yellow print with an ultra-high density.

The printing results are shown in Table 1. Example 3 To 15 parts of the raw dye powder used in Example 1, 3 parts of polyvinyl alcohol having an average degree of polymerization of 1400 and a degree of saponification of 87 to 89 mol%, and a Pluronic antifoaming agent (manufactured by Asahi Denka Co., Ltd., Color paste and color glue were prepared using the same recipe as in Example 1 by adding 0.5 part of Pluronic L-61) and 81.5 parts of water, and the printing process was carried out in the same manner as in Example 1. A uniform, clear, beautiful, and highly concentrated yellow print was obtained.

The printing results are shown in Table 1. Example 4 Anthraquinone disperse dye raw material powder 15 represented by the following formula
part, the average degree of polymerization is 500 and the degree of saponification is 78 to 81 mol%.
25.5 parts of polyvinyl alcohol, nonionic surfactant (manufactured by Nippon Nyukazai Co., Ltd., trademark NewcOl7l4)
1 part, commercially available alcohol defoamer (octanol) 03 parts and water 58. ? A color paint and a color paste were prepared using the same recipe as in Example 1, and the printing process was carried out in the same manner as in Example 1 to obtain a uniform dark blue print.

The printing results are shown in Table 1. Example 5 To 15 parts of the raw dye powder used in Example 4, 3 parts of polyvinyl alcohol having an average degree of polymerization of 300 and a degree of saponification of 87 to 89 mol%, 0.5 part of polyethylene glycol having an average molecular weight of 400, and A color paste was prepared by adding 54.5 parts of water and processing in the same manner as in Example 1.

Using this color paste, a colored paste was prepared according to the following recipe and used for printing polyester fiber cloth.

However, the above-mentioned base glue was prepared and provided according to the following formulation.

The printing conditions were the same as in Example 1.

A uniform clear blue print with high density was obtained. The printing results are shown in Table 1. Example 6 Anthraquinone disperse dye raw material powder 15 represented by the following formula
1 part, 0.8 part of polyvinyl alcohol with an average degree of polymerization of 2000 and a degree of saponification of 87 to 89 mol%, a weak anionic nonionic surfactant manufactured by Taka Kagaku Co., Ltd., trademark Sunsolt 7
Example 1 by adding 0.5 parts of 000) and 83.7 parts of water.
A color paste and a color glue were prepared using the same recipe as in Example 1, and the printing process was carried out in the same manner as in Example 1 to obtain a dark and vivid red print.

The printing results are shown in Table 1. Example 7 To 15 parts of the raw dye powder used in Example 6, 6 parts of polyvinyl alcohol having an average degree of polymerization of 1700 and a degree of saponification of 79 to 82 mol%, and a commercially available Pluronic antifoaming agent (manufactured by NOF Corporation) were added. A color paste was prepared in the same manner as in Example 1 by adding 1 part of Dishome CE-457) and 78 parts of water.

Using this color ● paste, a bud bath was prepared according to the following recipe and subjected to thermosol dyeing.

For thermosol dyeing, the polyester knit fabric is immersed in the above bath, then squeezed with a pressure mangle to a squeezing rate of 90%, intermediately dried (130℃ x 2 minutes), and then dry heat fixed (2 minutes).
00° C. for 2 minutes), followed by reduction soaping and washing with water, to obtain a deep red, clear dyed product with good level dyeing properties and no migration of dye particles.

In addition, the same dyeing effect can be obtained even when the same thermosol dyeing as described above is carried out by adding a commercially available migration inhibitor (manufactured by Arakawa Chemical Co., Ltd., trademark Tamanoli SA-25) 2y/' used in normal thermosol dyeing to the above bad bath. It was done.

The staining results are shown in Table 2. Furthermore, instead of the above-mentioned polyester knit cloth, a 65:35 mixture of polyester and cotton is used.
Thermosol dyeing was carried out in the same manner as described above using the blended fabric.

As a result, we were able to dye the polyester side in deep red.

Furthermore, when the polyester side of the dyed blend fabric before reduction soaping was dissolved and removed, almost no staining by the disperse dye was observed on the cotton side. Comparative Examples 1 to 6 In Examples 1 to 6 above, the polyvinyl alcohol of the present invention was not added, but instead the anionic dispersant, sulfonic acid of phenol formalin low condensate, was added to the conventional disperse dye composition. Manufactured by Shiotamoto Emulsifier Co., Ltd., trademark Dl
A color paste was prepared in the same manner as in Example 1 by adding 2 times by weight of srOlSH) to the raw dye powder.

Subsequently, colored paste preparation and printing were carried out in the same manner as in each corresponding example, and as shown in Table 1, the dyeability was low.

Comparative Example 7 In Example 7, the polyvinyl alcohol of the present invention was not added, but instead an anionic dispersant, a sulfonate of phenol-formalin low condensate (Nippon Nyukazai) was added to the conventional disperse dye composition. Made by company, trademark Pls
rOlSH) was added twice by weight to the raw dye powder to form a color ● paste in the same manner as in Example 1.

Subsequently, a bad bath was prepared in the same manner as in Example 7, and the same thermosol dyeing treatment was performed. Ta.

1. Relative comparison of dyeing properties (deep dyeing properties) 1. Surface reflectance when the surface color development of the printed fabric fixed by high-temperature and high-pressure steaming in the comparative example is set as 100 using a color difference meter manufactured by Tamoto Denshoku ■ ).

2. Dye aggregation property The aggregation state of the dye was determined by observing with the naked eye the state of aggregation of the dye by microscopic photography (magnification: 780) after leaving the colored paste for 3 days.

3 Coating Strength The friction comparison of the printed and dried cloth was determined using a Gakushin type friction fastness measuring device (load 200 f x 5 reciprocating friction).

4 sharpness The degree of weeping of the printed fabric was inspected and judged.

5. 0.5 wt% of carbon powder is blended into the color paste, and the cloth that has been printed and fixed with this color paste is dyed at a temperature of 20°C, for a time of 1 powder, and at a bath ratio (
The determination was made by observing the carbon removal properties after washing at a cloth/bath weight ratio of 1:50.

6. Wash polyester white cloth of the same quality as the stain-prone printed cloth in the following reducing cleaning bath (
One powder was treated with 7C) at a bath ratio of 1:20), and the staining property of the white cloth was determined.

(Manufactured by Dai-ichi Kogyo Co., Ltd., trademark Amylazine) Thermosol dyeing test method> 1 Relative comparison of dyeing properties (dark dyeing properties) Surface of dyed fabric in which 2,y/' migration inhibitor was added and fixed by dry heat in comparative example The surface reflectance was determined using a color difference meter (manufactured by Nippon Denshoku ■) when the coloring property was set as 100.

2. The state of aggregation of the dye was visually observed and determined by microscopic photography (magnification: 780) after leaving the dye aggregating bud bath for 24 Tf.

3. Level dyeing property The level dyeing property was observed and compared based on the degree of level dyeing on the cloth surface of a dyed fabric in which 2 g/e of migration inhibitor was added and fixed by dry heat in Comparative Example.

4 Migration prevention properties Observe and compare the migration prevention properties based on the difference between the surface concentration of the dyed fabric (polyester knit) which was dry-heat-fixed with 2y/e of migration prevention agent added in the comparative example and the internal concentration of the fabric structure. I judged it.

The results of the above tests (excluding the relative comparison of stainability) are indicated by symbols in the table.

Claims (1)

[Claims] 1 A water-insoluble or slightly water-soluble dye and an average degree of polymerization of 0.05 to 2.0 times the weight of the dye is 300 to 20
00 and polyvinyl alcohol having an oxidation degree of 97 to 75 mol%.