JPS6019935B2 - disperse dye composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a disperse dye composition that can be used for printing or thermosol dyeing synthetic fibers such as polyester fibers and triacetate fibers, or blended fibers of the above synthetic fibers and natural fibers such as cellulose fibers. be.

Accordingly, disperse dye compositions are prepared by adding an anionic dispersant, such as sulfonate salts of phenol formaldehyde low condensates, to the dye base material in an amount of 0.5 to 2 times the amount of the dye base material. It is usually produced by micronizing the active substance in water.

Although such disperse dye compositions maintain very good dispersibility, these dispersants are all discarded into dyeing wastewater after dyeing, so the content of dispersants in disperse dye compositions is Less is better. The present inventors conducted various studies in order to reduce the amount of additives such as dispersants that are used in large amounts in conventional disperse dye compositions and to increase the concentration of the dye base material. As a result, the general formula (1 ) (In the formula, RI represents a hydrogen atom or a Q-methylbenzyl group, R2 represents a hydrogen atom or a Q-methylbenzyl group, R3 represents a hydrogen atom or a methyl group, and R4 represents a hydrogen atom, a methyl group or a Q-methylbenzyl group. , 1 and n, one of which is 0 and the other is an integer of 7 to 30, and m is an integer of 0 to 20.

) By using the water-dropping surfactant shown in ) as a dispersant, it is possible to obtain a disperse dye composition that maintains very good dispersibility and has a high concentration of dye base material with an extremely small amount used. This is the heading that led to the present invention. The present invention will be explained in detail below.

The essential components of the disperse dye composition of the present invention are a water-insoluble or water-soluble dye and a water-soluble surfactant represented by the general formula (1).

As the dye that is insoluble or sparingly soluble in water, any of the usual disperse dyes such as anthraquine, azo, quinophthalone, methine, and heterofused ring dyes can be used.

The concentration of these disperse dyes in the composition is between 10 and 6% by weight.
, preferably from 15 to 5% by weight. The water-soluble surfactant represented by the general formula (1) can be easily produced, for example, by reacting phenol, metacresol, or para-cresol with styrene, ethylene oxide, and propylene oxide, and can be used alone. It can be used or used as a mixture of two or more types, and in the present invention, it is possible to use 0 in the disperse dye composition.
．． It is contained in an amount of 5 to 10% by weight, preferably 1 to 5% by weight.

The disperse dye composition of the present invention has the above disperse dye represented by the general formula (1).
It can be obtained by dispersing in water using a water-soluble surfactant shown in
It can also be obtained by dispersing it in a water-soluble organic solvent such as alcohol, propanol, ethylene glycol, tetrahydrofuran, dioxane, or a mixed solution of the water-soluble organic solvent and water.

The disperse dye composition of the present invention may contain optional components such as an anti-drying agent, an antifoaming agent, a hydrotrope, an anionic dispersant, and the like.

As anti-drying agents, ethylene glycol, propylene glycol, glycerin, 1,5-pentanediol,
Examples include ethylene glycol, low molecular weight polyethylene glycol having a molecular weight of 200 to 40 G, and the like. Examples of antifoaming agents include silicone antifoaming agents such as FS Antiform 544 (trademark) made by Dow Corning, Pluronic antifoaming agents such as Adekanol LG-21 (trademark) made by Asahi Denka, and Surfi made by Nissin Chemical. Examples include alcohol defoaming agents such as Knoll 10 Misaki (trademark). Examples of hydrotropes include urea and dimethylurea. Examples of the anionic dividing agent include lignin sulfonates, sulfonate salts of phenol-formaldehyde low condensates, and sulfonate salts of naphthalene-formaldehyde low condensates. The disperse dye compositions of the present invention are manufactured in the same manner as conventional disperse dye compositions.

For example, by finely pulverizing a water-insoluble or soluble dyestuff, 10 to 6 parts by weight of the dyestuff, preferably 15 to 6 parts by weight, are prepared.
50 parts by weight, 0.5 to 1 part by weight of a water-soluble surfactant represented by general formula (1), preferably 1 to 5 parts by weight, and if necessary, an anti-drying agent, an antifoaming agent, an anionic dispersant, After adding a hydrotrope or the like to water and/or a water-soluble organic solvent to bring the total to 100 parts by weight, use a pulverizer such as a sand grinder or paint conditioner to grind the dyestuff into 0.01 to 10 parts by weight. Preferably 0.0
A liquid disperse dye composition can be obtained by crushing and dispersing into particles of 1 to 1 particle size. The disperse dye composition of the present invention has a very low viscosity and good fluidity because the amount of water-soluble surfactant used as a dispersant is small.
Good workability and yield during production.

Since it has a low viscosity, it has good dilution and dispersibility with water and is easy to handle. In addition, by using a surfactant represented by general formula (1), the dispersibility of the dye becomes extremely high, and the concentration of the dye source in the composition can be increased to about twice that of conventional products. In addition, although the dye particles have a very low density, there is almost no sedimentation of the dye particles over time, so it can be stored for a long period of time.

In addition to these advantages, the disperse dye composition of the present invention has a very high dye pick-up rate during dyeing, and when compared with conventional disperse dye compositions, it provides a similar surface concentration to the fibers. Dyeing processing costs are significantly improved due to the fact that the amount used for dyeing is significantly reduced, there is no need to use color development aids such as deep dyes, and the burden of dyeing wastewater is reduced. It has the following characteristics.

Next, 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 the gist of the present invention is exceeded. Test methods for various physical properties of disperse dye compositions, dyeing methods, and methods for measuring deep dyeability of beam cloth in the following Examples and Comparative Examples are as follows.

1 Dye Concentration Weigh 0.5 mm of the disperse dye composition and dilute it with water to make 100 mm.
Dilute to 100% with 1% acetic acid (acidic acid).

The absorbance (nm) of this solution at ^Max was measured and relatively compared. (The comparative example was set as the standard (100).)
2 Viscosity The viscosity of the disperse dye composition was measured under the following conditions using a BL viscometer manufactured by Tokyo Keiki Co., Ltd.

Measured temperature: 2 pi○ Used temperature: Chest. 1 Rotor rotation speed 6 and 35 pm 3 Particle size Disperse dye composition 0.5 liters was accurately weighed, diluted with water and 100'
Make it.

This aqueous dye solution was filtered using the following quantification paper made by Toyo Roshi Co., Ltd., and the particle size was determined based on the state of dye particles remaining on the paper. (Furnace particle size test method) Furnace paper type Passing particle guideline 5A ~ 7r ~ or less ~ 3 ~ or less wide ~ 1' ~ or less 4 Water dispersion rate Precisely weigh 0.4 mm of disperse dye composition and dilute with water 100'
Make it.

Transfer this aqueous dye solution to a 100ml measuring cylinder and let it stand at room temperature for 2 hours, then add 10' from the top and 10' from the bottom.
Remove the top. This extracted aqueous dye solution was used in step 1 of this journal's experimental method. Measure the dye concentration using the dye densitometry method.

Then, the water dispersion rate was calculated using the following formula. Shizukubishi Minato was succeeded to Rokuno ×・〇.

=Water dispersion rate (%) 5 The heat-stable disperse dye composition was heated under the following conditions and maintenance of its fluidity was observed.

Dry heat constant temperature bath 60°C x 1 hour 6 Stability over time The disperse dye composition was stored statically at room temperature for 180 days, and the presence or absence of sedimentation of the dye particles was observed.

7 Dyeing method and deep dyeing measurement method '1' Printing method The following composition Disperse dye composition 3% by weight Original Paste
60 Tartaric acid 0.3 Equalizing agent (manufactured by Nicca Chemical Co., Ltd., trademark: Neotex CTP) 0.1 Anti-reduction agent (manufactured by Meisei Chemical Co., Ltd., trademark: MS Powder) 0.3 Water Balance total 10% by weight Color Screen print on polyester silk satin cloth using glue and dry (100 qo x 2 minutes).

Next, this was fixed using high temperature normal pressure steaming method (175℃ x 7
After treatment with 10 minutes), reduction cleaning is performed to obtain a printed cloth. However, in the comparative example, in addition to the color paste of the above-mentioned composition, 3% by weight of crosslinking agent (manufactured by NICCA Chemical Co., Ltd., trademark: Sunfloren SN) was used.
We also used colored paste with the addition of , and the resulting beam cloth was used as the standard.

'21 Thermosol dyeing method The following composition Disperse dye composition 2% by weight Medium viscosity sodium alginate (manufactured by Kamogawa Kasei Co., Ltd., trademark: Duck Algin NSPN) 0.1 water
97.9 A polyester knit cloth is soaked in a total of 100 pads, squeezed with a pressure mangle to a squeezing rate of 90%, and dried at 130°C for 2 minutes.

Next, this is treated by a dry fixing method (200°C x 2 minutes), and then reduction washing is performed to obtain a dyed fabric. [3] Method for measuring deep dyeing property The surface reflectance of the dyed fabric was determined using a color difference meter (manufactured by Nippon Denshoku ■), and the value was calculated with the dyed fabric obtained in the comparative example as 100 (standard).

Example 1 Parts by weight of azo disperse dye source powder 3 represented by the following formula, 1 mole of a mixture of meta and para-cresol, 1 mole of styresol, and 7 moles of ethylene oxide were reacted to produce a dye represented by the following formula and 1 part by weight of a water-resistant surfactant mainly composed of compounds, 0.05 parts by weight of a Pluronic antifoaming agent (manufactured by Asahi Denri Co., Ltd., trademark Pluronic L-61), an anionic dispersant of phenol formaldehyde low condensate. 1 part by weight of sulfonate (manufactured by Nippon Nyukazai, trademark isroISH) and 6 parts of water
7.95 parts by weight were mixed and ground in a sand glider at room temperature to prepare a disperse dye composition.

When polyester fibers were printed using this disperse dye composition, no speckling was observed, and a beautiful print with a uniform, clear, dark yellow color was obtained. In addition, when polyester fibers were subjected to thermosol dyeing, a bright yellow dyed product with excellent level dyeing properties and a good texture was obtained. Table 1 shows a comparison of various physical properties of the disperse dye compositions and deep dyeing properties of dyed fabrics.

Example 2 30 parts by weight of the same dye source powder used in Example 1, 1 mole of a mixture of meta and para-cresol, 2 moles of styrene and 15 moles of ethylene oxide were reacted to produce a compound represented by the formula and 5 parts by weight of a water-borne surfactant, 1 part by weight of ethylene glycol, and 0.0 parts by weight of a commercially available Bluronic foaming agent (manufactured by Toho Kagaku Co., Ltd., trademark Bronal 502).
Example 1
Micronization was carried out in the same manner as above to prepare a disperse dye composition.

Table 1 shows various physical properties of the obtained disperse dye composition and deep dyeing properties of the dyed fabric obtained by printing and thermosol dyeing. Example 3 3 parts by weight of the same dyestuff powder as used in Example 1, 5 parts by weight of the water-soluble surfactant used in Example 1, and 5 parts by weight of the water-soluble surfactant used in Example 2. and 6 parts by weight of water to prepare a disperse dye composition in the same manner as in Example 1.

Table 1 shows the physical properties of the obtained disperse dye composition and the deep dyeing properties of the beam cloth by printing and thermosol dyeing. Further, when a blended fiber of polyester fiber and cellulose fiber was thermosol dyed using this disperse dye composition, a yellow marbled dyed product with a good texture and no appearance of specks was obtained.

Example 4 25 parts by weight of an anthraquinone disperse dye source powder represented by the formula, 1 mole of phenol, 2 moles of styrene and 1 mole of propylene oxide were reacted, and then 7 moles of ethylene oxide were reacted. A compound represented by the formula obtained by reacting 9.5 parts by weight of a water-soluble surfactant mainly composed of the compound shown above, 1 mole of phenol, 3 moles of styrene, 1 mole of propylene oxide, and 7 moles of ethylene oxide was prepared. 0.5 parts by weight of a water-soluble surfactant, 0.0 part of a commercially available alcoholic antifoaming agent (octanol)
5 parts by weight, 10 parts by weight of urea, and 54.95 parts by weight of water were mixed and micronized in the same manner as in Example 1 to prepare a disperse dye composition.

Table 1 shows the physical properties of the disperse dye composition obtained and the deep dyeing properties of beam cloth. Example 5 25 parts by weight of the raw dye powder used in Example 4, 2.5 parts by weight of a water-soluble surfactant represented by the formula, 2.4 parts by weight of a water-dropping surfactant represented by the formula, 25 parts by weight of the water-soluble surfactant represented by the formula, 0.1 parts by weight of a water-soluble surfactant, 0.05 parts by weight of a commercially available silicone antifoaming agent (manufactured by Dow Corning Co., Ltd., trade mark SA Yamachi am) and 69.95 parts by weight of water were mixed. A disperse dye composition was prepared by micronizing in the same manner.

The physical properties of the bound disperse dye composition are shown in Table 1. Table 1 also shows the deep dyeing properties of polyester beam fabrics obtained by printing and thermosol dyeing using this disperse dye. Example 6 25 parts by weight of the raw dye powder used in Example 4, 2 parts by weight of the water-soluble surfactant represented by the formula, and 73 parts by weight of water were mixed, and the mixture was converted into fluid particles in the same manner as in Example 1. A disperse dye composition was prepared.

Table 1 shows the physical properties of the disperse dye composition obtained. Also,
Table 1 also shows the cross-crossability of polyester dyed fabrics obtained by printing and thermosol dyeing using this disperse dye composition. Example 7 50 parts by weight of the anthraquinone disperse dye raw material powder represented by the formula and 1 mole of a mixture of meta and para-cresol were reacted with 2 moles of styrene, then 1 mole of propylene oxide, and then 10 parts by weight of ethylene oxide. 5 parts by weight of a water-soluble surfactant containing the compound represented by the formula obtained by reacting the moles and 45 parts by weight of water were mixed, and the mixture was made into fine particles in the same manner as in Example 1 to obtain a disperse dye composition. I prepared something.

Table 1 shows the physical properties of the obtained disperse dye composition. Also,
Table 1 also shows the deep dyeing properties of polyester dyed fabrics obtained by printing and thermosol dyeing using this disperse dye composition. Example 8 Parts by weight of raw dye powder 5 used in Example 7, mixture 1 of meta and para-cresol
Formula obtained by reacting 2 moles of styrene with 2 moles of styrene, followed by 1 mole of ethylene oxide, and then 1 mole of propylene oxide, and 5 weights of a water-soluble surfactant mainly consisting of a compound represented by the formula. 5 parts by weight of glycerin, 0.05 parts by weight of a commercially available silicone antifoaming agent (manufactured by Shin-Etsu Chemical Co., Ltd., trademark Shin-Etsu Silicone KS502) and 39.95 parts by weight of water, and disperse dye was prepared in the same manner as in Example 1. A composition was prepared.

Table 1 shows the physical properties of the disperse dye composition obtained. Also,
Table 1 also shows the beam properties of polyester dyed fabrics obtained by printing and thermosol dyeing using this disperse dye composition. Example 9 Parts by weight of the raw dye powder 5 used in Example 7, 2.5 parts by weight each of the water-soluble surfactants used in Examples 7 and 8, and a commercially available silicone antifoaming agent (manufactured by Asahi Chemical Co., Ltd., Trademark Asahi Silicone AF-145) 0.05 parts by weight, anionic dispersant lignin sulfonate (Wes
2 parts by weight of Reax 8 (trade name, manufactured by tvaco) and 42.95 parts by weight of water were mixed and micronized in the same manner as in Example 1 to prepare a disperse dye composition.

Table 1 shows the physical properties of the obtained disperse dye composition and the deep dyeing properties of polyester dyed fabrics by printing and thermosol dyeing.
Shown below. Comparative Example 1 As a comparative example for Examples 1 to 3, parts by weight of the raw dye powder 3 used in Example 1 and a phenol-formalin low condensate as an anionic fractional agent instead of the lagoonal surfactant of the present invention were used. A disperse dye composition was prepared by mixing 45 parts by weight of a sulfonic acid salt (manufactured by Nippon Nyukazai Co., Ltd., trademark: Niji isroISH) with 25 parts by weight of water, and micronizing the mixture in the same manner as in Example 1.

The physical properties of the obtained disperse dye composition and the deep dyeing properties of polyester beam cloth by printing and thermosol dyeing are shown in Table-
Shown in 1. Comparative Example 2 As a comparative example for Examples 4 to 6, 25 parts by weight of the dye source powder used in Example 4 and lignin sulfonate (Westvaco A disperse dye composition was prepared in the same manner as in Example 1 by mixing 5 parts by weight of 5 parts by weight of 5 parts by weight of 5 parts by weight of 5 parts by weight of 25 parts by weight of water.

Table 1 shows the physical properties of the bound disperse dye composition and the deep dyeing properties of beam cloth. Comparative Example 3 As a comparative example for Examples 7 to 9, phenol-formalin was added as an anionic dispersant to parts by weight of the dye base powder 6 used in Example 7 above, instead of the water-soluble surfactant of the present invention. Examples were prepared by adding 2 parts by weight of a lignin sulfonate (manufactured by Nippon Nyukazai Co., Ltd., trademark DismISH) and 5 parts by weight of a lignin sulfonate (manufactured by Westvaco Company, trademark Mushi eax8hiro), and mixing with 25 parts by weight of water. A disperse dye composition was prepared in the same manner as in Example 1.

Table 1 shows the physical properties of the disperse dye composition obtained and the deep dyeing properties of polyester beam cloth by printing and thermosol dyeing. -[1

Claims (1)

[Claims] 1 10 to 60% by weight of a dye that is insoluble or poorly soluble in water and a general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^1 represents a hydrogen atom or an α-methylbenzyl group) where R^2 represents a hydrogen atom or an α-methylbenzyl group, R^3 represents a hydrogen atom or a methyl group, R^4 represents a hydrogen atom, a methyl group or an α-methylbenzyl group, and R^1 , R^2 or R^4 represents an α-methylbenzyl group, one of 1 and n is 0, the other is an integer of 7 to 30, m
is an integer from 0 to 20. ) A disperse dye composition containing 0.5 to 10% by weight of a water-soluble surfactant.