JPS6028952B2 - Exhaust dyeing and continuous dyeing methods for synthetic fiber materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to exhaust dyeing or continuous dyeing of synthetic fiber materials from a solution or dispersion of a water-immiscible organic solvent using a dye represented by the following general formula '1}. .

(In the formula, ○ and E represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a lower alkyl group, a lower alkoxy group, and an alkylsulfonyl group, and R, and R2 are independently a hydrogen atom, a lower alkyl group, and 3 -Bidroxethyl group, 8-
Cyanoethyl group, trifluoromethyl group, 8-chloroethyl group, B-fromethyl group, or one or more bidroxy groups, nitro groups, carboxyl groups, lower alkoxy groups, carbamoyl groups, sulfamoyl groups, acylamino groups, lower alkylsulfonyl groups , represents a phenyl group substituted with a bidroxhethylsulfonyl group, a cyanoethylsulfonyl group, R3 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, R represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, It represents a halogen atom or an acylamino group.

However, when R is an acylamino group and R and R2 are both alkyl groups, and when R is an acylamino group and R,
Excluding the case where either one of and R2 is a hydrogen atom and the other is a lower alkyl group. The number of carbon atoms in the lower alkyl group, lower alkoxy group, and lower alkylsulfonyl group shall not be more than 4. ) The water-immiscible organic solvent suitable for the method of the present invention has a boiling point of 60qo to 180qo.
o aliphatic halogenated hydrocarbons such as 1,1,1-
Trichloroethane, 1,1,2-trichloroethane, 1
, 1,1,2-tetrachloroethane, trichlorethylene, tetrachloroethylene, 1,1,1-trichloropropane, 1,2,3-trichloropropane, 2-ethylhexyl chloride, 1,2-dibromoethane, chlorfrommethane, There are 2-from-1-chloroethane, etc., but tetrachlorethylene, trichlorethylene, 1,
1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,1-trichloropropane have been found to be particularly suitable.

It is also possible to use mixtures of these solvents. Furthermore, other organic solvents such as alcohol, dimethylformamide, dimethylacetonamide, and dimethylsulfoxide may be added to the above-mentioned solvents. It has been found that dyes of particular value in the present invention are dyes represented by the following general formula (2).

Here, B is a nitro group, a sia/group, a chlorine atom, and R',
, R'2 are each independently a hydrogen atom, a methyl group, an ethyl group, a propyl group, a P-hydroxycetyl group, a B-cyanoethyl group, or one hydroxy group, a nitro group, a carboxyl group, a carbamyl group, or a sulfamoyl group. , a phenyl group having a pidroxychetylsulfonyl group, or a cyanoethylsulfonyl group. (R7 and R8 have the same meanings as above.) The dye used in the method of the present invention is sparingly soluble or almost insoluble in water or water-immiscible aliphatic halogenated hydrocarbons; has far superior affinity color tone and sublimation resistance, light resistance, solvent resistance (dry cleaning), water resistance, and cover IJ resistance than dyes commonly used in the past for dyeing synthetic fiber materials from organic solvents. It is to have gender, etc.

Two or more types of dyes represented by the general formula '1} can be used in combination, which may provide a better dye fixation rate.

In many cases, the dyeability can be further improved by adding a small amount of water (0.5 to 1% by weight based on the weight of the organic solvent) to the liangge.

It may also be advantageous to add nonionic auxiliaries such as aliphatic alcohols, alkylphenols, aliphatic amides, ethoxylated or propoxylated fatty acids to the dyeing process.

This additive should be added in an amount of 0.1 to 5% based on the weight of the organic solvent.
．． Addition of 5 to 1% is preferred.

Furthermore, when preparing a uniform dispersion, an inorganic or organic acid salt of an aliphatic amine may be used as a dispersant. The synthetic fiber materials to be dyed by the method of the present invention are mainly polyester fibers, such as fiber materials having a basic composition of terephthalic acid and ethyl glycol, fiber materials having a basic composition of terephthalic acid and 1,4 dividroxymethylcyclohexane, and triacetyl fibers. Cellulose fibers, cellulose diacetate fibers, fiber materials of synthetic polyamides such as polygocabrolactam, polyhexamethylenediamine adibate, or 4-aminoundecanoic acid, and fiber materials of polyurethanes. When dyeing these fiber materials, it can be applied to various process steps.

Examples include para-hair, sliver, filament yarn, spun yarn, woven fabric, knitted fabric, or ready-made products such as undercoats, sweaters, slacks, etc.

The dyeing method according to the method of the present invention may be either an exhaust dyeing method or a continuous dyeing method. In other words, in the exhaust dyeing method, the dye, solvent, and fiber material are introduced into a sealable dyeing container at room temperature, the liangge is heated to 80-150℃, and the dyeing is continued at this temperature until the dye is completely exhausted. . This exhaustion is usually 20~
Complete in 90 minutes. The amount of solvent used may be 5 to 50 times the weight of the fiber material, but it is preferably 5 to 2 pm. After the exhaustion is completed, it is cooled in a greenhouse, the dyeing residue is separated, and after a short wash with fresh solvent in a hot bath, the solvent adhering to the fiber material is removed and it is dried in warm air. By the above method, synthetic fiber materials can be dyed in a simple manner from organic solvents, and dyed products having excellent dye fixation and high fastness properties can be obtained. Continuous staining can be carried out by methods known as so-called thermosol staining and pad steam staining.

That is, the fiber material is immersed in a padding liquid prepared by dissolving or finely dispersing the dye of the present invention in a solvent, and the excess liquid is uniformly removed by a mulch machine, followed by intermediate drying, and then in a hot air phase. This method fixes the dye by introducing the dye into the water vapor or solvent vapor phase, or by intermediate drying, or by introducing the dye into a steam or solvent vapor phase after the intermediate drying.

For example, the object to be dyed is immersed in a padding liquid of a desired concentration, and
00% weight increase, 40-100℃, 30-6
Intermediate drying is carried out in a tumbler, followed by dry heat treatment at a temperature below the softening point of the fiber material, i.e., at 120-230° C. for 30-120 seconds.

Steaming with water vapor or solvent vapor
~15000, done with 30-12 inkstone sand.

Even in continuous dyeing, the undyed dyes are trichlorethylene,
Washed briefly in a warm bath with a solvent such as trichloroethane. The dyed product obtained has excellent dyeing properties and fastness similar to those obtained by the exhaust dyeing method. The present invention will be specifically described below with reference to Examples.

The parts shown in the examples are parts by weight. Example 1 10 parts of a polyester fiber fabric prepared from 1 part of a dye represented by the following formula '3} and 160 parts of tetrachloroethylene was introduced at room temperature during dyeing, and the mixture was dyed at the above temperature while allowing Liangge to fly. Stained for 60 minutes.

Next, after cooling to room temperature, the dyed residual liquid was separated, and the dyed polyester fibers were washed with 160 parts of trichlorethylene containing 4 degrees of acetosol at 5,000 °C for 5 minutes. After separating the washing solution, centrifuge the excess adhering solvent, and
Dry in a hot air stream at 0qC. Light resistance with good texture,
A vivid red dyed product with excellent sublimation resistance and solvent resistance (dry cleaning) was obtained. A polyester fiber material whose basic composition is terephthalic acid and 1,4-dividroxymethylcyclohexane, triacetyl cellulose fiber, cellulose diacetate fiber, polycaprolactam fiber, hexamethylene diamine azivate was prepared in the same manner as above. A satisfactorily vivid red dyed product was also obtained for textile materials. Examples 2 to 21 When post-dyeing treatments were carried out in the same manner as in Example 1 using the dyes shown in the table below and represented by the formulas, satisfactorily dyed products with similar high affinity tones and bright colors were obtained. .

Example 22 10 pieces of polyester fiber fabric were introduced at room temperature into a dye bath prepared from 1 part of the dye of Example 1, 160 parts of tetrachlorethylene, and 8 parts of water, and dyed in the same manner as in Example 1. The Kafu value of the dyed product obtained by post-treatment was about 40% higher than that of the dyed product of Example 1.

Example 23 10 parts of acetate twin yarn was introduced at room temperature into a liangge prepared from 1 part of the dye of Example 2 and 1500 parts of trichlorethylene, the temperature of the liangge was raised to 80 qo within 20 minutes, and the dye solution was slowly heated. Staining was carried out at the above temperature for 45 minutes while shaking the stain.

After staining, separate the beam solution and add 150 ml containing 20 parts of butanol.
Foundation county triku. After washing for 5 minutes at 40°C with Lechlene solution, the wash solution was centrifuged and dried in a hot air stream at 6,000°C. A yellowish-red dyed product with good affinity and fastness and good hand was obtained. Example 24 A 100% acetate fabric prepared from 1 part of the dye of Example 5, 160% of tetrachlorethylene and 2 parts of butanol was introduced at room temperature into a 10% acetate fabric, and the coat was heated to 80°C within 20 minutes.
The temperature was raised to 0.000 C, and dyeing was carried out at this temperature for 45 minutes.

By post-processing and drying in the same manner as in Example 23, a dyed product with good affinity and fastness and a good texture was obtained. Examples 25 to 41 When dyeing was carried out by the method of Examples 23 and 24 using the dye shown in the table below and represented by formula (1), dyed products having similar high affinity and high fastness were obtained.

Example 42 A solution consisting of 20 parts of the dye represented by the following formula (■), 10 parts of laurylamine acetate, and 70 parts of tetrachlorethylene was treated in a ball mill for 2 hours, and 10 parts of the dye paste solution was processed into lauryl. A padding solution was prepared by gradually dropping the solution into 140 parts of tetrachloroethylene containing 10 parts of amine acetate while stirring vigorously to separate it.

After soaking the polyester fiber fabric in the padding liquid, squeezing it to a weight increase of 80%, and performing intermediate drying for 80,001 minutes,
The mixture was introduced into a hot air phase heated to 18 psi and subjected to sand treatment in step 6. Next, it was immersed in a trichlorethylene solution containing 150 quarts of acetone and washed at 50 qo for 5 minutes, and the washing solution was squeezed out with a mangle roll and then introduced into a hot air phase heated to 60 qo for drying. A red dyed product with good texture and excellent sublimation resistance, light resistance, solvent resistance (dry cleaning), and washing resistance was obtained. The same method as above is used to prepare polyester fiber materials whose basic composition is terephthalic acid and 1,4-dividroxymethylcyclohexane, polyamide fibers such as polydocaprolactam hexamethylene diamine adibate fiber materials, and polyurethane fiber materials. A dyed product with a satisfactory red color was obtained. Example 4
3 A polyester fiber material was immersed in a dye solution prepared from 1 part of the dye represented by the following formula (■), 9 parts of dimethylformamide, and 90 parts of trichlorethylene, reduced to a weight increase of 80%, and placed in a hot air phase of 70 qo. It was introduced and dried for an intermediate period.

Next, this fabric was introduced into a hot air phase heated to 18,030 ℃, and subjected to four inkstone sand treatments. By post-treating and drying the heat-treated polyester fiber fabric in the same manner as in Example 42, it is possible to obtain a clear texture with excellent light resistance, sublimation resistance, solvent resistance (dry cleaning), and washing resistance. A good red dyeing was obtained. Also, instead of {5', '61, the same amount of Examples 1, 2, 5, 7, 9, 10, 11, 18, 19,
When the dyes were dyed using the dyes No. 22 and 23 by the method of Examples 42 and 43, similar satisfactory dyed products were obtained which were clear and had a good texture. Comparative Test Dyes of the Method of the Invention Dye of Example 4 (1) Dye of Example 8 (A) Dye of Example 13 (2) Dye of Other Structures Using the method of Example 1, 1 part of each of the dyes was used. Polyester fiber fabric 10 Noto was dyed.

To compare the dyeability, the reflectance of these dyed products was measured using a self-recording spectrophotometer, and based on these measurements, Kubelka-M
The unk coefficient K/S=(1-R)2/Fox (where R is the reflectance of monochromatic light from an infinitely thick material, K is the absorption coefficient of the material, and S is the scattering coefficient) was determined. It is known that this function holds true over a wide range of dye concentrations when the hues are similar, so the dyeing densities of each dye were compared using this value. The K/S relative value is the K/S of dye (a)
This is the concentration value of each dye when the S value is 100. It is clear from the results of comparative tests that the dyes produced by the method of the invention exhibit excellent dyeing properties.

Claims (1)

[Claims] 1. A synthetic fiber material is depleted from a solution or dispersion of a water-immiscible organic solvent having a boiling point of 60°C to 180°C using a dye represented by the following general formula (1). A method of staining or continuous staining. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, D and E are hydrogen atoms, halogen atoms, nitro groups,
It represents a cyano group, a lower alkyl group, a lower alkoxy group, an alkylsulfonyl group, and R_1 and R_2 are independently a hydrogen atom, a lower alkyl group, a β-hydroxyethyl group, a β-cyanoethyl group, a trifluoromethyl group, a β- Chloroethyl group, β-bromoethyl group or one or more hydroxy groups, nitro group, carboxyl group, lower alkoxy group, carbamoyl group, sulfamoyl group, acylamino group, lower alkylsulfonyl group, bidroxyethylsulfonyl group, cyanoethylsulfonyl group represents a phenyl group substituted with , R^3 represents a hydrogen atom, a lower alkyl group, or a lower alkoxy group, and R represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, or an acylamino group. However, this excludes cases where R is an acylamino group and R_1 and R_2 are both lower alkyl groups, and cases where R is an acylamino group and one of R_1 and R_2 is a hydrogen atom and the other is a lower alkyl group. The number of carbon atoms in the lower alkyl group, lower alkoxy group, and lower alkylsulfonyl group shall not exceed 4. )