JPS62253663A - Dyeing liquid and dyeing using same - Google Patents

Abstract

PURPOSE:To provide a thermally stable dyeing liquid capable of clearly dyeing with outstanding uniform dyeability, etc., such textile fibers as of cellulose fiber, wool, silk, nylon, PVA fiber, etc., containing, in a liquid medium, specific alkali metal sulfonate substituent-contg. copper phthalocyanine dye(s). CONSTITUTION:The objective dyeing liquid containing, in a liquid medium, pref. 0.01-30wt% of at least one kind of copper phthalocyanine dye carrying alkali metal sulfonate substituent. Said dye is such that when analysed by liquid chromatography, if the retention time for the main peak is assumed as 1, the ratio of the total area A of the peaks corresponding to the retention time <=0.8 to the total area B of the peaks corresponding to the retention time 0.85-4.0 falls >=1/6. Preferably, the above dyeing liquid is further incorporated with 3-30wt% of a water-soluble inorganic salt (e.g. sodium sulfate).

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a thermally stable dyeing solution and a dyeing method using the same, particularly for dyeing natural cellulose fibers, raw cellulose fibers, wool, silk, nylon , excellent level dyeing properties for fibers such as polyvinyl alcohol fibers, woven or non-woven fabrics made of these fibers, or blended woven fabrics or blended non-woven fabrics made of these fibers and other fibers, and the light fastness of dyed products. , relates to a dyeing solution that exhibits extremely good washing fastness and a dyeing method using the same.

(Conventional technique ff) Conventionally, fibers such as natural cellulose fibers, regenerated cellulose fibers, wool, silk, nylon, and polyvinyl alcohol fibers, woven or nonwoven fabrics made of these fibers, or blended fabrics made of these fibers and other fibers have been used. Dyeing of cloth or blended nonwoven fabric is carried out using a dyeing solution in which a reactive dye or dye is dissolved in an aqueous medium, for example, by dyeing methods such as dip dyeing or badging. In particular, the method of dyeing using a dyeing method, which requires only one bath and the dyeing process is simple, can be done using relatively small-scale equipment, and is widely practiced in various places.

(Problems to be Solved by the Present Invention) However, when using a dyeing solution using the currently available dyeing solution, the properties that those skilled in the art particularly desire during the dyeing process or in the dyed product, namely (1) ) Excellent level dyeing properties for dyed products.

(2) The dye is thermally stable in an aqueous dyebath and has extremely good dissolution stability even at high concentrations.

(3) The light fastness and washing fastness of the dyed product should be sufficient for practical use.

There are very few things that have all of these properties.

Therefore, the purpose of the present invention is to solve the problems of level dyeing, color tone, dyeing process problems, and various fastness of dyed products in dyeing using a dyeing solution using a conventional commercially available dye as mentioned above. It is an object of the present invention to provide a staining solution and a staining method using the same, which can solve the problems of not being able to do it at the same time.

These objects of the present invention are achieved by the following invention.

(Means for Solving the Problems) That is, the present invention provides at least one alkali metal sulfonate j! & In a dyeing solution containing a dye containing a copper phthalocyanine dye having a substituent in the liquid medium, at least one of the direct dyes has a retention time of 1 for its main peak when analyzed by liquid chromatography. When, the ratio (A/B) of the total area A of the peaks at a retention time of 0.8 or less to the total area B of the peaks at a retention time of 0.85 to 4°O shows a value of 1/6 or more. It is a staining liquid characterized by:

(Function) The main peak in liquid chromatography analysis according to the present invention is defined below.

That is, 0.15% diptylamine carbonate aqueous solution/acetonitrile = 4/1 (V/V ratio) was used as the moving phase at a flow rate of 1 ml and 111 minutes for the column.

ODS (octadecylsilane treated) - In fluid chromatography analysis using a silica gel column 4.6 mφ x 150 m+s and using 340 n+s as the detection wavelength, the maximum intensity observed during a retention time of 4 to 7 minutes. The peak is called the main peak. Further, the total area 8IA and the total area 4'fB referred to in the present invention are measurement areas in liquid chromatography analysis under the same conditions as above, and these are schematically illustrated in FIG. 1.

As the alkali metal used to form the dye in the dyeing solution of the present invention, sodium, potassium, and lithium are suitable, but rubidium and the like can also be used. The dye used in the present invention, in which the copper phthalocyanine nucleus is substituted with at least one alkali metal sulfonate, is generally obtained as a mixture substituted with several of the above substituents, and their exact Although the chemical structural formula and its composition ratio are not certain, if the total area A and total area B are measured as described above and the ratio A/B is determined, as this value increases, the dye Solubility as well as solution stability increases. If the value of A/B is 1/6 or more, it has sufficient characteristics as a dye for dyeing solution, but if the value of A/B is 1/6 or more,
More preferably, it is 4 or more.

The copper phthalocyanine dye having at least one sulfonic acid alkali metal salt substituent used in the present invention can be prepared using known methods such as, for example, reacting copper phthalocyanine and crosssulfonic acid to form chlorosulfonate, followed by hydrolysis and neutralization. By following the method described above and appropriately adjusting the reaction conditions, it is possible to produce a product in which the area ratio A/B is 1/6 or more.

The above dye (often a mixture) added to the entire dye solution
The content is preferably 0.01 to 30% by weight. When the content is less than 0.01% by weight, almost no coloring effect can be expected on the dyed object even in light color dyeing, and when the content exceeds 30g% by weight, the amount of dye in the dyebath is It is not preferable because the solution stability and the level dyeing property of dyed articles are reduced.

The medium for dissolving the dye is mainly water, but a mixture of water and a water-soluble or hydrophobic organic solvent can yield favorable results in terms of dyeing workability and dyeing speed improvement. . Furthermore, depending on the type of object to be dyed, for example, in the case of objects to be dyed other than fibers such as synthetic resin filaments and molded articles, a water-soluble or hydrophobic organic solvent may be mainly used.

Examples of suitable water-soluble organic solvents used in combination here include: Alkyl alcohols having 1 to 4 carbon atoms such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol: Tetrahydrofurfuryl alcohol: ethylene glycol, diethylene glycol, triethylene Glycols such as glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, thiodiethylene glycol, hexylene glycol, trimethylene glycol, and their mono- or di-low-1
& (C1-4) alkyl ether; Dimethylformamide, dimethylacetamide: Ketone or ketone alcohols such as acetone and diacetone alcohol: Ethers such as tetrahydrofuran and dioxane: Polyalkylene glycols such as polyethylene glycol and polypropylene glycol : Glycerin; N-methyl-2-pyrrolidone: 1,3-dimethyl-2-imidazolidinone: Alkanolamines such as triethanolamine, jetanolamine, and monoethanolamine: Sulfolane, etc.

The content of these water-soluble organic solvents in the liquid medium is
Generally 1 to 50% by weight, preferably 5 to 40%,
More preferably, it is within the range of 10 to 30%.

The water content is preferably in the range of 50 to 95% by weight.

Moreover, it is preferable to adjust the pH of the staining solution to a range of 5 to 10.

Although the essential components of the dyeing solution used in the present invention are as described above, it is preferable to add water-soluble inorganic salts to the dyebath in order to control the dyeing speed and dye dyeing rate. Specific examples include (fi water) sodium sulfate, sodium chloride, ammonium acetate, ammonium sulfate, etc., and the content thereof is preferably in the range of 3 to 30% by weight of the dyeing solution.

In addition, various conventionally known pH adjusters, penetrants,
Antifoaming agents, bath softeners, solubilizers, reduction inhibitors, level dyeing agents, slow dyeing agents, carriers, migration inhibitors, etc. can be added as necessary.

Typical examples include alkali metal hydroxides, aqueous ammonia, etc. as pH adjusters, and urea, etc. as solubilizers. In addition, it also has the effects of penetrating, level dyeing, and slow dyeing agents, such as fatty acid salts, alkyl f & acid ester salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate ester salts, and naphthalene sulfonic acid. formalin condensate,
Polyoxyethylene alkyl sulfate salt, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester, oxyethylene Of particular interest are various anionic and nonionic surfactants such as oxybrobylene block polymers.

As mentioned above, the dyeing solution of the present invention does not necessarily satisfy the problems of level dyeing, color tone, problems in the dyeing process, and various fastnesses of dyed products when dyeing with a dyeing solution using a conventional commercially available dyeing solution. We wanted to solve this problem at the same time, and we arrived at this result after careful consideration, paying particular attention to the structure of dyes.

The dyeing method of the present invention uses the dyeing solution as described above to dye fibers such as natural cellulose fibers, regenerated cellulose fibers, wool, silk, nylon, polyvinyl alcohol fibers, etc. or their ia.
Woven or non-woven fabrics containing lm, or blended woven fabrics or blended non-woven fabrics made of these fibers and other fibers,
It is applied to shapes other than fibers by conventionally known dyeing methods such as dip dyeing, badging, and printing.

The temperature during dyeing, for example, the temperature of the dye bath and badging bath, etc., depends on the dyeing concentration, the type of dye, the type of object to be dyed, and the temperature of the bath.
If the dyeing is insufficient, for example, dyeing treatment is performed using the steaming method, HT steaming method, thermofix method, or thermosol method, and then, Undyed dye is removed by a known cleaning process such as soaping. Further, depending on the case, a fixing treatment is performed to obtain the final dyed product.

Next, the present invention will be explained in more detail by giving dye synthesis examples, examples, and comparative examples. In addition, parts in the text are based on weight unless otherwise specified.

Synthesis Example 1 50 parts of copper phthalocyanine was added to 400 parts of chlorosulfonic acid, and the mixture was heated to 125 to 130°C with stirring.
Heat for 4 hours. After cooling the reaction mixture, add 5 liters of water.
00 parts of ice and 2,0 parts of ice, then filtered and the filter cake washed with cold water. The obtained filter cake was neutralized by adding it to an equivalent part of 5% sodium hydroxide solution, the solvent was evaporated, and the solid content was dissolved in methyl cellosolve, followed by a qualitative filtration. 2 (manufactured by Toyo Kagaku Sangyo)
The solvent was evaporated from the filtrate again to obtain a sodium salt of copper phthalocyanine having a sulfonic acid substituent (dye 1).

When this 0.4% aqueous solution of Dye 1 was subjected to liquid chromatography analysis under the following measurement conditions, the results shown in FIG. 2 were obtained. The area ratio A/B was 1/2.8.

Measurement conditions Equipment used: Hitachi 635 high performance liquid chromatography column: Senshu Chemical Senshu Back N+uyl
pn<if Fl “Hl 1L Rn
+5rAy150 ugly mobile phase: 0.15% dibutylamine carbonate aqueous solution/acetonitrile = 4/l (V/V ratio) flow rate + 1 mj2/min.

Detection wavelength: 340r+@ Sample injection amount: 5μU Synthesis example 2 150 parts of 4-sulfophthalic acid, 135 parts of urea, 24 parts of cupric chloride, and 0.5 parts of ammonium molybdate were mixed with 300 parts of trichlorbenzene at 200°C for 2 hours. After stirring and reacting, the obtained reaction product was filtered when ripe, and the filter cake was treated in the same manner as in Synthesis Example 1 to obtain Dye 2. This dye was analyzed in the same manner as in Synthesis Example 1, and the results are shown in FIG. The area ratio A/B was 1/1.4.

Synthesis Example 3 Commercially available dye Aizen Pr1IIIula Turq
oise Blue GHL.

(trade name, manufactured by Ho-Lgaya Chemical Industry Co., Ltd.) was dissolved in methyl cellosolve, and then filtered through Qualitative Filtration Filter 2 (manufactured by Toyo Kagaku Sangyo), and the solvent was evaporated from the filtrate to obtain Dye 3. FIG. 4 shows the results of a similar analysis of this dye. The area ratio A/B was 175.1.

Comparative Synthesis Example 1 Commercially available Dye C.1 and Direct Blue 86 (manufactured by Chugai Kasei) were treated in the same manner as in Synthesis Example 3 to obtain Dye 4. FIG. 5 shows the results of a similar analysis of this dye. Area ratio A/
B was 176-7.

Example 1 (Preparation of dyeing solution) Sodium carbonate 2 parts Anhydrous sodium sulfate 15 parts Dye 1 of Synthesis Example 1 7 parts Leveling agent (Tex Boat OL
-:14, manufactured by NICCA CHEMICAL INDUSTRIES))
1 part water
75 parts All of the above components were stirred for 3 hours, and the pH was adjusted to 8 with sodium hydroxide to obtain a dyeing solution (a) of the present invention.

Example 2 (staining liquid manufactured by No. 31) Urea 10 parts Sodium alginate 0.2 parts Dye 2 of Synthesis Example 2
8 parts triethylene glycol
5 parts water
77 parts All of the above components were stirred for 3 hours, and the pH was adjusted to 8 with sodium hydroxide to obtain a dyeing solution (b) of the present invention.

Example 3 (Preparation of staining solution) Sodium chloride 4-part synthesis example 3
dye 3 5fi thiodiethylene glycol 5 parts leveling agent (Disper N
-550, manufactured by Sensai Kagaku Kogyo) 0.1 parts Water 86 parts All the above ingredients were stirred for 3 hours, and the pH was adjusted to about 8 with sodium bicarbonate II! ! C, the staining solution of the present invention (
c) was obtained.

Comparative Example 1 (Preparation of Dyeing Solution) A comparative dyeing solution (d) was obtained by carrying out exactly the same treatment as in Example 1, except that Dye 1 of Synthesis Example 1 was replaced with Dye 4 of Comparative Synthesis Example 1.

The staining solutions (I to H) of Examples and Comparative Examples were all uniform solutions. In order to compare the thermal stability of these dye solutions, when they were stored in an oven at 60°C for one month,
A slight amount of dye precipitation was observed only in the comparison staining solution (d).

Example 4 (Dyeing method) A cotton broadcloth thoroughly scoured and impregnated with water was added to the dyeing solution (Iruni) of the example and comparative example at a bath ratio (1:
30), heated to 40°C and left for 10 minutes. Thereafter, the temperature was gradually raised and dyeing was carried out at 90°C for 50 minutes. The dyed material was soaped and thoroughly washed repeatedly.

Example 5 (Dyeing method) The dyeing solution (Iruni) of the example and comparative example was buzzed with sufficiently purified regenerated cellulose fiber cupra fabric (buzzing bath 50°C), and steamed at 100°C for 8 minutes. . After staining, soaping treatment was performed and washing was repeated thoroughly.

Properties of the dyed products obtained in Examples (4-5) are shown in Tables 1-3.

Level dyeing Umbrella l -Rice and fish liquid-U Cross application 1 Dyeing solution (A) OO Staining solution (Exit > 0 0 Staining solution (C) OO Staining solution (D) △ × (Comparative example) Light fastness *2 1 rack 1 side A 500 million 1 staining solution (
A) OO Staining solution (B) OO Staining solution (C) O○ Staining solution (2>0 0~Δ (comparative example) Washing fastness $3 )
OO Staining Solution (B) OO Staining Solution (C) OO Staining Solution (D) Δ × (Comparative Example) The evaluation and evaluation criteria in the above table are shown below.

*1 Level dyeing property The dyeing was visually judged.

〇--No unevenness at all.

8-1 There is some unevenness.

*2 Light fastness Irradiation was performed using a xenon arc fade-o-meter C135 (manufactured by Atlas Corporation) under the conditions of a black panel temperature of 63° C. for 250 hours.

The evaluation is L*a1b according to the CIE LAB color system of the test piece.
Find the point on the coordinate system using the conversion formula to the umbrella, and use the color k (ΔEab*) of the two points with the sample after irradiation.
5 0-1 ΔEab*<5 △----5≦ΔE ab*≦10 X-----ΔEab*>10 3 Washing fastness synthetic detergent The product was washed 10 times using a washing machine according to the method, and evaluation was made using ΔEab* in the same manner as in the case of light fastness.

〇--ΔEab min. All of the dye compounds showed excellent effects as in the examples.

(Effects) The dyeing solution of the present invention is thermally stable, and can be used to dye fibers such as natural cellulose fibers, regenerated cellulose fibers, wool, silk, nylon, polyvinyl alcohol fibers, etc., or fibers containing these fibers. When dyeing woven fabrics, non-woven fabrics, blended woven fabrics, blended non-woven fabrics, or blended non-woven fabrics made of these fibers and other fibers, the dyeing is more level compared to when dyeing liquids using conventional commercial dyes are used. In addition, the dyed product has excellent light fastness and washing fastness.

[Brief explanation of drawings]

FIG. 1 is a diagram schematically showing evaluation criteria based on a liquid chromatography analysis diagram of the dye used in the staining solution of the present invention. Figures 2 to 4 show the results of liquid chromatography analysis of the dye used in the staining solution of the present invention.
The figure is that of a comparative example. Patent Applicant: Canon Co., Ltd. ) October 2, 1986

Claims (4)

[Claims] (1) In a dyeing solution containing a dye containing a copper phthalocyanine dye having at least one sulfonic acid alkali metal salt substituent in the liquid medium, when at least one of the dyes is analyzed by liquid chromatography, When the retention time of the main peak is 1, the retention time is 0.8
Total area A and retention time of the peaks below 0.85 to 4
．． The ratio (A/B) of the total area B of the peaks up to 0 is 1
A staining liquid characterized by exhibiting a value of /6 or more. (2) The dyeing solution according to claim (1), which contains a water-soluble inorganic salt in an amount of 3 to 30% by weight based on the total weight of the dyeing solution. (3) In a method of dyeing an object to be dyed with a dyeing solution,
The staining solution is a staining solution containing in the liquid medium a dye including a copper phthalocyanine dye having at least one alkali metal sulfonic acid salt substituent, and at least one of the dyes is analyzed by liquid chromatography. When the retention time of the main peak is 1, the total area A of the peaks below the retention time of 0.8 and the retention time of 0.8
5 to 4.0 to the total area B (A/
A staining method characterized in that B) exhibits a value of 1/6 or more. (4) The material to be dyed is natural cellulose fiber, regenerated cellulose fiber, wool, silk, nylon, polyvinyl alcohol fiber, etc., or a woven fabric or non-woven fabric containing these fibers, or a blended fabric consisting of these fibers and other fibers. Alternatively, the dyeing method according to claim (3), which is a blended nonwoven fabric.