JPH0252031B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for dyeing fibers, particularly a printing method, and more specifically, it provides a method for high-quality printing and ironing dyeing using an improved foam composition having a microspatial structure. Conventionally, methods for increasing the viscosity of printing liquids include emulsifying hydrocarbons such as mineral turpentine and using natural polymer thickeners. On the other hand, there is a method of obtaining a foaming composition by using a dyeing liquid slightly thickened with a small amount of a sizing agent and a dyeing liquid containing a dye fixing agent using a nonionic surfactant and an anionic surfactant as a foaming agent. This was proposed in Publication No. 38474 and Japanese Patent Application Laid-Open No. 52-5383. According to Japanese Patent Publication No. 47-38474, when dyeing thick fabrics such as felt, carpet, and blanket, a dyeing solution containing a foaming agent and adjusted to a viscosity of 100 to 900 cps with a sizing agent has an apparent volume of 2 to 5 cps. A method of foaming to double the foam has been proposed. A detailed study of this method revealed that it was difficult to obtain a reproducible foaming dye solution due to the small amount of natural polymer thickeners such as sodium alginate and carboxymethyl cellulose used, and that dyeing during use was difficult. This tends to cause changes in volume and viscosity, making it difficult to apply to textiles that require strict dyeability, such as for general clothing. If the foam composition has a high viscosity, the volume change during printing will be small, but the viscosity change will be large, making it difficult to supply a stable printing amount, and practical processing cannot be expected. . On the other hand, in order to solve this problem, an aqueous dispersion of natural or synthetic resin used as a pigment binder was used in combination, and the foaming agent worked to form spherical cells with a diameter of 200μ or less without increasing the viscosity of the dye solution. including,
JP-A-52-5383 describes the preparation of a foam composition in which the volume ratio of dye liquor to air is 1:1.5 to 4.
It is proposed in the Publication No. However, the colorants that can be used are limited to pigments, and dyes such as disperse dyes, basic dyes, reactive dyes, and direct dyes may have insufficient color development or a decrease in fastness due to the presence of a fixing agent. It also had the disadvantage that the texture became extremely rough and stiff. The present invention was achieved as a result of intensive research aimed at developing a method that can overcome the drawbacks of both of these two types of dyeing methods. As a result of studying various thickening products, the present inventor found that those containing large amounts of natural polymer thickening agents tend to have problems with desizing properties, color development, and fastness after drying, and also cause large changes in viscosity. On the other hand, if the amount of sizing agent is reduced to make a low viscosity liquid, the viscosity of the foamed product will be low, and it will easily separate water if left to stand, and the foaming ratio will decrease. It was found that stable dyeing was difficult to achieve depending on the glue used.
Furthermore, although this type of processing is suitable for printing water-absorbing fibers such as cotton and cotton blends, printing of polyester fibers, nylon fibers, acrylic fibers, etc. with low water absorption tends to cause the printing area to bleed, making the printing difficult. It was also discovered that there is a problem with foam stability during printing, which poses a problem for practical use. Therefore, in the present invention, a foam composition with high viscosity and stable viscosity and foaming ratio is prepared using a water-soluble synthetic polymer thickener, so that it can be stably used regardless of the type of material to be dyed. Enables high quality dyeing. The present invention involves applying a foam composition foamed to 1.5 to 10 times the apparent volume of an aqueous dyeing solution containing a water-soluble synthetic polymer thickener, a foaming agent, and a dye to an object to be dyed;
It is characterized by color development. Here, as the water-soluble synthetic polymer thickener, the type is not limited, but it is preferable to use a polyethylene oxide derivative, and in particular, the general formula (1) R ₁ O (C ₂ H ₄ O) _o R ₂ , R ₁ and R ₂ each represent a hydrogen atom, an alkyl group having 4 to 24 carbon atoms, an alkenyl group, a saturated fatty acid residue or an unsaturated fatty acid residue, and n is 50 to 500.
one or two compounds represented by
or more, with an etherification rate and/or esterification rate of 40% or more, and general formula (2) (However, R ₃ and R ₄ each represent a hydrogen atom, an alkyl group having 4 to 24 carbon atoms, an alkenyl group, a saturated fatty acid residue, or an unsaturated fatty acid residue, and x+y is 50
is an integer of ~500, and X is an alkylene group having 2 to 8 carbon atoms or a urethane residue having an aromatic ring having 6 to 20 carbon atoms. It is preferable to select one having a ratio and/or an esterification ratio of 60% or more. In the above compounds, when the number of carbon atoms in R ₁ to R ₄ is smaller than 4, the water solubility is too high and it is difficult to obtain a thickening effect, the viscosity stability during foaming is poor, and the foaming ratio is difficult to maintain. If the number of carbon atoms is greater than 24, the water solubility is low and it is necessary to heat it during use, resulting in poor workability and difficulty in utilization. The compound most suitable as a thickener in the present invention is
Diesterized products, dietherized products, and monoether monoesterified products of polyethylene oxide, in which R ₁ to _{R 4} are alkyl groups, alkenyl groups, saturated fatty acid residues, or unsaturated fatty acid residues having 8 to 18 carbon atoms, and monoesterified products of polyethylene oxide It is a crosslinked product (the crosslinking rate is preferably 40% or more) of an esterified product and/or a monoetherified product using a diisocyanate compound. The number of moles of ethylene oxide added in the above compound is preferably 50 to 500 moles;
Preferably it is between 80 and 200 moles. If the number of moles of ethylene oxide added is small, sufficient water solubility will not be obtained, it will easily gel, and it will be difficult to foam.
Furthermore, if the number of moles of ethylene oxide added is too large, production becomes difficult in terms of equipment. The amount of these thickeners used is preferably 0.1 to 10.0% by weight, particularly 0.5 to 3.0% by weight in the dyeing solution.
In the present invention, a stable foam composition can be obtained by preparing a dye solution with a viscosity of 1000 cps or less at room temperature and foaming it, but the use of such a thickener
Even if the dyeing liquid has almost no perceivable viscosity below 100 cps, by foaming, a composition with very high viscosity and fluidity suitable for textile printing can be obtained. Further, as the foaming agent, any surfactant having good compatibility with the dye can be used, and two or more types can be used in combination. The amount used is preferably 0.1 to 2.0% by weight, particularly 0.2 to 1.0% by weight in the dyeing solution.
If it is less than that, the foaming property will be inhibited by the dyeing auxiliary agent necessary for dye color development, and stable foaming will not be obtained. Also, when soaping after dyeing, a large amount of foam is generated, which tends to cause problems such as poor workability. Highly foaming surfactants particularly suitable for the foaming agent of the present invention include lauric acid diethanolamide,
Nonionic surfactants such as stearic acid diethanolamide, nonylphenyl pentadeca glycol ether, stearyl dimethylamine oxide, lauryl deca glycol ether; sodium dodecylbenzenesulfonate, sodium laurate, sodium lauryl sulfate salt, α-sulfolauric acid Sodium, sodium dodecane sulfonate, N-lauroyl-L-glutamate monosodium salt, lauroyl sarcosine sodium, N-lauroyl-N-methyl-β-alane sodium salt, nonylphenyl decaglycol ether sulfate sodium salt, perfluoro Anion activators such as sodium octylsulfonate, sodium perfluorooctylcarboxylate; laurylmethyl betaine, lauryl dimethyl betaine, 2-lauryl-N-carboxylmethyl-N-hydroxyethylimidazolinium betaine, N-lauryl-β Ampholytic active agents such as sodium aminopropionate; β-hydroxylauryl trimethylamine chloride, β-hydroxylauryl N,N, dihydroxyethylbenzylammonium chloride, myristyl N,N,
Dihydroxyethylbenzylammonium chloride, lauryltrimethylammonium chloride, N-laurylpyridinium chloride, N-
[3-(Perfluorooctane sulfonamide)
[propyl]N,N,N, trimethylammonium iodide, myristyldimethylbenzylammonium chloride, stearylpicolinium chloride, and other cationic activators. In addition, in the present invention, disperse dyes, acid dyes,
All common dyes such as basic dyes, reactive dyes, and direct dyes can be effectively used, and it goes without saying that ordinary dyeing aids may be added to the dyeing solution. The dyeing solution can be prepared by selecting appropriate dyes and dyeing aids depending on the material of the object to be dyed, dissolving or dispersing them in water, and then adding foaming agents and thickeners previously dissolved in water. The staining solution is an oak mixer,
It is used after being foamed using a suitable foaming device such as a Viking mixer so that the apparent volume is 1.5 to 10 times larger, but in order to achieve a more stable foam, the diameter is increased using a colloid mill, homomixer, high-speed mixing, etc. Fine bubbles of 200μ or less may be included. Inert gas such as air or nitrogen gas can be mixed in to form bubbles. In the present invention, the foam composition thus obtained is applied to the object to be dyed, for example, clothing fabric, etc., to develop color. As the application method, ordinary textile printing method, ironing method, etc. are used. Either can be used effectively. For the coloring process, known methods such as steaming, dry heat treatment, fixing treatment, etc. can be used depending on the dye, followed by finishing processes such as soaping, water washing, and drying as usual. In the present invention, sodium alginate as a thickener,
It is possible to obtain a very stable foam composition that cannot be obtained with dye solutions using natural polymer thickeners such as carboxymethyl cellulose and guar gum, making it possible to dye with good quality and good reproducibility. For example, products dyed according to the present invention have significantly better level dyeing properties than those dyed with a foam composition made by foaming a dye solution containing a water-soluble natural polymer paste to the same foaming ratio. It also shows good desizing properties during soaping and excellent color fastness to rubbing. In the present invention, the thickener has no ionic properties, and unlike conventional natural thickening agents, there is no need to use different types of dye depending on the type of dye, and it has good viscosity and fluidity even when dyeing synthetic fibers with low water absorption, especially when printing. It exhibits excellent wetting effects even when dyeing unscoured synthetic fiber fabrics to which raw fiber oil is attached. For this reason, uneven dyeing and irritated dyeing caused by insufficient wetting, which are common in foam dyeing, are greatly improved, and practical dyeing becomes possible. The reason why the thickener of the present invention can achieve better results than common water-soluble thickeners such as sodium alginate and guar gum is thought to be due to its lower ability to reduce interfacial tension. This is thought to be because it encapsulates an inert gas such as air, tends to exhibit a fine spatial structure, and can provide optimal fluidity during dyeing. Therefore, the viscosity stability of the foam composition can be obtained, and at the same time, it is easy to wet water-repellent fibers such as synthetic fibers and wool, and level dyeing with superior permeability can be achieved. Furthermore, the effect of the present invention is largely influenced by the fact that some thickening effect can be obtained by blending a water-soluble synthetic polymer (thickener) with a surfactant (foaming agent). it is conceivable that. In addition, in the present invention, a stable foam composition can be prepared using the dyeing liquid as described above, and the purpose is achieved.
A dimethyl silicone or modified methyl silicone antifoaming agent may be added to the dyeing solution in an amount of 10% by weight or less, preferably 1 to 0.01% by weight of the foaming agent, resulting in a stable foam composition with a low foaming ratio. This allows for more reproducible staining. Next, examples of the present invention will be shown. In each example, % indicates weight % unless otherwise specified. Examples 1 to 13 and Comparative Examples 1 to 7 Thickener x% Dimethyllaurylbenzyl chloride 0.5% Acetic acid (98%) 1.0% Astrazone Blue FRD (basic dye manufactured by Bayer) 1.0% Water balance 100% Prepare the dyeing solution and stir gently using a household hand mixer (Model MK-1000 manufactured by Matsushita Electric Co., Ltd.) on scale 1 for the first minute, then on scale 2 for 1 minute, and finally on scale 3. The mixture was stirred at high speed for 3 minutes to obtain a foam dyeing solution with a predetermined foaming ratio. The viscosity stability of the foam dye solution upon standing was investigated. The results are shown in Table 1.

【table】

[Table] Example 14 Thickener x % Hostapur SAS-60 (60% secondary alkanesulfonate sodium salt manufactured by Hoechst Japan) 1% Astrazon Blue FRD (basic dye manufactured by Bayer) 1.0% A dyeing solution with 100.0% water content was prepared, and stirring was continued at scale 2 using an improved household hand mixer (Model MK-1000 manufactured by Matsushita Electric Co., Ltd.) with a longer mixer section. The relationship between foaming ratio and time was investigated. The results are shown in the graph of FIG. A uses 2.0% of Faing Gum G-5 as a thickener, B uses 2.0% of PEG-6000 distearate (diesterification rate 98%), and C uses , Antiform (100% modified dimethyl silicone manufactured by Dow Corning) was added to the staining solution of B.
It was added at 0.01%. Comparative Example 8 The dyeing solution of Comparative Example 2 was prepared into a foam dyeing solution with an air expansion ratio of 4.5 times using an oak mixer.
The dye solution was printed on an acrylic fabric using a 120 mesh screen, and high-pressure steam dyeing was performed at 102°C for 20 minutes. As a result, the obtained product had smudges in the direction of the squeegee, was not uniformly dyed, and had poor commercial value. The reason for this is thought to be that the foaming ratio changes when the foamed product is doctored through the mesh. Furthermore, when printing with the same foam composition continuously, the initial coating amount was large and the color became darker, making it impossible to print continuously using the foam composition that was left to stand. Example 15 The dyeing solution of Example 9 was stirred for 5 minutes using an improved large high-speed mixer, and the volume ratio of the dyeing solution to air was 1:1.
A foam composition with a stable microspatial structure with a diameter of 4.5 or less than 30μ was obtained. This foam composition was printed on acrylic fabric with a 120 mesh screen, and 102
High-temperature steam coloring at ℃×20 minutes was applied. As a result, a vivid print with sharp edges was obtained. It has excellent level dyeing properties, and even when printed repeatedly with the same foam composition, the coating amount was always almost the same, and printing was possible with reproducibility. This printed product exhibits color fastness that can withstand the need for special soaping, and has sufficient commercial value. Example 16 Dicetyl ether of PEG-10000 (dietherization rate 90%) 3.2% Diacrylic Red CS-N (basic dye manufactured by Mitsubishi Chemical Corporation) 1.5% Acetic acid 1.5% Tartaric acid 0.5% Lauryl diethanolamide Prepare a staining solution (viscosity 100 cps) consisting of 0.50% myristin-N,N-dihydroxyethylbenzyl ammonium chloride, 0.30% and 100% water , and stir this with a high-speed mixer for 5 minutes until the volume ratio of the staining solution and air is adjusted. A foam composition with a stable microspatial structure with a diameter of 1:40 or less of 30 μm was obtained. This foam composition had a viscosity of 4500-4000 cps and exhibited flow properties similar to mineral turpentine emulsion paste. This foam composition was printed on a raised acrylic fiber (Cashmilon manufactured by Asahi Kasei Corporation) using a 60 mesh screen, and then heated at 102°C x 2 using a high-pressure steamer.
The color was allowed to develop for a minute and then soaped dry. The product was dyed to the base, resulting in a permeable, solid, and commercially valuable print that could not be obtained with the dyeing solution of the comparative example. Example 17 TDI crosslinked product of 100 moles of ethylene oxide adduct of cetylstearyl alcohol (crosslinking rate
70%） 2.5% Diacrylic Brilliant Blue H2R―
N (basic dye manufactured by Mitsubishi Chemical Industries, Ltd.)
0.4% Acetic acid 0.5% Lactic acid 0.5% Polyethylene glycol nonyl phenol ether (=9.5) 0.3% Octyltrimethylammonium chloride
Prepare a staining solution (viscosity 25cps) consisting of 0.7% and 100% water, stir this at high speed with a hand mixer for 5 minutes, and form a stable product with a diameter of 30μ or less with a volume ratio of staining solution and air of 1:3.5. A foam composition having a microspatial structure was obtained. This foam composition had a viscosity of 4600 cps, and showed optimal viscosity and fluidity for post-ironing by rotary printing. This foam composition was applied to an acrylic fiber fabric (Exlan manufactured by Japan Exlan Industrial Co., Ltd.) with a basis weight of 150 g/m ² that was fed at a speed of 12 m per minute using a rotary screen using a 60-mesh screen.
Printing was done by post-ironing, followed by cylinder drying and color development in a high-pressure steamer at 105°C for 10 minutes. The product is a brightly printed textile with sharp edges.
It was confirmed that the above foam composition had excellent level dyeing properties and permeability, and there was almost no change in the amount applied over time, and that it could withstand rotary printing. In addition, the color fastness to rubbing and the fastness to washing of the printed product were both grade 3 or higher, and the texture was also good. Example 18 Ethylene oxide of myristyl alcohol
120 mol adduct stearate (esterification rate 95%) 0.5% Kaya Acrylic Blue GRL (basic dye manufactured by Nippon Kayaku Co., Ltd.) 1.5% Lauryltrimethylammonium chloride
Printing liquid consisting of 0.2% polyethylene glycol lauryl ether (=13) 0.1% acetic acid 1.0% ammonium tartrate 100% water balance (viscosity is almost undetectable)
was prepared and stirred at high speed for 25 minutes with a hand mixer to obtain a foam composition having a stable microspatial structure with a diameter of 50 μm or less and a volume ratio of dyeing liquid to air of 1:8. The viscosity of this foam composition is 2200cps
It was hot. The composition is coated with a foam coater,
Apply the dye solution to an even thickness on the surface of the acrylic pile carpet fabric at a rate of 200 g/m ² , then gently suction from the back side to penetrate the dye solution into the fabric, and then dry at 100℃.
After steaming for 20 minutes, a bright blue carpet was obtained. This carpet has a fastness of grade 3 or higher, has sufficient commercial value even without special soaping, and saves a large amount of water during soaping and thermal energy during drying. It has been found that to further improve the fastness properties it is advantageous to pre-wet the carpet before applying the foam composition. Examples 19-26 and Comparative Examples 9-16 Thickener x % Sodium lauryl sulfate 1% Acetic acid (98%) 1% Dianex Scarlet 3G-FS
(Disperse dye manufactured by Mitsubishi Chemical Industries, Ltd.)
A dyeing solution consisting of 2% water and 100% water was prepared and stirred in the same manner as in Example 1 to obtain a foam dyeing solution with a predetermined foaming ratio. Table 2 shows the results of examining the viscosity stability of the foam dye solution upon standing.

【table】

[Table] Loin.
*2 Snow Algin is sodium alginate manufactured by Fuji Chemical Industry Co., Ltd.
Example 27 Distearate of PEG-6000 (esterification rate 90%) 2.0% Kayalon Polyester Light Red BLF (disperse dye manufactured by Nippon Kayaku Co., Ltd.) 2.5% Acetic acid 1.0% Hostapur SAS-60 (secondary alkane) Prepare a staining solution (viscosity 10cps) consisting of sulfonate sodium salt, anionic activator manufactured by Hoechst Japan Co., Ltd. (60% product), 2.0% water and 100% water, and stir this with a high-speed mixer for 5 minutes. A foam composition having a stable microspatial structure with a diameter of 30 μm or less and a volume ratio of air to air of 1:5.0 was obtained. The viscosity of this foam composition was approximately 8000 cps. the composition
It was printed on polyester fabric using a 120-mesh screen, color-developed using a high-pressure steamer at 125°C for 30 minutes, and dried after soaping. The edges of the dyed product had a sharp finish, and adhesive removal was very good compared to ordinary dyed textiles. Furthermore, compared to the case of using a foam composition of the same viscosity containing sodium alginate, carboxymethyl cellulose, etc., which are the most common thickening agents for textile printing, the dyeing property is far superior, and the fading phenomenon does not occur. Nakatsuta. As with the other examples, the foam composition of this example also has excellent storage stability, and even when used repeatedly, there is almost no change in viscosity or foaming ratio, which is typical for general compositions. It did not show any poor gauze separation or bleed phenomenon. Example 28 Dicetyl etherified product of PEG8000 (dietherization rate 85%) 2.5% Diacyt Fastread 6B (acid dye manufactured by Mitsubishi Chemical Industries, Ltd.) 2.0% Acetic acid (98%) 1.0% Ammonium tartrate 2.0% Sodium lauroyl sarcosinate Prepare a staining solution (viscosity 100 cps) consisting of 1.0% laurylamine polyethylene glycol ether (30), 0.2% urea , 5.0% and 100% water, stir this with a high-speed mixer for 5 minutes, and adjust the volume ratio of the dyeing solution and air. A foam composition having a stable microspatial structure with a diameter of less than 50μ with a ratio of 1:3.5 was obtained. viscosity
This foam composition, which was 8000 cps, was printed on wool muslin fabric using an 80 mesh screen, and color development was performed using a high-pressure steamer at 105°C for 40 minutes. Then, after soaping, it was dried. The obtained print is a product with sharp edges and excellent level dyeing properties, and is a water-repellent foam composition containing natural polymer pastes such as guar gum, carboxymethylated cellulose, and hydroxyethylated cellulose. No irritation caused by scratches, excellent fastness,
It had commercial value for use in general clothing. Example 29 Distearate of PEG8000 (esterification rate
98%) 2.0% Remazol Black B (reactive dye manufactured by Hoechst Japan) 2.0% urea 2.0% soda ash 1.0% sodium stearate 0.2% sodium lauryl sulfonate salt 0.5% water balance 100% staining solution ( (viscosity 2000 cps) was prepared and stirred for 10 minutes with a hand mixer to obtain a foam composition exhibiting a stable microspatial structure with a diameter of 100 μm or less and a volume ratio of staining liquid to air of 1:5.0.
The viscosity of this foam composition was approximately 4500 cps. The composition was printed on 60-count cotton broadcloth using a 100-mesh screen and heated at 100°C using a high-pressure steamer.
Heat treated for 10 minutes. Next, it was soaped at 60°C for 20 minutes and then dried. The product was dyed dark blue with good leveling properties. The fastness was much better than that of ordinary printed materials, the texture was good, and the product had high commercial value. On the other hand, in a foam composition thickened using a general natural polymer glue instead of the dicetyl ether of PEG8000, bleeding can be prevented by containing 1 to 2% of the glue, but it is not uniform. The drawback was that it had poor dyeing properties and could not be dyed to a reproducible staining density.

[Brief explanation of the drawing]

The drawing is a graph showing the relationship between foaming ratio and stirring time during the preparation of foam compositions in Examples of the present invention.

Claims (1)

[Claims] 1. A foam composition obtained by foaming an aqueous dyeing solution containing a water-soluble polymer thickener, a foaming agent, and a dye to 1.5 to 10 times its apparent volume is applied to an object to be dyed. The above-mentioned thickener has the following general formula R ₁ O (C ₂ H ₄ O) _o R ₂ (1) (where R ₁ and R ₂ are each a hydrogen atom and a carbon number of 3). ~24 alkyl group, alkenyl group, saturated fatty acid residue or unsaturated fatty acid residue, and n is 5~
(which is an integer of 500) has an etherification rate and/or an esterification rate of 40% or more, and the general formula (However, R ₃ and R ₄ are each a hydrogen atom, an alkyl group having 3 to 24 carbon atoms, an alkenyl group, a saturated fatty acid residue, or an unsaturated fatty acid residue, and x+y is 50
- 500 integer, and X is an alkylene group having 2 to 8 carbon atoms or a urethane residue having an aromatic ring having 6 to 20 carbon atoms.
The dyeing solution contains 0.1 to 10.0% by weight of the thickener and the foaming agent. 0.1
A dyeing method characterized by containing at a proportion of ~2.0% by weight. 2. The method according to claim 1, wherein the foam composition contains fine bubbles with a diameter of 200 microns. 3. The method according to claim 1 or 2, wherein the aqueous staining solution has a viscosity of 1000 cps or less at room temperature. 4. Claim 1, wherein the foaming agent is selected from surfactants having high foaming properties.
3. The method according to any one of Items 3 to 3. 5. Any one of claims 1 to 4, wherein the dyeing solution contains a dimethyl silicone-based or modified methyl silicone-based antifoaming agent in a proportion of 10% by weight or less based on the foaming agent. or the method described in item 1.