JPS6246673B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a treatment method for improving the depth of color of dyed polyester fiber structures.

Fiber structures based on polyester fibers are widely used in all types of fiber structures due to their excellent functional properties. It is said that the depth of color of dyed products is inferior. Particularly in the field of formal wear, etc., there is a problem in that it is not possible to obtain a deep black color, which is commonly referred to as "crow's feather color" or "telephone black."

For this reason, various methods have been attempted, such as improving the dyeing aspect and improving the fibers, but none of them have achieved sufficient results at present.

By the way, we have experienced that when an organism gets wet, its color becomes more bathochromic, as seen in the example of "the color of a crow's wet feathers." The reason why the bathochromic degree increases due to this "wetting" is explained as follows.

Except for objects that emit light themselves, such as radiators, the color of an object is generally determined by the reflection and absorption of light, but in order to make the color appear deeper, it is necessary to reduce the reflection of light and increase the absorption of light. It is. Regarding light reflection, it is particularly important to reduce surface reflected light. This is because the surface reflected light hardly contributes to the deepening of the color of the colored body since the light is reflected as white light.

As a method for reducing the amount of surface reflected light, it is known both theoretically and empirically to apply a substance having a lower refractive index than the object constituting the substrate to the surface of the object substrate. An example of this is lens coating technology, which reduces the amount of surface reflected light by coating the lens surface with a transparent thin film that has a lower refractive index than glass. The above-mentioned phenomenon of increased bathochromicity due to wetting is also the result of a reduction in the amount of surface reflected light by covering the surface with a thin film of water, which has a lower refractive index than the substrate. Several attempts have been proposed to apply such principles to improve the bathochromic properties and sharpness of fibrous structures. For example, a method of attaching silicone to the surface of a fiber structure (Japanese Unexamined Patent Publication No. 48-1989)
13695), a method of forming a thin polymer film with a refractive index lower than that of the constituent fibers on the surface of a fiber structure by plasma polymerization or discharge grafting (Japanese Patent Laid-Open No. 111192/1989)
No.) etc. However, even if silicone is simply applied as an aqueous dispersion or an organic solvent solution and applied to the surface of a fiber structure by padding, as in the former method, the silicone will not adhere sufficiently and a satisfactory deep color effect will not be obtained. In addition, the state of silicone adhesion itself becomes uneven, the color depth becomes uneven, and the texture becomes hard. Also,
In order to form a thin polymer film on the surface of a fibrous structure using the plasma polymerization method or electric discharge grafting method, such as the latter method, very expensive special equipment is required, and it cannot be called a general processing method. .

In order to overcome the drawbacks of such conventional methods, the present inventors first dipped the dyed fiber structure into a treatment bath in which a hydrophobic polymer with a low refractive index was emulsified or dispersed, and then immersed the dyed fiber structure in the bath. We proposed a processing method that can obtain the desired deep color effect without causing hardening of the texture by attaching a cationic compound to the dyed structure in advance. However, this method is generally performed through a step of imparting a cationic compound to the dyed structure after drying, a step of drying, and a step of adsorbing a hydrophobic polymer, so it is extremely complex and is not necessarily economically advantageous. I can't say that.

The present invention improves the method proposed above by paying particular attention to the reduction cleaning process unique to the dyeing of polyester fibers. As a result, the reduction cleaning and cation attachment treatment of dyed products are advantageous even when a cationic compound is coexisting in the reduction cleaning agent. It turns out that both are compatible.

Thus, according to the present invention, a cationic compound is attached to the dyed polyester fiber structure during reduction cleaning, and then the dyed fiber structure is treated with a hydrophobic material having a lower refractive index than the polyester fiber. 1. A method for deep coloring a polyester fiber structure, which comprises immersing a polymer in a treatment agent bath in which a polymer is emulsified or dispersed, and performing an in-bath treatment.

is provided.

Furthermore, in the above-mentioned bathochromic processing method, the present inventors have also found that the most preferable bathochromic effect can be obtained when an electrolytic substance is added to the emulsion or dispersion of the hydrophobic polymer and the bath treatment is carried out. I knew.

The term "polyester" used in the present invention mainly refers to polyethylene terephthalate, but it is of course not limited to this.

Further, these fiber structures include all forms such as tows, filaments, yarns, woven and knitted fabrics, and nonwoven fabrics.

The cationic compound as used in the present invention refers to alkyl quaternary ammonium salts such as (1), alkylbenzyl quaternary ammonium salts such as (2), and nitrogen ring-containing quaternary ammonium salts such as (3). etc., but are not limited to these.

(X=Cl, Br, CH ₃ SO ₄ , NO ₃ , ClO ₄ , R: alkyl group having 1 to 22 carbon atoms) (X=Cl, Br, CH ₃ SO ₄ , NO ₃ , ClO ₄ , R: alkyl group having 1 to 22 carbon atoms) (X = Cl, Br, CH ₃ SO ₄ , NO ₃ , ClO ₄ , R: alkyl group having 1 to 22 carbon atoms) These cationic compounds are generally added to the reduction cleaning solution at a rate of 1 g/~5 g/. and use it. Also, in terms of the amount of adhesion to fibers, it is generally 0.001~
The object of the present invention can be achieved within the range of 5% by weight.

On the other hand, examples of hydrophobic polymers with a low refractive index as used in the present invention include polytetrafluoroethylene, tetrafluoroethylene-propylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, and tetrafluoroethylene-propylene copolymer. Fluorine-containing polymers such as ethylene-tetrafluoropropylene copolymer, polyfluorovinylidene, polybentadecafluorooctyl acrylate, polyfluoroethyl acrylate, polytrifluoroisopropyl methacrylate, polytrifluoroethyl methacrylate, polydimethylsilane, poly Examples include silicon-containing compounds such as methylhydrodiene siloxane and polydimethylsiloxane, acrylic acid esters such as ethylene-vinyl acetate copolymer, polyethyl acrylate, and polyethyl methacrylate. It is sufficient to select and use a material with a small refractive index.

As the emulsifying or dispersing agent for emulsifying or dispersing these hydrophobic polymers, acids and/or anionic activators are suitable. Examples of acids include hydrochloric acid, sulfuric acid, formic acid, phosphoric acid, aliphatic carboxylic acid, aliphatic sulfonic acid, alkylbenzenesulfonic acid,
Organic and inorganic acids such as alkylnaphthalene sulfonic acid, halogen-substituted aliphatic carboxylic acid, and polyoxyethylene alkyl ether sulfate can be mentioned, and anionic activators include higher fatty acid salts,
Examples include higher alcohol sulfate ester salts, alkyl sulfonates, alkylaryl sulfonates, formalin condensed naphthalene sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, perfluoroalkyl phosphates, etc. . These emulsifying or dispersing agents may be added during the polymerization step of the hydrophobic polymer, or may be added when the hydrophobic polymer is emulsified or dispersed in water.

Electrolytic substances that can be added to the above emulsion or dispersion as necessary include common salt, sodium sulfate, potassium sulfate, sodium hydrogen sulfate, potassium hydrogen sulfate, ammonium sulfate, ammonium chloride, sodium nitrate, potassium nitrate, ammonium acetate, and sodium acetate. and organic and inorganic acids, among which inorganic salts are preferred, and particularly when potassium hydrogen sulfate is used, a large bathochromic effect can be obtained and favorable results can be obtained.

The treatment agent bath used in the present invention can be made apparently completely stable by combining an appropriate emulsifying or dispersing agent with an electrolytic substance. It is desirable to stir constantly. For this purpose, for example, for textile structures in the form of fabrics, it is suitable to use a jet dyeing machine or the like. The temperature of the treatment bath may be any temperature, but 50 to 90°C is suitable for shortening the treatment time and preventing dyeing of the dyed fiber structure, and a treatment time of 1 minute to 30 minutes is sufficient.

In addition, the polymer concentration in the treatment bath is usually 0.01 to 5.
% dispersion concentration electrolyte substance concentration may be set to a solution concentration of 0.01 to 5%.

The reason why the treatment of the present invention can produce an excellent deep color effect is not yet clear, but the following reasons can be considered. In other words, the dispersion stability of hydrophobic particles emulsified and dispersed with an anionic activator depends on the electrostatic repulsion formed around the particles,
A stable dispersion state is maintained due to balance due to mutual potential energy such as van der Waals attraction, but the presence of cationic compounds on the fiber surface or the addition of electrolytic substances to the bath may cause problems. This disrupts the balance near the fiber surface, greatly reducing the dispersion stability of hydrophobic particles, allowing them to selectively and easily adsorb to the surface of hydrophobic objects such as synthetic fibers, and furthermore, during bath treatment. Therefore, it is assumed that the hydrophobic polymer is uniformly attached to each fiber and is not selectively adsorbed between the fibers, so that hardening of the texture does not occur.

The method of the present invention is useful when the dyeing density is high regardless of the hue of the object to be dyed, but its effect is particularly remarkable on very dark dyed fabrics such as navy blue and black. in this case,
As for fibers, JP-A-52-99400 and JP-A-54-
As disclosed in Japanese Patent Publication No. 120728, Japanese Patent Publication No. 54-44800, etc., when applied to fiber structures in which deep coloring is achieved by imparting irregularities to the fiber surface, the deep color property can be further enhanced. can.

The present invention will be explained in more detail with reference to Examples below, and all proportions in the Examples mean percent by weight unless otherwise specified. In addition, the viscosity of siloxane indicates the viscosity of the siloxane itself, and all values are measured at 25℃.
It was measured with Furthermore, as a measure of the bathochromic effect,
Using the bathochromic index (K/S), this value is determined by measuring the spectral reflectance (R) of the sample using a Shimadzu RC-330 self-recording spectrophotometer, and using the Kubelka-Munk formula shown below. Obtained from the formula. The larger this value is, the greater the deep color effect is.

K/S=(1-R) ² /2R In addition, K shows an absorption coefficient and S shows a scattering coefficient.

Hereinafter, the present invention will be explained in more detail with reference to Examples, and all ratios in the Examples mean weight percentages unless otherwise specified. Furthermore, the bathochromic degree (K/S) is used as a measure to indicate the bathochromic effect, and this value is the spectral reflectance (R) of the sample compared to the Shimadzu RC-330.
It was measured using a type self-recording spectrophotometer and determined from the Kubelka-Munk equation shown below.
The larger this value is, the greater the deep color effect is.

K/S=(1-R) ² /2R In addition, K shows an absorption coefficient and S shows a scattering coefficient.

Example 1 [A] Preparation of emulsion of hydrophobic polymer: 200 g of deionized water in a 400 c.c. stainless steel autoclave under a protective atmosphere of nitrogen;
Add 1.1 g of ammonium persulfate, 3.0 g of sodium pyrophosphate, 0.25 g of sodium bisulfite, and 0.15 g of ammonium perfluoro-n-octoate as an emulsifier, close the container, cool in a dry ice/acetone bath, and vacuum to 1 mmHg. 40g of tetrafluoroethylene,
Introduce 20g of propylene and shake the container.
The temperature was raised to 80°C and polymerization was carried out for 8 hours. The reaction was then stopped and cooled to room temperature to obtain an extremely stable emulsion of tetrafluoroethylene-propylene copolymer with a dry solids content of 20%.

[B] Reduction cleaning of dyed product and treatment with emulsion of [A]: Dianix 100% polyester dioset fabric with a basis weight of 150 g/m ² that has been subjected to alkali reduction treatment.
Black HG-FS (Mitsubishi Chemical Industries, Ltd. product) 15%
After dyeing using a jet dyeing machine at 130°C for 60 minutes with OWF, dyeing with an aqueous solution containing 1 g of caustic soda, 2 g of hydrosulfite, and 2 g of trimethylbenzylammonium chloride.
℃ for 20 minutes and bathochromicity (K/S measurement wavelength)
A water-washed black dyed cloth of 1.65 (500 μm) was obtained. Subsequently, without drying this black coating, the above black coating was used for dyeing in a processing agent bath consisting of [A] tetrafluoroethylene-propylene copolymer emulsion, 0.5% OWF in terms of solid fraction, and 1 g of potassium hydrogen sulfate. 80℃ using the same jet dyeing machine as
It was treated in a bath for 20 minutes, dehydrated and dried.

The bathochromic degree (K/S measurement wavelength) of the obtained treated cloth
500mμ) was 27.2.

On the other hand, for comparison, the bathochromic degree (K/S measurement wavelength
500mμ) was 25.3.

Example 2 [A] Production of emulsion of hydrophobic polymer Dimethylpolysiloxane 30 with viscosity 1000CS
g, tall oil fatty acid 2 containing basic oleic acid
g, 0.5 g of 28% by weight ammonia water, 0.75 g of triethanolamine, and 66.75 g of water were mixed using a homogenizer to obtain an emulsion.

[B] Reduction cleaning of the dyed product and treatment with the emulsion of [A] A 100% polyester processed fabric with a basis weight of 120 g/m ² was dyed using a jet dyeing machine, and Miketon Poly-
ester Black TSL (Mitsui Toatsu Chemical Industry Co., Ltd. product)
Stained at 130℃ for 60 minutes at 20% owf, 2g/methyldodecylbenzyltrimethylammonium chloride, 2g/hydrosulfite.
, 1 g of caustic soda/20 at 80℃ in aqueous solution
After cleaning for a minute, K/S value (measurement wavelength 500m)
μ) A washed black dyed cloth of 19.8 was obtained.

After that, the above emulsion was added to 1% owf of the dyed cloth in terms of individual pieces, and potassium hydrogen sulfate 1g/
The dyeing machine was treated in the same treatment bath at 80°C for 20 minutes, washed with water for 10 minutes, dehydrated, air-dried, and heat set at 160°C for 1 minute.

K/S value of the obtained treated cloth (measurement wavelength 500m
μ) showed 26.2.

On the other hand, for comparison, the K/S value (measurement wavelength 500 mμ) of a treated cloth processed under the same conditions as above except that methyldodecylbenzyltrimethylammonium chloride was not added during reduction cleaning.
was 23.5.

Example 3 The same procedure as in Example 2 was carried out except that the dye was changed. i.e. Dianix Red as dye
The results of resistance to dyeing with 3% (OWF) TB-SE (product of Mitsubishi Chemical Industries, Ltd.) were as follows.

K/S (measurement wavelength 620mμ) 1 Untreated dark colored cloth 0.40 2 Treated cloth 0.61 3 Treated fabric (comparative example) 0.48

Claims (1)

[Claims] 1. A cationic compound is attached to the dyed polyester fiber structure during reduction cleaning, and then the dyed fiber structure is made into a hydrophobic material having a refractive index lower than that of the polyester fiber. 1. A method for deep coloring a polyester fiber structure, which comprises immersing a polymer in a treatment agent bath in which a polymer is emulsified or dispersed, and performing an in-bath treatment. 2. A method for deep coloring a polyester fiber structure according to claim 1, wherein a cationic compound is allowed to coexist in the reducing cleaning solution. 3. The method for deep coloring a polyester fiber structure according to claim 1, wherein the cationic compound is an alkyl quaternary ammonium salt. 4. The method for deep coloring a polyester fiber structure according to claim 1, wherein the cationic compound is an alkylbenzyl quaternary ammonium salt. 5. The method for deep coloring a polyester fiber structure according to claim 1, wherein the cationic compound is a quaternary ammonium salt containing a nitrogen ring. 6. A method for deep coloring a polyester fiber structure according to claim 1, which comprises emulsifying or dispersing a hydrophobic polymer with an acid and/or anionic activator. 7. The method for deep coloring a polyester fiber structure according to claim 1, wherein the hydrophobic polymer is a fluorine-containing polymer or a silicon-containing polymer. 8. A deep color processing method for a polyester fiber structure according to claim 1 or 6, wherein an electrolytic substance is present in a treatment bath in which a hydrophobic polymer is emulsified or dispersed. 9. The method for deep coloring a polyester fiber structure according to claim 8, wherein the electrolytic substance is an inorganic salt. 10. The method for deep coloring a polyester fiber structure according to claim 9, wherein the inorganic salt is potassium hydrogen sulfate.