JPH0555635B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a dyeing method useful for coloring fiber molded articles using a noble metal hydrosol.

Conventional technology Because precious metals such as gold and silver are rare and expensive,
Items using this material have been considered luxury items since ancient times. A precious metal hydrosol that is uniformly dispersed in water as extremely fine particles is called a noble metal hydrosol, and the precious metal fine particles that make up this are called a noble metal colloid. A noble metal colloid with a positive charge is called a positive noble metal hydrosol, and one with a negative charge is called a negative noble metal hydrosol.

Noble metal hydrosols are generally strongly colored transparent liquids (for example, gold is red, silver is yellow, etc.), but the precious metal colloids contained therein have the property of coloring the surface of a solid when it is adsorbed. For example, it is known as ``Cassius Purple'' made of colloidal gold. If it is possible to dye cloth for clothing using these precious metal hydrosols,
It is thought that precious metals are given a high-class image and their value is increased, but with negative precious metal hydrosols containing water-soluble polymers such as gelatin and polyvinyl alcohol, which have been known so far, it is not possible to directly dye cloth or thread. I couldn't.

From this point of view, the inventors previously discovered a method for dyeing fiber moldings in purple-based colors by using a positive gold hydrosol containing a cationic surfactant (Tokukaisho et al. 62−299587). The positive gold hydrosol used in this method is obtained by reducing gold ions in the presence of a cationic surfactant, or by reducing gold ions in the presence of a water-soluble polymer or a nonionic surfactant. Once a negative gold hydrosol is obtained, a cationic surfactant is added thereto.

Generally, noble metal fine particles such as gold tend to be negatively charged in water, so it is easy to create a negative noble metal hydrosol. However, when a cationic surfactant is added to a noble metal hydrosol and converted to a positive charge, the colloid passes through a state where the charge is zero (called the isoelectric point) during the process, which may cause some aggregation. is unavoidable. This aggregation becomes more pronounced as the scale of production of noble metal hydrosol increases.
This is a major problem in industrial production.

Means for Solving the Problems The inventors have conducted extensive research in search of a method for dyeing fabrics, threads, and other fibrous articles using easily produced negative noble metal hydrosols instead of positive noble metal hydrosols. As a result, the inventors discovered that dyeing with a negative noble metal hydrosol becomes possible by pre-treating a fiber molded article with a metal salt mordant, leading to the present invention.

That is, in the present invention, after the metal salt mordant treatment,
The present invention provides a method for dyeing a fiber molded article, which is characterized by immersing it in a negative noble metal hydrosol.

In the method of the present invention, common metal salt mordants comprising polyvalent metal ions such as aluminum acetate, basic chromium acetate, and sodium stannate are used for mordant treatment.

The negative noble metal hydrosol used in the method of the present invention can be obtained by a conventional method of reducing an aqueous solution of a noble metal salt with sodium borohydride, sodium citrate, or the like. As a noble metal salt,
For example, chloroauric acid, silver nitrate, palladium chloride, chloroplatinic acid, rhodium chloride, ruthenium chloride, etc. are used. In addition, as stabilizers to prevent noble metal colloids from aggregating, water-soluble polymers such as polyvinylpyrrolidone and polyvinyl alcohol, anionic surfactants such as sodium dodecylbenzenesulfonate, polyethylene glycol mono-p-nonyl phenyl A nonionic surfactant such as ether is appropriately added (for example, Japanese Patent Application Laid-Open No. 120249/1983).

To carry out the present invention, the fiber moldings are mordanted and then immersed in a negative noble metal hydrosol. The mordant treatment is performed by immersing the fiber molded article in an aqueous solution of a metal mordant. The temperature and time of mordant treatment vary depending on the metal salt mordant used, but
Normally, at room temperature or below 100℃,
Complete within a few hours. After washing the fiber molded article mordanted in this way with water, it is immersed in a negative noble metal hydrosol for a certain period of time. During immersion, the fiber molded product may be stirred as appropriate by shaking or the like. Next, it is pulled up, washed with water, and then dried. In this way, the fiber molded product is colored in a color appropriate to the noble metal colloid (for gold, from reddish-purple to dark purple, for silver, from yellow to yellow-brown, etc.). The time required for immersion in a noble metal hydrosol varies depending on the type and amount of stabilizer contained in the hydrosol and the type of noble metal, but it is usually selected in the range of several minutes to several days. The fiber molded product will be colored in a light color, and if left for a long time, it will be colored in a deep or dark color. The temperature of the noble metal hydrosol to be immersed is usually room temperature, but the immersion time can also be shortened by heating it in a range of 100°C or less.

The fiber molded articles to which the method of the present invention is applied are woven fabrics, knitted fabrics, nonwoven fabrics, and yarns whose constituent fibers are silk or wool.

Examples Next, the present invention will be explained in more detail with reference to examples.

Example 1 0.05 mmol of chloroauric acid, 10 mg of sodium dodecylbenzenesulfonate and sodium citrate
0.05 mmol was dissolved in 100 ml of pure water and heated under reflux for 1 hour to obtain a dark red transparent gold hydrosol.

A 6 cm x 10 cm 14 momme plain weave silk cloth (Japanese Standards Association, attached white cloth for dye fastness test) was immersed in 100 times the volume of 1% aluminum acetate (Al ₂ O (OCOCH ₃ ) ₄ ) aqueous solution for 20 minutes at room temperature. After mordant treatment,
It was washed with water and immersed in the above gold hydrosol for 1 hour. This was pulled up, washed with water, and dried to obtain a reddish-purple colored silk cloth.

Example 2 Dissolve 0.05 mmol of silver nitrate in 91.5 ml of pure water, and add 10 mg of sodium dodecylbenzenesulfonate while stirring.
1 ml of an aqueous solution of was added, followed by 5 ml of an aqueous solution of 0.2 mmol of sodium borohydride to obtain a yellow-brown transparent silver hydrosol. In this silver hydrosol,
A silk cloth that had been mordanted in the same manner as in Example 1 was soaked for 1 hour, washed with water, and dried to obtain a yellow colored silk cloth.

Example 3 0.05 mmol of palladium chloride was added to sodium chloride
Dissolve 0.25 mmol in pure 91.5 ml, add 1 ml of an aqueous solution of 10 mg of polyvinylpyrrolidone (molecular weight approximately 40,000) under stirring, and then add 5 ml of an aqueous solution of 0.2 mmol of sodium borohydride to obtain a dark brown transparent palladium hydrosol. Ta. A silk cloth that had been mordanted in the same manner as in Example 1 was immersed in this palladium hydrosol for 1 hour, washed with water, and dried to obtain a silk cloth colored light brown.

Example 4 0.05 mmol of chloroauric acid was dissolved in 95 ml of pure water, and 5 ml of an aqueous solution of 0.2 mmol of sodium borohydride was added under stirring to obtain a dark red transparent gold hydrosol.

A plain weave silk cloth similar to that used in Example 1 was heated at 70°C.
100 times the amount of 0.1% chromium acetate (Cr
(OCOCH ₃ ) ₃ H ₂ O) After being immersed in an aqueous solution for 20 minutes for mordant treatment, it was washed with water and immersed in the above gold hydrosol for 1 hour. This was pulled up, washed with water, and dried to obtain a reddish-purple colored silk cloth.

Example 5 0.05 mmol of chloroauric acid was dissolved in 91.5 ml of pure water, 1 ml of an aqueous solution of 10 mg of polyethylene glycol mono-p-nonyl phenyl ether (degree of polymerization of polyethylene glycol moiety = 10) was added under stirring, and then hydrogenated. 5 ml of aqueous solution of 0.2 mmol of sodium boron
was added to obtain a dark red transparent gold hydrosol. A silk cloth that had been mordanted in the same manner as in Example 4 was immersed in this gold hydrosol for 1 hour, washed with water, and dried to obtain a dark purple colored silk cloth.

Example 6 0.05 mmol of chloroplatinic acid and 0.02 mmol of sodium citrate were dissolved in 100 ml of pure water and heated under reflux for 4 hours to obtain a blackish brown transparent platinum hydrosol.

A plain weave silk cloth similar to that used in Example 1 was heated at 50°C.
Contains 0.1% sodium stannate (Na ₂ SnO ₃ 3H ₂ O) and 0.3% citric acid kept at
After being immersed in a 100 times the amount of aqueous solution for 20 minutes for mordant treatment, it was washed with water and immersed in the above platinum hydrosol for 1 hour. Pull it up, wash it with water, dry it,
A gray colored silk cloth was obtained.

Effects of the Invention The colored fiber molded products obtained by the method of the present invention all exhibit a high-quality color, and do not change color even if left in a bright place for a long period of time. In addition, silk fabrics are inherently expensive, and
Because it was dyed using rare precious metals,
This has the effect of further enhancing the image of luxury goods.

Claims (1)

[Claims] 1. A dyeing method characterized by treating a fiber molded article with a metal salt mordant and then immersing it in a noble metal hydrosol in which the constituent noble metal colloid has a negative charge.