JPS62184178A - Coloration of fiber - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] The present invention relates to a method for coloring fibers.

Various attempts have been made to improve the added value of fibers by coloring them into various colors. For example, carbon fibers, which have excellent properties such as high strength and high elasticity, are generally difficult to color, and various methods of coloring have been studied to improve their decorative properties. Methods for coloring carbon fiber products include methods of coloring the surface of the fiber itself, methods of coloring a composite material of carbon fiber and plastic with pigments or dyes, methods of adding a third fiber to the composite material, and methods of adding a third fiber to the composite material. There are methods such as painting the surface with Metsugyu or painting. Among these methods, methods of coloring the surface of carbon fibers by forming a metal film on the surface of the fibers using methods such as electrolytic feeding, electroless feeding, and vapor deposition are known. There is. The metals used in this method include Ni, AI, etc. After forming a Ni film, it is also possible to form a gold metal film. However, in such a method,
There is a restriction that the colors that can be colored are limited to the inherent colors of metals that can form a metal film on the fibers.

Means for Solving the Problems The present inventor has conducted extensive research in order to find a method of directly coloring fiber surfaces in which fibers can be colored in various colors. As a result, after forming a copper film on the fiber surface, which has traditionally been used not for the purpose of coloring but to make it conductive and to enable soldering, the fiber is heat-treated in the presence of oxygen. , depending on the heat treatment conditions,
They discovered that fibers can be colored in various colors, and thus completed the present invention.

That is, the present invention relates to a method for coloring fibers, which is characterized by heat-treating fibers on which a copper coating has been formed in the presence of oxygen.

The fibers used in the present invention are not particularly limited,
Any material may be used as long as it is capable of forming a copper film and is stable under the applied heat treatment conditions. Such fibers include carbon fiber, glass fiber, etc.
Examples include fibers with heat resistance of C or higher. These fibers may be either short fibers or long fibers.

In the present invention, first, a copper film is formed on the fiber.

The method for forming the copper film is not particularly limited, and may be, for example, an electrolyte method, an electroless method, a vapor deposition method, etc., and a copper film may be formed according to known processing conditions. good. Among these methods, the electric metsushi method is
It is advantageous in terms of cost, cutting speed, ensuring sufficient cutting thickness, etc., and it varies depending on the situation, but it is usually 0.3 to 0.5 μm.
In order to uniformly color the fibers, it is preferable to form a copper coating with as uniform a thickness as possible so that the degree of heating is constant.

Below, a preferred embodiment will be shown in which a copper coating is formed on the surface of carbon fibers by an electrometallurgical method.

First, a noble metal film is formed on the surface of the carbon fiber as a pretreatment before electrocuting the carbon fiber. If the surface of the carbon Nk male is clean, it is possible to form a film on it, but it is usually preferable to perform a cleaning treatment such as washing with water in advance, or use a silicic acid or phosphorus film to obtain surface wettability. After degreasing with an acidic alkali, wash with water or use alcohol, acetone, ethyl acetate, dimethylformanide (DM
After treatment with solvent such as F), wash with hot water (approximately 40°C) and perform the following treatment. When the carbon fibers are covered with a coating material such as ebo-shi, the coating material is removed using a solvent such as sulfuric acid, and then the same treatment as described above is performed.

The subsequent noble metal thin film formation process can be carried out as follows, regardless of whether the noble metal is palladium or silver. That is, when forming a palladium thin film, carbon fibers are mixed with palladium chloride (PdC12) and tin chloride (5
After immersing in a mixed solution of 98% sulfuric acid or 36% hydrochloric acid for about 5 seconds to 10 minutes, preferably about 30 seconds to 3 minutes, at about 0-40°C, preferably at room temperature,
20 volumes, preferably 7 to 13 volumes, or a mixture thereof, or 5 to 15% by weight of sodium hydroxide
A suitable method is immersion in a solution at about 0 to 60° C. for about 5 seconds to 10 minutes, preferably about 30 seconds to 3 minutes. The PdC4,/5nCI2 mixed solution used in the above method is usually PdC4/Sm (EJL of 42, ratio 0).
．． 06-0.008, preferably 0.02-0.015
PdClI2 in the range of 0.002~l 51/
1, preferably 0.01 to 5 Vl, and 30 to 1501/1f as C4 to maintain stability.
A part of the solution can be replaced with NaC4 or H2SOI), and a solution with -H of about 1.0 or less is preferred.

Another suitable method for forming a radium thin film is to first prepare tin chloride (SHCl a ) and hydrochloric acid (HCl).
The carbon fibers are heated in a mixed solution of about 0 to 40°C, preferably at room temperature, for about 5 seconds to 10 minutes, preferably about 30 seconds to 30 minutes.
The surface of the material is sensitized by dipping for minutes, and then soaked in a mixed solution of palladium chloride (Pet(42) and hydrochloric acid (II(4)) at about 0 to 40°C, preferably at room temperature, for about 5 seconds to
A method of immersing for IO minutes, preferably about 30 seconds to 3 minutes can be mentioned. In the method 5RCI2/BC
1 mixed solution is 5 s Cj 2 / HCj
molar ratio of 0.8 to 0.1, preferably 0.7 to 0.3
Adashi, 0.2-20 as 5HC12.2 H2O
f/1. Solutions containing preferably 3 to 12 Vl can be advantageously used. In addition, as a PdCl2/H(4 mixed solution, the t ratio of PdCl2/HCj is 0.5 to 0.03, preferably 0.5 to 0.1, and PdCl2 is 0.002 to 15 f/l. , preferably 0.01 to 5
Solutions containing f/l are effective.

When forming a thin silver film, carbon fibers are first treated with tin chloride (SmC4□) and hydrochloric acid (H(4)) as described above.
After being similarly sensitized by immersion in a mixed solution of about 0 to 40°C, preferably at room temperature for about 5 seconds to 10 minutes, preferably about 30 seconds to 3 minutes, 0 to 40°C, preferably at room temperature for about 5 seconds to 10 minutes,
The most preferred method is preferably immersion for about 30 seconds to 3 minutes. In this method, as the silver nitrate solution, AlN03t
o, OO2~20y/1. Preferably 0.005-5
A solution containing y/l can be preferably used.

By washing the treated material with water after forming each of the metal thin films mentioned above, a desired treated material is obtained in which a thin film of palladium or silver, which is a special name used as a catalyst during electroplating, is formed on the surface of carbon fibers. can.

After forming the noble metal thin film, copper plating is performed by electroplating according to a conventional method. For copper plating, all currently used raw temperature baths, including the well-known copper sulfate baths, copper diazide baths, and copper diphosphate baths, can be applied. The conditions are not particularly limited, and any conditions may be used as long as a normal copper film is formed on the fibers. As an example of a raw temperature of copper meth that is suitable for use, a mixture of regular sulfuric acid sulfuric acid and a brightening agent, such as Torazurutina 7'-10 (trademark, manufactured by Okuno Pharmaceutical Co., Ltd.), is used. EPC-Ligyutsudo Cm is a special medium wave of copper phosphate type that enables
(Trademark, manufactured by Okuno Pharmaceutical Co., Ltd.). When a copper film is formed using such raw temperature, the mechanical strength of the fiber is hardly reduced.

After forming the copper film, before the next heat treatment process,
In order to prevent the copper coating from discoloring, it is desirable to treat it with an anti-discoloration agent, if necessary. As the discoloration inhibitor, any known commercial discoloration inhibitor can be used.

In the present invention, the copper coating is oxidized by heat-treating the fiber on which the copper coating has been formed in the presence of oxygen in the atmosphere, thereby changing the color of the coating. Since the color of the copper film can be changed by appropriately selecting the heating temperature and time, the heat treatment conditions are not particularly limited, but in practice, 18
It is appropriate to perform heating at about 0 to 230'C for about 2 to 20 minutes. If the heat treatment temperature is too low,
On the other hand, if the heat treatment temperature is too high, the oxidation of the copper film will proceed rapidly, making it difficult to obtain a film of the desired color.

The heat treatment time is not constant depending on the heat treatment temperature, and may be set to the time required for the copper film to change to a desired color, but generally, as described above, the time may be set to about 2 to 20 minutes. Generally, as the treatment time increases, the oxidation of the copper film progresses and the film changes from dark red to black.

As a heat treatment method, heating with hot air may be used, but a method of heating by placing fibers in sand, so-called sand, is preferred because it can heat uniformly and avoids the rapid oxidation reaction of copper. A heating method is more preferred.

After the copper coating has been changed to a desired color, it is preferable to treat it with an anti-tarnishing agent in order to prevent further discoloration of the copper.

Effects of the Invention According to the method of the present invention, fibers can be easily colored in various colors simply by using a simple heat embedding process.

In addition, the strength of the fibers hardly decreases after the treatment.The method of the present invention has the above-mentioned excellent features and can improve the commercial value of reeds and fibers as decorative materials. For example, composite materials of fibers and resin made by the filament wind schiff method (using long fibers) and SMC (
5heet pneldiyrg tagdoor-5ped
.

(Using short fibers), B, MC (Bulk moldin)
ram door oszmd.

By using the colored fibers obtained by the method of the present invention, the decorative properties of textile-containing products can be further improved.

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

Example! Using a bundle of 12,000 wood carbon fibers as a sample, a copper-metallic skin was formed in the following manner.

First, the above carbon fibers (length 200111, 4 bundles) were fixed to a jig, and in order to obtain surface wettability, Bridiz EPC
,-1 (manufactured by Okuta Pharmaceutical Industry) for 4 minutes, and then washed with hot water at 40°C for 100 m as a preliminary treatment for catalyst application.
/j hydrochloric acid solution for 2 minutes. Then, PdC4□/
S#C12 mixed solution (PdCl2fold 1/I, PdC
Ia/”Cla molar ratio-0,02,36%HCl150
d/1 containing, H1 or less) at 27°C for 3 minutes, washed with water, and then 98% H2so410 volumetric solution VC2
After being immersed at 5°C for 2 minutes, it was washed with water and further neutralized with a neutralizing agent.

Next, using a %eO copper ricinate + bath (trademark: EPC-Rigyutsudo C11, manufactured by Okuno Pharmaceutical Co., Ltd.), the bath was stirred with air and a cathode locker at pH 8.8 and bath temperature of 21°C. While doing this, electrometallurgical treatment was performed for 2 minutes at 10.4 and then 3 minutes at 18J to form a copper membrane coating on the carbon fibers.
It was formed to a thickness of 5 to 0.7 μm.

Next, after a copper membrane was formed and the carbon fibers were washed with water and dried, they were subjected to heat treatment using the sacid heating method under the conditions shown in Table 1 below. Table 1 shows the color, fiber diameter, and tensile strength of the fibers after heat treatment.

Table 1 After heat treatment, rust preventive agent 51! (manufactured by Okuga Pharmaceutical Industries) 2
After soaking at 5°C for 2 minutes, washing with water and drying, no discoloration occurred even after 30 days.

(that's all)

Claims (1)

[Claims] [1] A method for coloring fibers, which comprises heat-treating fibers on which a copper coating has been formed in the presence of oxygen.