JPS6380405A - Conducting processing - Google Patents

Abstract

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

Description

[Detailed description of the invention] (Industrial application field) TECHNICAL FIELD The present invention relates to a method for electrically conductive processing of a fibrous sheet-like structure.

More specifically, the present invention relates to a method for uniformly processing a long fiber sheet-like structure.

(Prior Art) In recent years, with the progress of the electronics industry, the demand for conductive materials has increased, and various new products have been proposed in response to this demand. Among them, nine conductive fibers have been proposed by attaching copper sulfide to acrylic fibers, polyamide fibers, polyester fibers, or natural animal or vegetable fibers containing cyan groups (Japanese Patent Laid-Open No. 56-12
No. 8311, No. 56-169808 and No. 5
7-21570). These conductive fibers can be made, for example, by treating the fiber threads in a solution containing copper salts and reducing sulfur compounds, or by contacting them under pressure with reducing sulfur compounds such as hydrogen sulfide and then removing steel ions. By treating with a solution containing copper sulfide, a conductive layer made of copper sulfide is formed on the surface of the fibers.
This makes it possible to obtain conductive fibers.

In this treatment of copper sulfide formation and adhesion, fibrous sheet-like structures have been packed into bags and stuffed into the bath, but #R#! There is no limit to the shape of the sheet-like material, and with this method, it is difficult to always produce copper sulfide uniformly in the bath, and the uniformity of the obtained fibrous sheet-like material is low. Unfortunately, there are still problems in terms of processability as the fiber sheets become entangled.

(The problem to be solved by the invention) A conductive layer containing copper sulfide is uniformly formed, so that the resulting product has uniform conductivity, excellent processability, and good conductivity. It is an object of the present invention to provide a method for industrially producing a fibrous sheet-like structure.

(Means for Solving the Problems) The present invention involves forming a long fiber sheet-like structure into a comb shape, and then subjecting it to a copper sulfide forming treatment to form a conductive layer containing copper sulfide on the fiber surface. This is a conductive processing method that is characterized by

In the present invention, the term "comb shape" refers to a shape such as shown in FIG. 1, in which long fiber sheet-like structures are piled up and wound up. The skein-like form depends on the length and width of the elongated fiber sheet-like structure, or the inner diameter (Ll) and outer diameter <Ll) of the rolled form,
Various packing densities can be considered, but they are not particularly limited. Preferred ridge-like forms are determined in various ways depending on the processing method, but from the viewpoint of processing convenience, those having an inner diameter (Ll) of 2 m or less and a packing density o of 5t7- or less are usually used. Moreover, the comb-shaped form can be determined as appropriate depending on the use of the conductive fiber sheet-like structure. However, from the convenience of subjecting the fibrous sheet-like structure to copper sulfide generation and adhesion treatment, and the conductive performance of the conductive fibrous sheet-like structure obtained by the treatment, it is more preferable that the inner diameter (LH) be 3.
~15 am, an outer diameter (L) of 10 to 30 pieces, and a packing density of 0.2 to 0.25 f/cd.

The elongated fibrous sheet-like structure as used in the present invention is a fibrous sheet-like structure that has a constant width and is elongated in the vertical direction. The long fiber sheet-like structure, such as the ribbon shape of @151 and the shape of a 1 m long woven fabric, can have various shapes depending on its width and length, but there is no particular limitation on it. It can be determined as appropriate depending on the use and processing method of the conductive fiber sheet-like structure.

The fiber sheet-like structure used in the present invention is not limited to woven fabrics, knitted fabrics, or nonwoven fabrics.

It can be determined as appropriate depending on the use of the conductive fiber sheet-like structure. It is also possible to subject the fabric to a copper sulfide formation adhesion treatment as a woven or knitted fabric and then defibrate or knit it.

There are no particular limitations on the type of fiber yarn used in the method of the present invention, but examples include polyamide fibers (including aromatic polyamide fibers), polyester fibers, polyacrylic fibers, polyolefin fibers, and polyurethane fibers. ,
Polyester ether fiber, polyvinyl alcohol fiber, polyvinyl chloride fiber, polyvinylidene chloride fiber, rayon fiber, cupro fiber, cellulose acetate fiber,
Preferably, the fiber is made of at least one type of fiber selected from animal rut fibers, vegetable fibers, and the like. These fiber yarns are used in the form of spun yarn, monofilament yarn, or multifilament yarn, and may be mixed fiber yarn or composite yarn.

Furthermore, there is no particular limitation on the method of forming conductive Wl made of copper sulfide on the VC fibers. For example, JP-A-57-3
In accordance with the method described in Publication No. 5078, a fibrous sheet-like structure made of a synthetic polymer is brought into contact with a reducing sulfur compound such as hydrogen sulfide under pressure, and then treated with an aqueous solution of a copper salt. It is possible to use a method in which a reducing agent is applied simultaneously with or subsequently to this treatment. Alternatively, according to the method described in JP-A No. 56-128311, - After adsorbing the image-forming ions to the fibers, the fibers are treated with a compound capable of releasing sulfur atoms and/or sulfur ions. You may also use the method of

Alternatively, according to the method described in JP-A No. 57-21570, a divalent copper ion, a reducing agent capable of reducing the divalent copper ion to a monovalent one, and a sulfur atom and/or a sulfur ion are used. A method of treating a fibrous sheet-like structure using a treatment liquid containing a compound capable of releasing .

Copper salts used in the above method include divalent copper salts such as cupric chloride, copper sulfate, steel nitrate, cupric acetate, and copper oxalate; cuprous chloride, cuprous iodide, and cyanide. There are copper salts such as cuprous chloride and cuprous thiocyanate. However, examples of reducing agent sulfur compounds include sulfoxylates,
Nithionite, thiosulfate, sulfite, bisulfite, pyrosulfite, thiourea, etc. can be used.

Further, examples of reducing agents capable of reducing divalent copper ions to t-1 valent copper ions include metallic copper, hydroxylamine sulfate, ferrous sulfate, ammonium vanadate, furfural, sodium hypophosphite, and sugar. I can list them.

Furthermore, compounds that can release both or either one of sulfur atoms and sulfur ions include sodium sulfide, sulfite, dithionite, sodium dithionite,
Sodium thiosulfate, acidic sodium sulfite, sodium pyrosulfite, bifurcated sulfur, ditrithiourea, hydrogen sulfide,
Examples include Rongarit C10 and Rongarit 2.

As mentioned above, among the treatment methods for forming a conductive layer made of copper sulfide on a fiber sheet, for example, in the case of a method in which the fiber sheet is treated in one bath with an aqueous solution containing a copper salt and a reducing sulfur compound, the treatment The conditions are usually 10 minutes to 5 hours at a temperature of 20 to 150°C, preferably 3G to 100°C, and a bath ratio of 1:10.
-100 is adopted.

When heat treatment is used in conjunction with this copper sulfide generation and adhesion treatment,
It is preferable to gradually heat the treatment bath from room temperature to a temperature of 0.5 to b. The pH of the treatment bath is usually 1.5 to 6], and if necessary, inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid, organic acids such as citric acid and acetic acid, and disodium hydrogen phosphate, sodium citrate, and acetic acid are added. p consisting of at least 1 m selected from salts such as sodium
H regulator is used. It is also effective to add a nitrile group-containing compound and/or a mercapto group-containing compound to the treatment bath for the purpose of promoting the formation of copper sulfide.

Furthermore, in order to prevent the deformation of the shape and the occurrence of defects in the fiber sheet-like structure during the wet processing to form copper sulfide, the material to be processed is generally placed in a bag made of coarse silk or fabric. It is preferable to subject it to treatment.

In the method of the present invention, the amount of the copper sulfide conductive layer contained in the copper sulfide-containing fibrous sheet-like structure obtained in the conductive layer forming treatment step is determined so that the amount of the copper sulfide conductive layer contained in the copper sulfide-containing fibrous sheet-like structure obtained in the conductive layer forming treatment step is determined to meet the electrical conductivity required for the intended conductive fiber sheet-like structure. It can be arbitrarily determined by taking into consideration the type of fiber sheet material, usage, etc., but in general, it is 0.5 to l.
It is preferable that it is within the range of G weight %.

In addition, in order to impart high resistance and durability against physical friction, abrasion, etc. to the conductive fiber sheet-like structure obtained by the treatment, a wear-resistant additive such as polyester A resin that is film-forming and becomes water-insoluble after drying, such as a polyamide-based, polyamide-based, or polyacrylic acid-based polymer, may be applied, preferably in a tray of 3 to 4 oz. .

In the method of the present invention, the fibrous sheet-like structure is packed in the bath for copper sulfide formation and adhesion reaction in the form of strands, so the object to be treated is uniformly filled in the bath, the processing solution is uniformly passed through the bath, and The reaction does not proceed too much in the middle part, and the copper sulfide is evenly deposited on the fibers, thereby improving the uniformity of the conductive performance. Additionally, an overall improvement in conductive performance was observed.

Furthermore, by processing the fiber sheet-like structure in the form of skeins, it has become extremely easy to stuff the fiber sheet-like structure into bags and baths. Furthermore, the fiber sheet-like structure is free from bending, twisting, etc., and subsequent steps such as rewinding can be easily carried out.

(Example) The present invention will be further explained by examples.

Example 1 and Comparative Example 1 One-piece knitted fabric t'' knitting ratio using raw yarn of nylon 66 filament yarn 20d/3f (trade name: Leona, manufactured by Asahi Kasei Kogyo Co., Ltd.). 5, outer diameter (L2
) 24 cm, packing density 0.25P/l-11! Then, put the pieces into a nylon net knitted fabric, set it on the spindle of an Obermeyer dyeing machine, and add it at a bath ratio of 1:15. 2 t/l of Score Roll FC-250 (manufactured by Kao Atlas Co., Ltd.) was added to the solution and scouring was carried out at 60°C for XIO minutes. After scouring, the treatment solution was heated from room temperature to 110 °C at a temperature increase rate of 2 °C/min while circulating the treatment solution in a solution containing 5 g of SH group-containing silane coupling agent and 10 g of tartaric acid from inside to outside and from outside to inside. ’cK and then further heated to 110°C for 30
The treatment was carried out for minutes.

After that, in a bath containing 12-4 f/L of copper sulfate, 12.4 f/L of sodium thiosulfate, and 1.3 α of acetic acid, the flow direction of the treatment solution was changed to the inside →
The temperature was raised from room temperature to 45° C. over 20 minutes while circulating from the outside, from the outside to the inside, and the treatment was further carried out at 45° C. for 150 minutes. After the treatment, the knitted fabric was washed with water, dehydrated, and then taken out of the nylon bag and dried in a dryer. After drying, the copper sulfide-containing knitted fabric exhibits an overall glossy dull brown color.
Approximately 2.5% by weight of copper sulfide was uniformly adhered, and the surface electrical resistance of the resulting copper sulfide-containing knitted fabric was 0.5 #2 x 10
'Ω/It was almost uniform at the mouth level. Further, there was no deformation of the overall shape, and no folding or twisting of the silk fabric was observed.

In Comparative Example IVc, the same one-piece knitted fabric as in Example 1 was randomly packed into bags and stuffed into the basket of an Obermeyer dyeing machine, and the same treatment as in Example 1 was performed. The obtained sample had uneven glossy brown parts and dark brown parts, the copper sulfide adhesion was uneven, and the conductivity was 2 x 1.
A variation of 03 to l x 10'Ω/mouth was observed.

Example 2 The same one-piece knitted fabric as in Example 1 was made into a skein under the conditions shown in Table 1, packed in a bag, and dyed using an Obermeyer dyeing machine.
The same process was performed. The conductivity of the obtained sample is shown in Table 1.

Table 1 Table 1 Inner diameter (Ll) 5 cm, outer diameter (Ll) 2
4cm.

It is believed that the ridge-shaped one with a packing density of 0.2 S seconds has the best conductive performance.

(Effects of the Invention) In the method of the present invention, a long fiber sheet-like structure is made into a skein shape, and then a copper sulfide forming treatment is performed, whereby a conductive layer containing copper sulfide is uniformly formed, and the processability is improved. It is possible to produce a conductive fiber sheet-like structure with excellent conductivity and uniform conductivity.

[Brief explanation of the drawing]

FIGS. 1(A) and 1(B) are perspective views showing an example of a long fiber sheet-like structure in the form of combs.
...Inner diameter, L2...Outer diameter Patent applicant Asahi Kasei Industries, Ltd. Figure 1 (A) (B)

Claims (1)

[Claims] A conductive processing method characterized by forming a long fiber sheet-like structure into a comb shape and then subjecting it to copper sulfide forming treatment to form a conductive layer containing copper sulfide on the fiber surface.