JPH05220439A - Electrostatically flocked product - Google Patents

Abstract

PURPOSE:To obtain a highly conductive electrostatically flocked product by uniformly and stably flocking a surface to be flocked without generating light and shade irregularity and a flaw such as entanglement by electrostatically flocking the surface to be flocked of a base material with conductive fibers subjected to dope removing treatment and subsequently applying doping treatment to the flocked fibers. CONSTITUTION:An electrostatically flocked product is produced by subjecting conductive fibers composed of natural or synthetic fibers coated with a conductive polymer to dope removing treatment before electrostatic flocking and subsequently electrostatically flocking the surface to be flocked of a base material with the treated fibers to apply doping treatment to the flocked fibers. The dope removing treatment means treatment such that the conductivity of fibers is lowered by removing the dopant contained in conductive fibers obtained by oxidative polymerization. The doping treatment means treatment such that the conductivity of fibers is enhanced by again applying a dopant to the electrostatic fibers of a flocked product after electrostatic flocking.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flocked product in which conductive fibers are electrostatically flocked on a surface thereof. INDUSTRIAL APPLICABILITY The electrostatic flocked product according to the present invention can be widely used in various applications such as carpets, flocky yarns, brush rolls, clothing, shoes, furniture, electronic devices and vehicles.

[0002]

2. Description of the Related Art Conventionally, this type of electrostatic flocking product is generally
Short fibers (pile) having a required diameter and cut into a predetermined length are passed through a sieve in a hair-implanting chamber, and then sprinkled on the space between the substrate to be hair-implanted and the electrode plate. On the other hand, it is usually produced by applying a high voltage of tens of thousands of volts between the base material and the electrodes to implant hair on the surface of the base material.

For example, Japanese Patent Publication No. 3-74176 discloses an electrostatic flocking technique for metal piles (copper and aluminum piles). Among them, in order to improve the dispersibility of the metal pile, it is proposed to perform a dipping treatment in advance in a solution of sodium silicate, colloidal silica or the like.

[0004]

By the way, in the technique of electrostatic flocking using a natural or synthetic (organic) conductive fiber, it is necessary that the conductivity of the conductive fiber is within a certain range. , When conductive fibers have better conductivity than that level, sparks are generated due to the approach or contact of fibers during electrostatic flocking, which causes the density of flocking on the surface of flocked products to vary. There is a problem that unevenness of the hair may be clearly shown, and that the fibers are easily entangled, entangled, and disturbed on the flocked surface.

As a method for solving this problem, a method of suppressing the generation of sparks by giving conductivity only to a necessary portion of the fiber can be considered, but it is necessary to mask the unnecessary portion. Is extremely complicated,
Such a method cannot be adopted immediately.

Further, even if the immersion treatment disclosed in Japanese Patent Publication No. 3-74176 is carried out, the above problems cannot be solved.

The object of the present invention is to solve the above-mentioned problems,
An object of the present invention is to provide an electrostatically-implanted article in which natural or synthetic conductive fibers are uniformly and evenly and stably entangled.

[0008] Another object of the present invention is to finally provide an electrostatic flocking product having high conductivity.

As a result of earnest research, the present inventor conducted a natural treatment by performing a procedure of de-doping treatment before flocking, then electrostatic flocking, and then dope treatment, preferably by performing these treatments under specific conditions. Alternatively, synthetic conductive fibers can be electrostatically flocked on the surface of the base material evenly with high and low flock density and without entanglement of flocked fibers, resulting in a highly conductive flocked product. It was found that the present invention has been completed.

[0010]

SUMMARY OF THE INVENTION That is, the present invention provides a method of dedoping conductive fibers, in which a conductive polymer is combined with natural or synthetic fibers, prior to electrostatic flocking and then flocking the fibers to a substrate. The present invention relates to an electrostatic flocked article, which is produced by electrostatically flocking a surface to be surfaced and then by doping the fiber that has been flocked.

The outline of the present invention will be described below by dividing it into conductive fibers, dedoping treatment, electrostatic flocking treatment, dope treatment and the like.

Conductive Fiber The conductive fiber used in the present invention is a natural or synthetic fiber in which a conductive polymer is bonded to the surface of the fiber or the whole fiber,
A certain level of conductivity, preferably from about 10 ^{4 to} about 10
^It has a conductivity of ⁸ Ω / cm.

The conductive polymer may be any polymer which imparts the above-mentioned conductivity, such as a polymer or a copolymer produced by polymerizing pyrrole, aniline, thiophene or a derivative thereof as a monomer.

The conductive fiber to which the conductive polymer is bound is
Usually, it is produced by a method in which a monomer is polymerized in a solvent containing fibers by using an oxidant as a catalyst, and the resulting conductive polymer is bonded to the inside and the surface of the fiber in the solvent to integrate them. It The polymerization is more preferably carried out while stirring or circulating the reaction mixture.

The monomer and the oxidizing agent may be added to the solvent to be used by adding them together, or by adding the monomer first and then adding the oxidizing agent.

Examples of the monomer capable of forming a conductive polymer include aniline, o-chloroaniline, m-chloroaniline, p-chloroaniline and o.
Aniline derivatives such as -methoxyaniline, m-methoxyaniline, p-methoxyaniline, o-ethoxyaniline, m-ethoxyaniline, p-ethoxyaniline, o-methylianiline, m-methylaniline, p-methylaniline; thiophene , And thiophene derivatives such as 3-methylthiophene and 3-methoxythiophene; pyrrole and 3,5-such as 3,5-dimethylpyrrole
Substituted pyrrole, 3,4-substituted pyrrole such as methyl 4-methylpyrrole-3-carboxylate, N-substituted pyrrole such as N-methylpyrrole, 3-substituted pyrrole such as 3-methylpyrrole and 3-octylpyrrole Various substituted pyrroles may be mentioned.

Basically, the monomer is required to be soluble in the solvent used before the polymerization and insoluble in the solvent after the polymerization. However, from this point of view, thiophene 3-sulfonic acid and the like are water-soluble even in the state of the polymer, and the binding to the fiber becomes insufficient, which is not preferable, but is insoluble due to copolymerization with other monomers. Can be used by adopting a method of obtaining a copolymer of

The above-mentioned monomers are usually added in an amount necessary so that the amount of the conductive polymer produced as a result of the polymerization is about 0.6 to about 10% based on the fiber. Further, the polymerization of the above-mentioned monomers conveniently proceeds in the state of pH 1 to 4, and the desired conductive polymer can be efficiently obtained within this range.

The solvent used for the production of the conductive polymer is mainly composed of water and additionally mixed with an organic solvent having a property of being miscible with water in order to improve the wettability of the fiber surface. used. The amount of the organic solvent added is usually in the range of about 0.1 to about 30% based on the weight of the whole solvent.

Examples of the organic solvent include alcohols such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, n-butanol, isobutanol, isoamyl alcohol, etc .; or tetrahydrofuran, methyl ethyl ketone, cyclohexanone, dioxane, dimethylformamide, Examples include acetamide, N-methylpyrrolidone and methyl isobutyl ketone.

Further, a surfactant may be further added for the purpose of improving the wettability of the fiber surface. The amount of the surfactant added is preferably about 0.
An amount in the range of 01 to about 2%.

Examples of the surfactant include anionic surfactants such as sodium alkylsulfate, sodium alkylbenzenesulfonate, sodium alkylsulfosuccinate, sodium polyoxyalkylenesulfonate and sodium alkylnaphthalenesulfonate; or polyethylene glycol / Nonionic surfactants such as polypropylene glycol block copolymers, polyethylene glycol alkyl ethers, polyethylene glycol alkyl phenyl ethers and the like can be mentioned.

As the oxidizing agent for the catalyst, any agent that promotes the polymerization of the above-mentioned monomers can be used, and examples thereof include ferric chloride, ferric perchlorate, ferric sulfate and ferric nitrate. Iron, ferric periodate, ferric citrate, p
-A ferric salt such as ferric toluenesulfonate; or
Peroxodisulfates such as peroxodisulfate, ammonium peroxodisulfate, potassium peroxodisulfate and sodium peroxodisulfate; or permanganate,
Permanganates such as potassium permanganate; Chromates such as chromium trioxide; or halogens such as chlorine, bromine, iodine; peroxides such as hydrogen peroxide and benzoyl peroxide; metal chlorides such as copper chloride Is mentioned.

The oxidizer may be used alone or in any suitable combination thereof, in the amounts mentioned above.
Generally, it will be in a ratio of about 1: 1 to about 1: 3 by weight of the monomer.

The natural or synthetic fibers used in the present invention include polyamide fibers such as 6-nylon and 6,6-nylon, regular polyester fibers, basic dye dyeable polyester fibers, acrylic fibers and aramid fibers. (Aromatic polyimide fibers), vinylon fibers, regenerated cellulose fibers, wool fibers, cotton fibers, hemp fibers, and polyethylene, polypropylene and other composite spun fibers.

These fibers may be dyed or undyed, and may be corona treated or the like. The fiber (pile) is used in a form having a required diameter and a length in a certain range. Short fibers are particularly preferred.

-De-doping treatment-The de-doping treatment is a treatment for reducing the conductivity of the conductive fiber obtained by the above-mentioned oxidative polymerization by removing the dopant contained therein. As an effective dedoping method, there are a method of treating with a reducing agent and a method of performing alkali treatment.

The former dedoping method is particularly effective for polyester fibers dyed with a disperse dye, while the latter dedoping method is advantageous for polyamide fibers such as nylon.

The dedoping treatment using a reducing agent is carried out by treating the conductive fiber with an aqueous solution of alkaline sodium hydrosulfite, sodium thiosulfate or the like at room temperature to 90 ° C. for 5 to 60 minutes, or by using an alkali. The de-doping process by the conductive fiber is sodium hydroxide,
It is carried out by a method of treating with potassium hydroxide or an aqueous solution of ammonia.

After this treatment, in order to smooth the electrostatic flocking of the dedoped fiber, it is treated with a siliceous compound such as sodium silicate or colloidal silica before the electrostatic flocking,
It is more preferable to facilitate loosening from the lump state. Since the siliceous compound dissolves only in strong alkali, it does not have a serious adverse effect on the subsequent dope treatment.

-Electrostatic Flocking- In the present invention, electrostatic flocking is basically performed by the same method as the conventional one. That is, while a fiber (pile) having a required diameter and length is passed through a sieve in a hair-implanting chamber and sprayed in the space between the base material and the electrode plate, a high voltage of tens of thousands of volts is usually applied. It is carried out by a method of applying a load between the material and the electrode and implanting hair on the surface of the base material.

-Doping Treatment-Doping treatment is a treatment for increasing the conductivity of the fibers by re-applying the dopant to the conductive fibers of the flocked product after electrostatic flocking, but generally, it is static. It is carried out by a method of immersing the electro-implanted hair product in a solution of a doping agent for a required time.

Suitable doping agents include, for example, p
-Toluenesulfonic acid, benzenesulfonic acid, monochlorobenzenesulfonic acid, dichlorobenzenesulfonic acid,
Trichlorobenzenesulfonic acid, naphthalenesulfonic acid, isopropylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenedisulfonic acid, naphthalenetrisulfonic acid, sulfosalicylic acid and other aromatic sulfonic acids; or perchloric acid, hydrochloric acid, sulfuric acid, nitric acid,
Trifluorosulfonic acid and the like are also used.

These doping agents preferably have a pH of 1
~ 5, more preferably used under conditions of pH 1-3.

The solution of the doping agent usually has an acid concentration of 0.
01 to 1 mol / L is used, and the doping treatment is preferably carried out by a method of immersing the electrostatic hair transplant in a doping agent solution at a temperature of 10 to 90 ° C. for 5 to 240 minutes.

Further, in this dope treatment, an appropriate amount of the above-mentioned surfactant or organic solvent (alcohols, etc.) applicable to the production of the conductive polymer is added to the doping agent solution so that the individual flocked fibers are added. It is more preferable to facilitate the penetration and penetration of the doping agent.

[0037]

In the present invention, the conductivity of the conductive fibers is remarkably lowered by dedoping the conductive fibers before the electrostatic flocking. Therefore, in the subsequent step of electrostatic flocking, spark reduction hardly occurs even if the fibers are in contact with or close to each other due to the reduction in conductivity. Moreover, the conductivity of the fibers of the hair transplant is restored to the initial level or a level close to it by performing the subsequent dope treatment.

Therefore, by preventing the occurrence of sparks,
The flocked product has a uniform density with respect to the denseness of the flock, and is free from defects such as fiber entanglement, disorder, and entanglement.

Further, by recovering the conductivity by the dope treatment, even if the conductivity is moderate at the beginning, the conductivity is not extremely deteriorated in the final product, so that the desired high conductivity is obtained. A flocked product having conductivity is obtained.

[0040]

EXAMPLES The present invention will be described in detail below with reference to examples.

Example 1 100 g of 1-denier 6-nylon fiber cut to a length of 0.5 mm was treated with a metal complex salt dye Kayakalan Red BL (Nippon Kayaku Co., Ltd.) 1.1% owf according to a conventional method. After dyeing and washing thoroughly with water, an aqueous solution 3 containing 12% of isopropyl alcohol, 0.03 mol of pyrrole monomer and 0.069 mol of ferric chloride at a liquid temperature of 12 ° C.
It was added to liter with stirring, and the polymerization reaction was continued for 4 hours. After that, the fibers were thoroughly washed with water, and it was confirmed that the detection of ferric chloride was not found in the filtrate.

The obtained conductive fiber was treated with sodium hydroxide 3
The dope treatment was performed by immersing the solution in g / l at a temperature of 60 to 70 ° C. for 20 minutes. Then, the fiber was repeatedly washed thoroughly with water, and then dried at 80 to 90 ° C. to obtain a fiber having reduced conductivity.

Then, 150 g / m ² of an acrylic resin emulsion (4000 cps / 25 ° C., manufactured by Boncoat Dainippon Ink and Chemicals Co., Ltd.) was applied on the polyester film as the base material, which was then sent to the hair-implanting chamber, and the above fibers were applied. While spraying between the polyester film and the electrode board,
The fibers were electrostatically flocked on the film surface by applying a voltage of 30,000 V between them. During this process, no sparks were found.

Thereafter, the flocked film is 120 to 1
The acrylic resin on the film surface was sufficiently cured with an epoxy curing agent by heating at 30 ° C for 15 minutes, and then the electrostatic flocked film was heated to 60 ° C in a 0.5 mol / L p-toluenesulfonic acid aqueous solution of 180 mol. The dope treatment was performed by immersing for a minute.

The electrostatic flocked product thus obtained is 1 to 2 ×.
It had a high conductivity of 10 ⁴ Ω / cm, and no frictional electrification by cotton occurred.

Comparative Example Except for the immersion treatment in a solution of sodium hydroxide 3 g / l,
A film-shaped electrostatic flocked article was produced by the same procedure and method as in Example 1.

However, spark sparks were generated in the process of electrostatic flocking, and the flocked product obtained had unevenness in density due to the denseness of flocking, and the presence of entanglement, entanglement, etc. on the flocked surface was not good. It was a product.

Example 2 100 g of a 1.3 denier basic dye dyeable acrylic fiber (Puron Asahi Kasei Corporation) cut to a length of 1.0 mm was dyed with Cathilon Blue (Hodogaya Chemical Co., Ltd.). Dyed in a conventional manner with 1.0% owf, and thoroughly washed with water, and then, this was heated to a liquid temperature containing 5% isopropyl alcohol, 0.045 mol of pyrrole monomer and 0.105 mol of ferric chloride. The mixture was dispersed in 3 liters of a 15 ° C. aqueous solution with stirring, and the polymerization reaction was continued for 4 hours. After that, the fibers were thoroughly washed with water, and it was confirmed that the detection of ferric chloride was not found in the filtrate.

The obtained conductive fiber was treated with sodium hydroxide 5
The dope treatment was performed by immersing the solution in g / l at a temperature of 60 to 70 ° C. for 20 minutes. Thereafter, the fibers were repeatedly washed thoroughly with water, and then dried at 80 to 90 ° C. to obtain latent conductive fibers.

Then, 150 g / m ² of an acrylic resin emulsion (4000 cps / 25 ° C., manufactured by Boncoat Dainippon Ink and Chemicals, Inc.) was coated on the polyester film as the base material, and then this was sent to the flocking chamber, and the above-mentioned fibers were used. While spraying between the polyester film and the electrode board,
The fibers were electrostatically flocked on the film surface by applying a voltage of 30,000 V between them. During this process, no sparks were found.

Thereafter, the flocked film is 120 to 1
The acrylic resin on the film surface was sufficiently cured with an epoxy curing agent by heating at 30 ° C for 15 minutes, and then the electrostatic flocked film was heated to 60 ° C in a 0.5 mol / L p-toluenesulfonic acid aqueous solution of 180 mol. The dope treatment was performed by immersing for a minute.

Thus, the obtained electrostatic flocked product had a desired high conductivity.

[0053]

As can be seen from the above description, according to the present invention, the natural or synthetic conductive fibers can be uniformly distributed according to the density of the flock without unevenness in density and stably without defects such as entanglement and entanglement. , Flocked electrostatic flocking products are provided,
Then, the effect of finally producing a highly conductive electrostatic flocked article is obtained.

Claims (1)

[Claims] 1. A conductive fiber in which a conductive polymer bonds with a natural or synthetic fiber is dedoped prior to electrostatic flocking,
An electrostatically-implanted article, which is produced by electrostatically-implanting the fibers on the surface of the base material to be implanted, and then by doping the impregnated fibers.