WO1994010371A1

WO1994010371A1 - Floc for electrostatic hair transplantation

Info

Publication number: WO1994010371A1
Application number: PCT/JP1993/001481
Authority: WO
Inventors: Ikuo Mizoguchi; Mamoru Ito
Original assignee: Achilles Corporation
Priority date: 1992-10-23
Filing date: 1993-10-15
Publication date: 1994-05-11
Also published as: EP0667413A4; KR950704564A; CN1111170A; DE69319738D1; EP0667413B1; EP0667413A1; TW253920B; DE69319738T2

Abstract

A floc for electrostatic hair transplantation wherein the entire surface (inclusive of the front and rear end faces) of a short fiber is covered substantially or completely (not more than 3 % of non-coated portions) with an electrically conductive polymer layer (preferred thickness: 0.01 to 0.1 νm on an average), a production method thereof, and an electrostatic hair transplantation product using the former. A preferred polymer layer comprises a polymer or a copolymer using pyrrole, N-methylpyrrole, aniline or thiophene as a monomer. Chargeability and separability of this floc are not affected by surrounding moisture and satisfactory flying force can be stably provided during an electrostatic hair transplantation process. Accordingly, the floc can be utilized repeatedly for electrostatic hair transplantation in a dry environment under any hair transplantation systems, and post-conditioning, etc. that has conventionally been necessary, can be eliminated. The resulting hair transplantation product has a uniform density of transplanted hairs and is free from entanglement of fibers.

Description

Description Technical Field for Electrostatic Flocking Block

The present invention relates to a floc for use in electrostatic flocking, and more particularly, it does not require moisture adjustment in the process of electrostatic flocking, so it is repeatedly used in a process of electrostatic flocking in a constantly dry environment. And a flock for electrostatic flocking.

Further, the present invention relates to a method for producing such flocks, and an electrostatic flocking product in which the flocks (which have intrinsic conductivity) are planted on the surface. Background art

In general, electrostatic flocking means that a short cut floc is caused to fly by electrostatic attraction in an electric field formed by applying a high voltage, and is planted on a substrate to which an adhesive has been applied in advance. This technology refers to various types of natural, regenerated or synthetic staple fibers cut to a length of about 0.5 to about 5 weeks.

However, simply cutting the fiber to such a length does not provide sufficient charge even in a high-voltage electric field, and therefore does not generate flying power. In addition, the fibers are easily entangled with each other, and the separability is poor. Here, so-called electrodeposition treatment is generally applied to cut fibers in order to improve the chargeability, the separability and the like and improve the flying power.

In the conventional electrodeposition process, the cut short fibers are treated with tannin, tartar, etc., to retain the water of the tannin compound formed on the fiber surface. A method of maintaining surface electrical conductivity by using a surface active agent, soda silicate, colloidal silica, etc. to the cut short fibers, and using the water of crystallization to make the surface conductive. There is a way to keep. The former method is mainly used in Europe, while the latter method is used in Japan.

In general, the electric leakage resistance value of the fiber surface during electrostatic flocking

Suitable as 0 ⁵ to 1 0 ⁸ QZcm those forces electrostatic flocking flock that are within the scope of, and is sufficient flying force.

However, even if such electrodeposition treatment is performed, it is not guaranteed that the above-described resistance value condition is always satisfied at the time of electrostatic flocking. Adjust to exactly 25%

(After-conditioning), it was common practice to set the surface electric leakage resistance within the above range and then start flocking.

However, the function of the conventional electrodeposition agent is easily affected by moisture, and the conductivity of the surface of the coated fiber fluctuates considerably sharply due to changes in ambient humidity. (4) It requires disadvantageous after-conditioning, and it is difficult to carry out stable work throughout the year. In particular, in the case of hydrophobic fibers, for example, polyester fibers, aromatic polyamide fibers, etc., it was particularly difficult to control moisture, and the quality was not stable.

In addition, if flocks that were not used for flocking to the base material are collected, and they are removed, and then used for continuous electrostatic flocking, which is used again for electrostatic flocking, the first flocking should be performed. At this time, even if the flock is conditioned to the optimal condition of a humidity of about 80%, after the flocking of the unused floc after the electrostatic flocking, the floc is in a remarkably dry state. To reuse for the next flocking, adjust the water content of the floc again There was a disadvantage that it was necessary.

In addition, in the case of continuous electrostatic flocking, as the flocks are reused several times and the electrostatic flocking is repeated, the hook used has a high and low moisture content and is mixed, causing unevenness. As a result, there is a problem that a non-uniform electrostatic flocking may occur over time.

Recently, an electrostatic flocking machine equipped with a humidity control device has also been developed. However, the moisture content of the raw material flocks and the humidity of the surrounding environment may fluctuate for some reason, and the equipment cannot cope with such fluctuations satisfactorily. However, there is a disadvantage that it is not always easy to adjust the flock to the optimal range. For example, if the flock is over-dried, its flying power will be greatly reduced.On the other hand, if the flock becomes unnecessarily wet, the flock will become entangled, sticky, and sometimes a dumpling. May occur, and the separability decreases significantly.

All of the above inconveniences and inconveniences are caused by the conventional electrodeposition treatment agent, which does not exhibit its function at all in the condition of absolute drying or in a state close to it, and fully demonstrates its function only in a certain range of humidified conditions. It comes from performance.

Conventional electrodeposition agents not only cause or cause such inconveniences and defects, but also have low color fastness in the case of tannins, and flocking in the case of sodium silicate and the like. In addition to the hardened texture of the fibers, they have the disadvantages of weakening the adhesive strength of the adhesive and promoting fiber aging. Further, in the latter case, there is a problem that a so-called white powder made of silicate powder or the like is generated during the electrostatic flocking process. White powder may be harmful to human health due to absorption by respiration. For example, it can be removed only under severe conditions such as -5% sodium hydroxide aqueous solution at 60 ° C for 30 minutes.

As a result of intensive studies, the present inventor has found that the entire surface including the end face of the floc fiber is now substantially or completely covered with a single layer of a conductive polymer such as polypyrrol, preferably the conductive polymer. By setting the average thickness of the layer to 0.01 to 0.1 / im, the charge and separability of the floc are always kept good without being substantially affected by the surrounding moisture, and therefore, the static state can be improved. It has been found that a satisfactory flying force can be obtained by electro-flocking, and a hook for electrostatic flocking that can perform continuous electrostatic flocking smoothly and stably in a dry environment can be obtained. Disclosure of the invention

One object of the present invention is to provide an electrostatic flocking floc that can stably perform electrostatic flocking in a dry environment and can be repeatedly used for electrostatic flocking. It is in.

An object of the present invention is to make continuous electrostatic flocking in such a dry environment possible, thereby making it unnecessary to adjust the water content of flocs during the conventional electrostatic flocking process. It is also to provide flocks for electric flocking.

Accordingly, the present invention eliminates the need for such water content adjustment, and thereby eliminates the necessity of installing a humidity control device in the electrostatic flocking machine or making the water content adjustment process of the raw material floc as a pretreatment unnecessary. It is intended to provide flocking for flocking.

Another object of the present invention is to provide a method of manufacturing a flocking for electrostatic flocking, which can reliably and easily manufacture a strong flocking for electrostatic flocking. It is in.

Further, another object of the present invention is to provide an electrostatic flocking product which is planted using such a conductive floc, in particular, the floc is uniformly and stably flocculated without entanglement and finally has a high conductivity. An object of the present invention is to provide an electrostatic flocking product having a property.

The present invention relates to an electrostatic flocking floc characterized in that all surfaces including short fiber end faces are substantially or completely covered with a conductive polymer layer. Preferably, the proportion of the portion of the flock surface not covered by one layer of conductive polymer to the total surface is not more than 3%. Accordingly, the floc according to the present invention is preferably tuned by the coating of the conductive polymer layer such that the surface electrical leakage resistance is in the range of 10 ⁵ to 10 ⁸ QZcni.

The staple fibers comprise natural, semi-synthetic or synthetic fibers, and preferably have an aspect ratio of the fibers in the range of 1:30 to 1: 100. The short fibers may be dyed.

In a preferred embodiment, the conductive polymer layer is formed by polymerizing one or two or more monomers selected from the group consisting of pyrrole, N-methylpyrrol, aniline, thiophene and thiophene-13-sulfonic acid. A particularly preferred conductive polymer layer is a polymer layer obtained by polymerizing pyrrole as a monomer.

The thickness of the conductive polymer layer is preferably or required to be in the range of 0.1 μπι to 0.1 μπι on average. A more preferred thickness is approximately 0.011 11 to 0.03) Ltm on average when the short fibers are permeable fibers, and on average when the short fibers are non-permeable fibers. It is about 0.02 m to 0.05 μπι. In addition, the present invention relates to a polymerization reaction of a monomer in a treatment solution containing short fibers (or long fibers), using a chemical oxidizing polymerizing agent as a catalyst, and optionally adding a dopant and / or a surface tension reduction. The coated conductive polymer is coated on the surface of the fibers in the treatment liquid, and in the case of long fibers, thereafter, the coated long fibers are cut into short fibers. The present invention relates to a method for manufacturing flocks for electrostatic flocking.

Further, the present invention uses the above-mentioned floc as a raw material, for example, according to an up-type electrostatic flocking method, a down-type electrostatic flocking method, an up-down type electrostatic flocking method or a side type electrostatic flocking method, or a fluidized tank type static flocking method. The present invention relates to an electrostatic flocking product manufactured by using an electro flocking machine. BRIEF DESCRIPTION OF THE FIGURES

Fig. 1 shows a photomicrograph of a conventional flocking floc for electrostatic flocking in which the electrodeposition treatment using sodium silicate was applied to a polyester fiber, using an electron microscope to enlarge the tip of the floc. The length of the white line in the lower right part of the photograph is 50 / zm.

Fig. 2 shows an electron microscopy of the flocking for electrostatic flocking according to the present invention, in which the entire surface including the end face of the polyester fiber (fineness: 1.5 denier) is completely covered with a single layer of polymer. A micrograph of the tip of the block magnified using this is shown. The length of the white line in the lower right part of the photograph represents 20 μηι.

FIG. 3 shows a micrograph of an enlarged tip of the original yarn of the polyester fiber of FIG. 2 (with no pyrrole polymer layer formed on its surface) using an electron microscope. The length of the white line in the lower right part of the photograph is 20. BEST MODE FOR CARRYING OUT THE INVENTION

Floc according to the invention, do not substantially by circumferential surface and the front-rear both end faces in the longitudinal direction of the fibers conductive polymer layer is completely covered, thus this coating, the electric leakage resistance value of the surface 1 0 ⁵ to so that the can be adjusted to be within the scope of 1 0 ⁸ Ω / cm.

Preferably, the ratio of the portion of the floc surface not covered by the conductive polymer layer to the entire surface is not more than 3%.

The type of fiber may be any of natural, regenerated (semi-synthetic) or synthetic fiber. Preferred fibers include aromatic polyamide fiber (trade names Kevlar, Nomex, Conex, etc.) and other polyamide fibers.

(6-nylon, 6,6-nylon, 4,6-nylon, etc.), Regula-polyester fiber, basic dyeable dyeable polyester fiber, acrylic fiber, vinylon fiber, regenerated cellulose fiber (rayon), wool fiber , Cotton fibers, hemp fibers, and polyethylene, polypropylene and other multi-spun fibers. The fiber may be dyed, and a so-called original fiber colored by mixing a pigment or the like at the spinning stage can be used.

The raw fibers of the electrostatic flocking floc are as follows: denier number: about 1 to 65 d, fiber length: 0.3 to 6.0 mm, and aspect ratio: 1: 30 to 1: 1 The above-mentioned fibers having a property of 100 are preferred. If the fiber has an aspect ratio exceeding 1: 100, uniform electrostatic flocking may not be achieved. The larger the fiber diameter, the higher the aspect ratio fiber can be used.However, if the fiber diameter is small, it is necessary to select and use a fiber with a smaller value. is there. ― In general, it is said that a fiber having a fiber length 0.3 times the denier number (瞧) is most suitable as a raw material fiber for electrostatic flocking.

The conductive polymer layer may be, for example, a polymer or a copolymer layer formed by polymerizing pyrrole, N-methylvirol, aniline, thiophene, thiophene-13-sulfonic acid, or a derivative thereof as a monomer. Any polymer may be used as long as it is a polymer layer that imparts the above-described conductivity.

Monomers used to form this conductive polymer layer include, for example, aniline, o-chloroaniline, m-chloroaniline, P-chloroaniline, o-methoxyaniline, m-methoxyaniline, P-methaniline. Aniline derivatives such as xianiline, o-ethoxyaniline, m-ethoxyaniline, p-ethoxyaniline, o-methylaniline, m-methylaniline, p-methylaniline; thiophene, and 3-methylthiophene, 3-methoxythiophene, etc. Thiophene derivatives of pyrrole; 3,5-substituted pyrroles such as 3,5-dimethylpyrrole; 3,4-substituted pyrroles such as 4-methylpyrroyl-3-methylpyruvate; N-methylbilol Of 3-substituted pyrroles such as N-substituted pyrrol, 3-methylpyrrol, Various substituted pyrroles can be mentioned.

A preferred conductive polymer layer is a polymer or copolymer layer formed by polymerizing pyrrole, N-methylpyrrole, aniline, thiophene, thiophene-13-sulfonic acid as a monomer. However, in view of the adhesive strength to the fiber, the degree of conductivity, the quality of workability, and the like, a particularly preferred conductive polymer layer is a polymer layer obtained by polymerizing pyrrole as a monomer. The thickness of the conductive polymer layer is basically arbitrary as long as it exhibits the above-mentioned conductivity and appropriate separation properties. If the average thickness of the conductive polymer layer is less than 0.01 urn, the conductive polymer layer must be formed to a uniform thickness due to the surface roughness of the fiber itself. As a result, in many cases, the conductivity required for obtaining satisfactory flying power cannot be imparted to the floc. On the other hand, if the average thickness of the conductive polymer layer exceeds 0.1 m, even if the required conductivity is secured, the frictional robustness of the conductive polymer layer is reduced, or the conductive polymer layer is As the thickness increases, the resistance becomes lower than the required resistance value and the conductivity increases.Therefore, at the time of electrostatic flocking, sparks are generated due to the approach or contact between the flocks, and as a result, in flocking products, Shading unevenness may appear clearly on the flocking density on the surface.

Therefore, it is more preferable or required that the thickness of the conductive polymer layer be in the range of 0.1Ομηι or 0.1 / Ltm on average. Since it is an ultra-thin film, the original texture and flexibility of the fiber are not greatly impaired by the presence of the conductive polymer layer. For example, when used in a user strip of an automobile window glass, since the fiber hardens very little, the inherent elasticity of the fiber is maintained and a stable sliding resistance value can be obtained.

In order to form a conductive polymer layer having a thickness within the above range on the surface of the fiber, the monomer used for producing the polymer has a somewhat different force depending on the type of the fiber. It must be added at a rate of 0.3 to about 1.0%. For example, when pyrrol, a kind of monomer, is added at a weight ratio of 0.75% to polyester fiber (specific gravity 1, 34) of 3 denier and 0.8 mm in length, the average thickness is about 0.7%. 044 (Calculated value) A m-layer of a pyropolymer is formed on the peripheral surface and both end surfaces of the fiber.

However, even when an equal amount of monomer is used, the thickness of the conductive polymer layer formed on the fiber surface varies depending on the fiber surface shape (roughness), porosity, fiber composition, and the like. For example, in the case of non-permeable fibers such as polyester fiber and aramide fiber, a conductive polymer layer having an average thickness substantially equal to the average thickness calculated from the amount of the added monomer is formed. ,

In the case of permeable fibers such as 6-nylon fibers and vinylon fibers, a conductive polymer layer having an average thickness somewhat smaller than the average thickness calculated from the amount of the added monomer is formed. In addition, the thickness of the conductive polymer layer also varies depending on the conditions for dispersing the fibers in the treatment solution described below.

The preferred thickness of the conductive polymer layer is generally about 0.01 to 0.03 for permeable fibers such as nylon fiber, vinylon fiber, and cellulose fiber, and polyester fiber, aramide fiber, and acrylic. In the case of non-permeable fibers such as fibers, it is generally 0.02 to 0.05 m

In general, when a polymerization reaction of a monomer is carried out in a treatment solution containing fibers using an oxidizing polymerization agent as a catalyst, the conductive polymer layer formed on the fibers in the treatment solution is formed on the conductive polymer layer as described above. It is formed by bonding and covering its surface.

Therefore, clearly, the present invention relates to a method in which a polymerization reaction of a monomer is carried out in a treatment solution containing short fibers (which may be dyed) using a chemical oxidizing polymerization agent as a catalyst, The present invention relates to a method for producing a floc for electrostatic flocking, which comprises coating a formed conductive polymer on the surface of a fiber in a treatment liquid by proceeding with Z or a surface tension reducing agent. You.

The addition of the monomer and the chemical oxidizing polymer to the treatment liquid may be performed by a procedure of adding both together, or by a procedure of adding the monomer first and then adding the chemical oxidizing polymer. . Further, the chemical oxidation polymer of the catalyst may be added all at once, may be added in several portions, or may be added continuously in small amounts.

Preferably, the polymerization reaction of the monomer proceeds as slowly as possible. The temperature condition is preferably a low temperature, 2 to 35, more preferably 2 to 25 ° C.

If the polymerization rate is extremely high, the reaction in the aqueous phase proceeds rapidly (in an instant), making it difficult for the polymer to adhere to the surface of the fiber and forming free polymer particles in the water tank.

The polymerization reaction is performed while stirring or circulating the treatment liquid. As the polymerization of the monomers progresses and the solubility decreases over time, the resulting polymer will selectively precipitate or adhere, especially on the fiber surface. For this reason, this reaction is extremely quantitative.

In order to generate satisfactory flying power in any of the flocked electrostatic flocking methods described below, the entire surface including the end face of the short fiber is substantially covered with a conductive polymer layer. It is desirable to coat substantially all surfaces of the fiber with a conductive polymer to a uniform thickness.

From this point of view, the floc of the present invention forms a conductive polymer layer on the fiber surface by polymerizing a monomer for electrodeposition treatment while stirring or circulating it in a slurry-type processing solution containing fibers. Most preferred to do. In this case, the fibers are processed in a slurry-type processing solution for a weight of 1. It is particularly preferred that the physical solution is present in a weight ratio of 8 to 15. The stirring speed is not particularly limited, but since it is necessary to prevent floc sedimentation, for example, the stirring speed in the case of using polyester fibers needs to be higher than in the case of using polyamide fibers.

The floc of the present invention can use a long fiber, perform a so-called electrodeposition treatment of the long fiber, and then cut the treated long fiber into a predetermined size to be a short fiber.

For example, if a circular tow is cut to make a straight line and then cut to a predetermined size to form a floc, no conductive polymer layer will be formed on the cut surface, that is, the end surface of the floc. Is about 0.3 to 1.2% of the total surface area of the flock, and does not substantially affect the flightability of the flock. Polyamide fiber, vinylon fiber, etc., have monomer diffused into the fiber. Therefore, even if the towel is subjected to electrodeposition treatment and then cut, the obtained floc is In some cases, the entire surface of the part or the end face may be made conductive. In this case, the ratio of the non-conductive area to the entire surface of the floc is further reduced.

When the electrodeposition treatment is performed in the state of the torsion, the bundled state of the fibers is a close-packed state, so that it is difficult to uniformly coat the surface of the fiber with a single layer of the conductive polymer. If a floc is used, a loss will occur. Therefore, in consideration of the cost of the electrodeposition process, it is also preferable to cut long fibers and then perform the electrodeposition process in a slurry-type processing solution.

Therefore, the present invention also relates to a method for polymerizing a monomer, which is carried out in a treatment solution containing long fibers (which may be dyed) by using a chemical oxidizing polymerization agent as a catalyst and adding a dopant and / or With surface tension reducing agent A method for producing flocks for electrostatic flocking, which comprises proceeding together to coat the generated conductive polymer on the surface of the fibers in the treatment liquid, and then cutting the coated long fibers into short fibers. About.

In both the production method using short fibers as a raw material and the production method using long fibers as a raw material, preferred monomers include pyrrole, N-methylpyrrol, aniline, thiophene and thiophene-3-sulfonic acid. Monomers selected from are applied singly or in combination of two or more. Pyrrole is particularly preferred.

As the chemical oxidative polymerization agent for the catalyst, any substance which promotes the polymerization of the above monomers can be used in general, and examples thereof include persulfates such as persulfuric acid, ammonium persulfate, persulfuric acid rim, and sodium persulfate; Alternatively, ferric chloride, ferric perchlorate, ferric sulfate, ferric nitrate, ferric periodate, ferric citrate, ferric P-toluenesulfonate, etc. Iron salts; or permanganates such as permanganic acid and permanganate potassium chromium; Chromic acids such as chromium trioxide; or halogens such as chlorine, bromine and iodine; hydrogen peroxide and benzoyl peroxide Peroxides; metal chlorides such as copper chloride; Particularly, a water-soluble ferric salt is preferable.

The chemical oxidative polymerization agent is used alone or in an appropriate combination of the above-mentioned compounds, usually in a ratio of about 1 to about 3 mol per mol of monomer.

Further, in the polymerization of the above monomer, if necessary, a dopant can be used in combination to increase the conductivity of the fiber. The dopant is suitably used under conditions of PH 1-5, more preferably PH 1-3. Suitable dopants include, for example, P-toluene sulfonic acid, benzene sulfonic acid, benzenesulfonic acid of monochrome mouth, dichlorobenzenes Sulfonic acid, trichlorobenzene sulfonic acid, naphthalene sulfonic acid, diphenyl sulfonic acid, naphthalene trisulfonic acid, sulfosalicylic acid and other aromatic sulfonic acids; or perchloric acid, hydrochloric acid, sulfuric acid, nitric acid, trifluoroacetic acid Sulfonic acid and the like. In particular, aromatic sulfonic acid or its metal salt is preferred.

Further, the treatment liquid may further include a surface tension reducing agent in order to uniformly form the conductive polymer film on the fiber surface.

Examples of surface tension reducing agents include surfactants, organic solvents, and defoaming agents such as silicones, acetylene glycols, and fluorines. Surfactants improve the wettability of the fiber surface, and alcohols are additionally mixed with water to improve the wettability of the fiber surface by mixing with water.

Examples of the above surfactant include anionic type such as sodium alkyl sulfate, sodium alkyl benzene sulfonate, sodium alkyl sulfosuccinate, sodium polyoxyalkylene sulfonate, sodium alkyl naphthylene sulfonate and the like. Surfactants; and nonionic surfactants such as polyethylene glycol, polypropylene glycol, block copolymer, polyethylene glycol alkyl ether, and polyethylene glycol alkyl phenyl ether.

Examples of the above organic solvents include alcohols such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, n-butanol, isobutanol, and isoamyl alcohol, dimethylformamide, tetrahydrofuran, and dioxane. Acetonyltril, cyclohexanone, methylethylketone, acetone and the like. The addition amount of the surface tension reducing agent is generally very small or small.For example, in the case of a surfactant, an amount in the range of about 0.01 to about 2% based on the total weight of the processing solution is sufficient. In the case of alcohols, the range of about 0.1 to about 5.0% is sufficient for the total weight of the processing solution.

In addition, the polymerization of the above-mentioned monomer advantageously proceeds in a state of PH 1 to 4, and a desired conductive polymer can be efficiently obtained within that range.

After the completion of the polymerization reaction, the fibers are washed with water.At that time, the entanglement of the flocks is prevented as necessary, and the fibers are transported by a screw or the like in the supply path from the storage tank in the electrostatic flocking machine. A softening agent or a leveling agent such as stearic acid amide may be added in a small amount in order to improve the quality.

In addition, when using raw fibers such as polyester as raw material fibers, before forming the conductive polymer layer, a surfactant or an oily substance that oozes out from the inside of the fibers into the treatment solution for the polymerization reaction is used in advance. It is preferable to wash and remove them.

Further, the electrodeposition treatment (formation of the conductive polymer layer) of the present invention may be performed after dyeing or may be performed before dyeing. However, alkaline dyeing of polyester fibers causes de-doping and lowers conductivity, so when alkaline dyeing is performed, it is necessary to perform the dyeing before the above electrodeposition treatment. It is preferable to perform acid washing just in case. Staining after electrodeposition treatment must be performed under acidic conditions.

By using the original fibers or by dyeing the fibers, the color of the dye and the color of the conductive polymer are combined, so that a variety of colors of flocs can be obtained.

Dyes used vary depending on the fiber, but acid dyes and black And metal complex salt dyes such as dye complexes, disperse dyes, cationic dyes, and reactive dyes.

In particular, for polyester fibers, dyeing with a disperse dye is a force that requires reduction cleaning. Since reduction cleaning promotes de-doping of the conductive polymer, it is necessary to make the fibers conductive after dyeing. No reduction cleaning is required for other polyamide fibers and acrylic fibers.

After the above electrodeposition treatment, the fibers are dried, but in the case of flocks, the fibers are dried in a slurry state or a state where they are dehydrated by centrifugation in order to minimize the entanglement between flocks. Most preferably, a fluidized-bed drying method is used, in which the flocs are dried by contact with a stream of hot air in a fluidized-bed. In the case of this drying method, in order to operate more conveniently, the conditions of a temperature of about 120 to about 180 ° C and a tank residence time of 0.1 to 5 seconds may be adopted. When dried under these conditions, the floc of the present invention having a water content of about 1 to 5% can be easily obtained. On the other hand, in the case of a drying method in which flocks packed in bags through dehydration by centrifugation are put into a rotating drum and heated by circulating hot air, not only a long drying time is required, but also flocks are required. It is not preferable because it has a drawback that the processing (separability) is deteriorated.

The floc of the present invention is manufactured through the above-described processes. Its moisture content is usually about 1 to 5%, which is about the official moisture content, and is significantly lower than the moisture content of the conventional floc, 20 to 25% (the value after flocking after conditioning). Therefore, the weight is reduced, which is convenient for transportation and handling. Since the conductive polymer layer is substantially unaffected by moisture, the moisture content of about 1 to 5% is maintained almost unchanged even when the surrounding outside air is in a high humidity range. Is almost absolutely dry It is kept dry. Therefore, the dyeing fastness of the floc is improved, and the transportation cost is further reduced.

In order to facilitate understanding of the flock of the present invention, typical characteristics of the flock are shown below.

Single yarn fineness D: about 1 to about 65 denier

Fiber length; 0.3 or 6 recitation

Aspect ratio; approx. 1:30 to approx. 1; 100

Surface electric leakage resistance value: Set to 10 ⁵ to 10 ⁸ QZcm.

(Based on the Japan Flocke Industry Association measurement method.)

Moisture content; about 1 to about 5%

Thickness of conductive polymer layer: about 0.01 1 11 about 0.1 lm Raw material of conductive polymer

Addition amount of monomer M; 0.3 to 1.0% (weight ratio to fiber) of conductive polymer layer coating

Conductivity of pure water used at the time: 5 μS or less

D / M. Ratio; 2.5 to 250

In determining the amount of raw material monomer to be added (weight ratio to fiber), since the raw fiber has a large aspect ratio, the area of both end faces is at most 1 to 3% of the total surface area. Very small and can be ignored enough. Therefore, when a raw fiber having a fineness of 1 to 65 denier and a fiber length of 0.3 to 6 mm, which is generally used, is preferably used, the amount obtained according to the following relational expression (1) should be used. Is led.

D / M = 2.5x… (i)

(In the formula, X represents a range of 1 to 100.)

Therefore, for 3 denier raw fiber, the DZM ratio is about 2 to 4, 15 For denier raw fibers, the DZM ratio is about 10 to 20; and for 65 denier raw fibers, the DZM ratio is about 150 to 250, respectively. It should be noted that the above relational expression is particularly suitable for polyester fiber, nylon fiber, acrylic fiber and the like.

The floc of the present invention can be used for the same electrostatic flocking as in the past, and thus various kinds of flocking products can be manufactured. The method of electrostatic flocking is not particularly limited, and the up-type electrostatic flocking method (place the hook on the lower electrode and the flocking object on the upper electrode, and apply the voltage between the upper and lower electrodes) The flocking method in which the flocks fly upward by performing the method. The down-type electrostatic flocking method. (A state in which the material to be planted is provided on the lower electrode and a grid or linear upper electrode is used, and voltage is applied between the upper and lower electrodes. The flocking method in which the flocks fly down by dropping the flocs through the grid of the upper electrode, or the side-type electrostatic flocking method (prepared by connecting the object to be implanted to the electrode beside the electric field) The flocking method is to drop the floc into the electric field from the hopper under the application of a voltage so that the floc flies first downward and then laterally from the middle. Fluid tank type electrostatic flocking machine (flocking machine of the type that uses a fluidized tank with a structure in which a perforated plate is stretched in the tank and vibration is applied as a flock supply tank. There are an up-down type and a side type. ) May be used to manufacture electrostatic flocking such as automobile interior parts from the floc of the present invention.

Therefore, the present invention further provides an up-type electrostatic flocking method, a down-type electrostatic flocking method, an up-down type electrostatic flocking method, or a side-type electrostatic flocking method using the above-mentioned flocking for electrostatic flocking as a raw material. Or by using a fluidized-bed electrostatic flocking machine to electrostatically flocking the surface of the substrate to be flocking. After the completion of the electrostatic flocking, an appropriate doping treatment, for example, acid concentration

0.01 to: L mol / L, preferably at a temperature of 10 to 9 (By immersion treatment in TC solution, it is possible to impart dopants to flocks of flocks to further improve conductivity. It is possible.

In the present invention, since the surface of the floc is substantially covered with the conductive polymer layer, the surface electric leakage resistance value can be easily adjusted to a range suitable for electrostatic flocking. By virtue of the powerful antistatic function, this floc obtained in an almost absolutely dry state can be used for electrostatic flocking.

In particular, the floc itself is less susceptible to moisture due to the nature of the coating layer, which is a conductive polymer, and its good antistatic function is almost constant irrespective of the ambient humidity (wet, dry). Will be kept. Therefore, a satisfactory flying force can be obtained with any of the up-type and down-type electrostatic flocking without performing after-conditioning as in the related art.

Further, in particular, in the present invention, in the case of a floc in which not only the peripheral surface of the floc but also all the surfaces including the front and rear end surfaces are coated with the conductive polymer layer, the floc is located on the surface of the base material on which the floc is to be implanted. The planting in a right angle direction can be made more reliable, thus reducing the incidence of product defects and enabling the production of higher quality flocked products. This is because during the electrostatic flocking process, when a high voltage is applied, ten charges are generated on one end face of the floc and one charge is generated on the other end face, so that polarization appears more clearly. This is probably due to the fact that the flocks are implanted in a direction perpendicular to the surface of the substrate to be implanted.

Furthermore, in the present invention, the conductive polymer which is hardly affected by moisture is used. Due to the nature of the layers, the separation of the flock is not adversely affected by ambient moisture and moisture levels. Therefore, there are no inconveniences such as sticking of the flock surface, tangling of the flock, generation of dumplings due to entanglement, and generation of sparks due to contact between the flocks. In short, according to the present invention, the charging and separating properties of the floc can be stably maintained within the intended range and conditions without being substantially affected by the surrounding moisture. As a result, a satisfactory flying force can be always obtained, and therefore, stable electrostatic flocking can be performed in any of the flocking methods. In particular, according to the present invention, since the floc is almost in an absolutely dry state, the floc can be repeatedly used for the electrostatic flocking in a dry environment, so that the continuous electrostatic flocking can be performed smoothly and stably. Can be performed.

Therefore, since continuous electrostatic flocking in a dry environment has become possible, the present invention eliminates the need for water conditioning (after-conditioning) of flocs during the conventional electrostatic flocking process. For example, it is not necessary to install a humidity control device in an electrostatic flocking machine, or to perform a step of adjusting the moisture content of a raw material hook as a pretreatment.

In addition, if the floc of the present invention is used, the flocks are electrostatically planted in a state of being orderly and standing upright on the surface of the base material, and the distribution thereof is even and uniform in density, and defects such as entanglement and entanglement also occur. No, high quality electrostatic flocking is provided. Example

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

Example 1

Cut 6,6-nylon fiber (fineness: 3 denier, fiber length: 0.5 mm) was dyed with a metal complex dye Kayakalan Black (manufactured by Nippon Kayaku Co., Ltd.) at 95 ° C. for 60 minutes, and then thoroughly washed with water. Next, a pyrrole monomer was used in an amount of 0.63% by weight based on the weight of the fiber, and this was stirred in water together with the dyed 6,6-nylon fiber while using a catalyst of ammonium persulfate as a catalyst. The polymerization reaction was continued for 240 minutes. Thereafter, the 6,6-nylon fibers were thoroughly washed with water and then dried until the water content became 2.5%.

The surface electric leakage resistance of the obtained floc was measured to be 3X

It was 10 ⁶ ΩΖαη.

Using this floc, three types of electrostatic flocking (applied voltage: 50-80 kV) were performed: up-type, down-type, and fluidized-bed type. The force was high enough, and the flocking on 2/1 weft-woven fabric (polyester Z cotton = 65Z35, 0.15 mm thick) coated with adhesive was uniform and good.

Example 2

The cut acrylic fiber (fineness: 1.3 denier, fiber length: 0.4 concealed) is thoroughly washed with water in advance to remove surfactants, oils, etc., then put into water, and then as monomer Add 0.35% (by weight to fiber) of N-methylpyrrole and 0.3% (by weight of fiber) of pyrrole, and stir with ferric chloride as a catalyst for 200 minutes at 5 ° C. During the period, the polymerization reaction was connected. After that, the acrylic fiber was thoroughly washed with water and then dried until the water content became 2.5%.

The surface electric leakage resistance of the obtained floc was measured to be 7 X

10 ⁷ ΩΖαη.

In addition, electrostatic flocking was performed under the same conditions as in Example 1 using this floc. As a result, as in Example 1, good flying properties were obtained for all the flocking methods and satisfactory results were obtained.

Example 3

The cut 6-nylon fiber (fineness: 1.5 denier, fiber length: 0.5 concealed) is turned 90 ° by a milling type acidic dye and a dyeing black dye (Nippon Kayaku Co., Ltd.). The cells were stained under the conditions of Cx for 60 minutes, and then sufficiently washed with water. Next, as a monomer, aniline P-toluenesulfonate was used in an amount of 1.0% in terms of fiber weight ratio, and this was mixed with dyed 6-nylon fiber in water using potassium persulfate as a catalyst. While stirring together, the polymerization reaction was continued at 5 ° C for an appropriate time. Thereafter, the 6-nylon fiber was thoroughly washed with water, and then dried until the water content became 3.5%.

The surface electric leakage resistance value of the obtained floc was measured and found to be IX 10 ^β QZcm.

In addition, when the flocking was used to carry out electrostatic flocking under the same conditions as in Example 1, good flying properties were obtained for all the flocking methods as in Example 1, and satisfactory results were obtained. .

Example 4

The cut para-aromatic polyamide fiber (fineness: 2.0 denier, fiber length: 0.5 dia.) And pyrrole monomer in an amount of 0.5% by weight relative to the fiber are put in water and stirred. The polymerization reaction was continued at 3 ° C. for 240 minutes using ammonium persulfate as a catalyst. Thereafter, the above fibers were sufficiently washed with water, and then dried until the water content became 0%.

The obtained floc was dark green, and its surface electric leakage resistance was measured to be 3 × 10 ⁷ QZcm. In addition, when the flocking was used to carry out electrostatic flocking under the same conditions as in Example 1, good flying properties were obtained for all the flocking methods as in Example 1, and satisfactory results were obtained. .

Comparative Example 1

Polyethylene terephthalate fiber (fineness: 15 denier, fiber length: 2. lmm) is dyed with a disperse dye, Yaron Polyester Black (manufactured by Nippon Kayaku Co., Ltd.) at 130 ° C for 60 minutes. Reduced washing was performed with 6 CTCX for 20 minutes using a mixture of mouth sulfate and sodium hydroxide. Next, electrodeposition treatment was performed using sodium silicate according to a conventional method to produce flocks for flocking.

Using a fluidized tank type electrostatic flocking machine, the moisture content of the floc was adjusted to 0.5%, 3.0% and 18%, and the flocking was performed on the same substrate as in Example 1 (applied voltage: 60kV). In the case of moisture content of 0.5% and 3.0%, insufficient flying power was obtained and uniform flocking could not be achieved, and in the case of moisture content of 18%, some flocking could be achieved, but flocking Continuous hair transplantation, which involves repeated collection and reuse, was not possible.

The results of the electrostatic flocking test for each of the above examples are summarized in Table 1 below.

Hook Moisture ratio Electrostatic flocking method Applied voltage o.l Example 1 2.5% up method 60 kV

No.2 Example 1 2 5% down method 60 kV

No.3 Example 1 2 5% Fluidized tank method 60 kV

No.4 Example 2 2 5% up method 60 kV

No.5 Example 2 2 5% down method 60 kV

No.6 Example 2 25% Fluidized tank method 60 kV

No.7 Example 3 3 5% up method 60 kV

No.8 Example 3 3.5% down method 60 kV

No.9 Example 3 3.5% Fluidized tank method 60 kV

No.10 Example 4.0 4.0% up method 60 kV

No.11 Example 4 1.0% down method 60 kV

No.12 Example 4 1.0% fluidized bed method 60 kV © No.13 Comparative example 1 0.5% Fluidized tank method 60 kV x No.14 Comparative example 1 3.0% Fluidized tank method 60 kV x No .15 Comparative Example 1 18% fluidized-bed method 60 kV 〇 Note) ◎ indicates that sufficient flying force was obtained for flocs, and that electrostatic flocking was uniform and very good.

〇 indicates that the required flying force was obtained for flocks, and electrostatic flocking was good, but continuous electrostatic flocking was not possible.

An X indicates that the required flying power for the flock was not obtained and the electrostatic flocking was defective. Example 5 '

—Polyester fiber cut to fixed length (fineness: 3.0 denier, fiber length: 0.8 dia.) 1 kg and 8.3 g of pyrolmonomer (0.83%, relative to fiber weight) Was poured into water, and the polymerization reaction was continued for 3 hours while stirring at a liquid temperature of 3 ° C. using 50.2 g of ferric chloride as a catalyst. Thereafter, the polyester fiber was sufficiently washed with water, and then dried by 16 (TC) according to a fluidized-bed drying method.

The obtained floc had a surface electric leak resistance of 4.0 × 10 ^ε QZcm and a water content of 1.5%.

In addition, electrostatic flocking (applied voltage: 50 to 8 OkV) was performed on the flocks using an up-type flocking machine, a down-type flocking device, a flow tank type side flocking device, and a fluidized tank type up flocking device. As a result, all of the flocking methods showed sufficiently high flight performance without special after-conditioning, and high-quality electrostatic flocking products were obtained.

FIG. 1 to FIG. 3 of the drawings show micrographs of the tip of a floc or the like enlarged by using an electron microscope in connection with the above-described examples and the like. Here, the length of the white line in the lower right part of the photo is 50

(Figure 1) or 20μπι (Figure 2, Figure 3).

Fig. 1 shows a conventional flocking flock for electrostatic flocking in which electrodeposition treatment using sodium silicate was applied to polyester fibers. Fig. 2 shows polyester fibers (denier: 1.5 denier). FIG. 3 shows the flocking for electrostatic flocking of the present invention corresponding to Example 5 in which all surfaces are completely covered with a layer of a pyropolymer; and FIG. 3 shows the flocking of FIG. The raw yarn of the polyester fiber, which is the raw material for (there is no pyrrole polymer layer formed on the surface). Example 6

According to the method of Example 1 in JP-A-3-163709, a 6,6-nain continuous fiber (denier: 3 denier) is wound around a bobbin, which is then wound on 20 liters of water and pyrrol 13. 4 g and ferric chloride 64.9 g were placed in a bath together with a treatment solution at 18 ° C, and the treatment solution was repeatedly passed through the fiber gap into the bobbin to conduct the conductivity, and the surface was treated. A long fiber having an electric leakage resistance of 1.0 × 10 ⁶ ΩΖαη was obtained.

Thereafter, the conductive 6,6-nylon filaments were cut to a length of 0.5, and then were subjected to electrostatic flocking using the same method and conditions as in Example 1. As for the flocking of the product, some fibers were not planted in the direction perpendicular to the surface of the base material, but a sufficient flying force was obtained, and continuous electrostatic flocking was possible. Industrial applicability

The floc of the present invention can be used for electrostatic flocking in general, and can be used for building interior materials (wallpaper, curtains, power supplies, mats, etc.), footwear (sandals, thongs, etc.), daily miscellaneous goods (decoration). Covers, decorative cords, jewelry boxes, stationery, etc.), automatic car accessories (dashboards, sun visors, leather strips, floppy yarns for car seats, etc.), cooling and heating equipment (kotatsu, foot warmers, etc.), clothing (hats, hats, etc.) It is suitable for the manufacture of various types of electrostatic flocking products in a wide range of applications, such as jackets, gloves, etc., and electronic equipment (brush rolls, etc.).

Claims

The scope of the claims

1. An electrostatic flocking floc characterized in that all surfaces including short fiber end surfaces are substantially or completely covered with a conductive polymer layer.

1. The floc according to claim 1, wherein a ratio of a portion of the floc surface that is not covered by the conductive polymer layer to the entire surface is 3% or less.

3. Flock according to claim 1 or claim 2, wherein the short fibers are dyed.

4. The method according to any one of claims 1 to 3, wherein the thickness of the conductive polymer layer is in a range of 0.1 to 0.1 / m on average. Flock.

5. The conductive polymer layer is a polymer layer formed by polymerizing one or two or more monomers selected from the group consisting of pyrrole, N-methylbilol, aniline, thiophene and thiophene-13-sulfonic acid. 5. The flock according to claim 1, wherein the flock is a single-layer copolymer.

6. The floc according to claim 5, wherein the conductive polymer layer is a polymer layer obtained by polymerizing pyrrole as a monomer.

7. The thickness of the conductive polymer layer is, on average, about 0.0 Olm to 0.03 m when the short fibers are permeable fibers, and when the short fibers are non-permeable fibers. The floc according to any one of claims 1 to 4, wherein the average is approximately 0.02 "m to 0.05 m. δ. The short fiber is made of natural fiber, semi-synthetic fiber or synthetic fiber, and the aspect ratio of the fiber is in the range of 1:30 to 1: 100. The flock according to any one of claims 1 to 7.

9. surface leakage resistance value of the flock, 1 0 ⁵ QZcm to 1 0 ⁸ floc as claimed in any one of claims 1 to 8, characterized in that in the range of Omegazetaarufaita.

10. The polymerization reaction of the monomer proceeds in the treatment solution containing the short fibers using the chemical oxidation polymerization agent as a catalyst together with the dopant and / or the surface tension lowering agent that are added as required, and the formed conductive polymer is formed. 3. The method for producing a floc for electrostatic flocking according to claim 1, comprising coating the surface of the fiber in the treatment liquid.

11. The polymerization reaction of the monomer proceeds in a treatment solution containing long fibers using a chemical oxidizing polymerizing agent as a catalyst together with a dopant and / or a surface tension lowering agent added as required. 3. The method for producing a floc for electrostatic flocking according to claim 1, comprising coating the surface of the fiber in the treatment liquid with the surface of the fiber and then cutting the coated long fiber into a short fiber. .

12. The method according to claim 10, wherein one or more monomers selected from the group consisting of pyrrole, dimethylpyrrolyl, aniline, thiophene and thiophene-13-sulfonic acid are used as monomers. Or the production method according to claim 11.

13. The production method according to claim 12, wherein pyrrole is used as the monomer.

14. Claim that the short or long fibers used are dyed fibers The production method according to any one of claims 10 to 13.

15. The method according to any one of claims 10 to 14, wherein the chemical oxidative polymerization agent used as a catalyst is a water-soluble ferric salt.

16. The method according to any one of claims 10 to 15, further comprising washing the coated fiber with a softener or a leveling agent after the polymerization reaction.

17. An electrostatic flocking floc manufactured by the method according to any one of claims 10 to 16.

18. Using the flocking for electrostatic flocking described in any one of claims 1 to 9 and claim 17 as a raw material, an up-type electrostatic flocking, a down-type electrostatic flocking, an up-down static An electrostatic flocking product made by electrostatic flocking on the surface of a substrate to be flocking, according to the electro flocking method or the side-type electrostatic flocking method, or using a fluidized-bed electrostatic flocking machine.

Amended claims

[Accepted by the International Bureau on March 15, 1994 (15.03.94); Claims 1-18 originally referred to were replaced by new claims 1-22. (Page 3)]

2. The floc according to claim 1, wherein a ratio of a portion of the floc surface not covered with the conductive polymer layer to the entire surface is 3% or less.

3. The conductive polymer layer is formed by polymerizing one or more monomers selected from the group consisting of pyrrole, N-methylpyrroyl, aniline, thiophene and thiophene-13-sulfonic acid. The floc according to claim 1, wherein the floc is a polymer layer or a copolymer layer.

4. The conductive polymer layer is formed by polymerizing one or more monomers selected from the group consisting of pyrrole, N-methylpyrrol, aniline, thiophene and thiophene-13-sulfonic acid. 3. The hook according to claim 2, wherein the hook is a single layer of polymer or single layer of Kobolima.

5. The floc according to claim 4, wherein the conductive polymer layer is a polymer layer obtained by polymerizing pyrrole as a monomer.

6. The method according to claim 1, wherein the conductive polymer layer has an average thickness in the range of 0.01 m to 0.1 Hm. Flock.

7. The floc according to claim 5, wherein the thickness of the conductive polymer layer is in the range of 0.1Ομηι to 0.1 μm on average.

8. The thickness of the conductive polymer layer is approximately 0.0 Olim to 0.03 ^ m on average when the short fibers are permeable fibers, and the short fibers are non-permeable fibers. 6. The floc described in any one of claims 1 to 5, wherein the average is approximately 0.02 μη to 0.05 / xm.

9. The staple fiber is made of natural fiber, semi-synthetic fiber or synthetic fiber, and the aspect ratio of the fiber is in the range of 1:30 to 1: 100. The floc according to any one of claims 5 and 7.

10. surface leakage resistance value of the flock, 10 ^s Ω / cm to claimed in any one of claims 1 to 5 and claim 7, characterized in that in the range of 10 ⁸ Q / cm Flock.

11. surface leakage resistance value of the flock, 10 ^s ΩΖαη to floc of claim 9, characterized in that in the range of 10 ⁸ QZcm.

12. The floc according to any one of claims 1 to 5, wherein the short fibers are dyed.

13. The hook according to claim 9, wherein the staple fibers are dyed.

14. The floc of claim 11, wherein the short fibers are dyed.

15. The polymerization reaction of the monomer proceeds in a treatment solution containing short fibers using a chemical oxidation polymerizing agent as a catalyst together with a dopant and Z or a surface tension-lowering agent added as required to form a conductive polymer. 3. The method for producing a floc for electrostatic flocking according to claim 1 or 2, comprising coating one of the fibers with a surface of a fiber in the treatment liquid.

16. One or two kinds of monomers selected from the group consisting of pyrrole, N-methylpyrrol, aniline, thiophene and thiophene-13-sulfonic acid: Claim: wherein LL monomer is used. 15. The production method according to 15.

17. The method according to claim 16, wherein pyrrole is used as the monomer.

18. The production method according to any one of claims 15 to 17, wherein the staple fibers used are dyed fibers.

19. The method according to any one of claims 15 to 17, wherein the chemical oxidative polymerization agent used as a catalyst is a water-soluble ferric salt.

20. The method according to any one of claims 15 to 17, further comprising washing the coated fiber with a softening agent or a leveling agent after the polymerization reaction.

21. An electrostatic flocking floc manufactured according to the method according to any one of claims 15 to 20.

22. The flock for electrostatic flocking described in any one of claims 1 to 14 and claim 21 is used as a raw material, and the flocking is performed on the surface of the base material where the flocking is to be performed. Electrostatic flocking products made.