JPH08309267A - Flock for electrostatic flocking - Google Patents

Abstract

PURPOSE: To obtain a flock excellent in conductivity, flying property, fluidity and classifying property by coating the surface of a fiber with at least one kind of superfine particle selected from a group consisting of the superfine particles of polypyrrole, acidic colloidal silica and acidic silica. CONSTITUTION: This flock for electrostatic flocking used in various flocked articles such as building inetrior material, footgear and automobile parts is formed by oxidation-polymerizing a pyrrole monomer in a processing soln. contg. a fiber and forming a polypyrrole coating on the fiber surface. Namely, at least one kind of superfine particle selected from a group consisting of acidic colloidal silica, acidic silica superfine particle and alumina sol is deposited on the fiber surface along with the polypyrrole to form a coating. In this case, the sp.gr. of the superfine particle is appropriately controlled to 2 to 3 and the diameter to 0.01 to 0.02μm, and the thickness of the superfine particle layer is preferably adjusted to 0.01 to 0.1μm.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flock for use in electrostatic flocking, and more particularly to a flock for electrostatic flocking which has a satisfactory flight property and has improved fluidity and flame retardancy. Regarding flock.

The flock of the present invention can be generally used for electrostatic flocking, and is used for interior materials for construction (wallpaper, curtains, carpets, mats, etc.), footwear (sandals, thongs, etc.), daily sundries (decorative covers, decorations). Cords, jewelry boxes, stationery, etc.), automobile supplies (dashboards, sun visors, weather strips, car seat flocky yarns, etc.), air conditioning equipment (kotatsu, foot warmers, etc.), furniture, upholstery materials, clothing (hats) , Jackets, gloves, etc.) and electronic devices (brush rolls, etc.), and are suitable for the production of various electrostatic flocking products in a wide range of applications.

[0003]

2. Description of the Related Art Heretofore, as a flock for electrostatic flocking, a flock in which sodium silicate or the like is attached to the surface of a fiber has been used. On the other hand, the present inventor has recently developed, as an electrostatic flocking floc, a novel floc in which all surfaces of short fibers are substantially or completely covered with a conductive polymer layer such as polypyrrole. . This is Japanese Patent Application 5-2
No. 80474 is also disclosed.

The developed flock for electrostatic flocking has a good flying property at all times because it is kept in a state of almost absolute dryness by covering the entire surface with the conductive polymer layer. Any of the flocking methods such as the above is characterized in that it can be stably used repeatedly in the electrostatic flocking process in a dry environment. Therefore, by using such flocs, there is an advantage that the conventional after-conditioning is unnecessary and, for example, the water content adjustment of the raw material flocs as a pretreatment becomes unnecessary.

[0005]

However, the above-mentioned electrostatic flocking flock is not completely satisfactory in fluidity and classification property, and these points should be improved. From the viewpoint of economy, it is more preferable that the amount of the conductive polymer coated on the flock surface is smaller. However, as the coating amount of the conductive polymer is reduced, the floc loses its rigidity and has a high flexibility comparable to that of the fiber of the base material. If the flocs are too flexible, they tend to flow in a lump in the electrostatic flocking process, which tends to cause the flock density to fluctuate more or less and is more consistent than aggregates of flock of various lengths. It becomes difficult to classify the flocs with the length of, and the efficiency is reduced, which leads to deterioration of the productivity of the electrostatic flocking product. Therefore, it has been required to improve the surface characteristics of the floc so that good fluidity and classifying property can be obtained even when the amount of the conductive polymer coated is small.

When electrostatic flocking is performed using the above-mentioned flocs, the amount required for electrostatic flocking is exceeded, mainly in the case of the down method, especially when the distance between the electrode and the surface to be flocked is narrow. When a large amount of flocs are supplied at once in a high-voltage electric field, the flocs are present in the electric field in an excessively dense manner, and the contact between them causes a current to flow between the electrode and the surface to be planted, causing frequent sparking. However, there is a problem in that the flock itself is heated and softened, and in some cases, the softened flock and the flock are fused and connected in a series in an instant.
Such a situation occurs particularly seriously in a flock in which the base fiber is a low-melting fiber such as 6-nylon or 6,6-nylon, and in such a flock, the fiber of the base material itself ignites and a fire occurs. There was a risk of causing an accident.
Therefore, it has been demanded to improve the surface characteristics of the electrostatic flocking flock so that the ignition phenomenon does not occur even if such excessive supply is performed.

The present invention has been made in view of the above circumstances, and its main purpose is to have high flight properties, to be able to repeat stable electrostatic flocking in a dry environment, and to have fluidity and classification property. It is further improved to prevent the generation of inhomogeneous flocking products and also improve the efficiency of the electrostatic flocking process,
Another object of the present invention is to provide a flock for electrostatic flocking, which has improved flame retardancy, does not generate sparks in the process of electrostatic flocking, and has no risk of ignition.

[0008]

As a result of earnest research, the present inventor has found that a pyrrole monomer is added to a treatment liquid containing fibers in the presence of ultrafine particles such as acidic colloidal silica, ultrafine particles of acidic silica and alumina sol. The flocks for electrostatic flocking obtained by polymerizing with a chemical oxidant as a catalyst in the above are not only satisfactory flight force in electrostatic flocking but also improved flowability and classification property, and are homogeneous and productive. The present invention has been completed by finding that good flocking is ensured, flame retardancy is improved, and sparks and ignition do not occur even under conditions of excessive supply.

That is, the present invention is characterized in that the surface of the fiber is coated with polypyrrole and at least one kind of ultrafine particles selected from the group consisting of acidic colloidal silica, acidic silica ultrafine particles and alumina sol. Flock for electrostatic flocking. Further, the present invention relates to the above-mentioned electrostatic flocking flock, wherein the ultrafine particles are ultrafine particles having a specific gravity of 2 to 3 and a particle diameter of 0.01 to 0.02 µm in a more preferred embodiment. Furthermore, the present invention, as a more practical aspect, the polymerization reaction of pyrrole, with the fibers, a treatment liquid containing at least one ultrafine particle selected from the group consisting of acidic colloidal silica, ultrafine particles of acidic silica and alumina sol. The above-mentioned electrostatic flocking flocs produced by coating the surface of the fibers in the treatment liquid with the produced polypyrrole by advancing with a chemical oxidant as a catalyst.

SUMMARY OF THE INVENTION The present invention is a process for producing a polypyrrole-coated electrostatic flocking floc (as previously disclosed by the present inventor), that is, by oxidatively polymerizing a pyrrole monomer in a treatment liquid containing fibers. The process of forming a polypyrrole coating on the surface of the fiber is performed by depositing at least one ultrafine particle selected from the group consisting of acidic colloidal silica, ultrafine particles of acidic silica and alumina sol on the surface of the fiber together with polypyrrole. To form those coatings. The acidic colloidal silica, the acidic silica ultrafine particles and the alumina sol have a bad influence on the polymerization of the pyrrole monomer even when they coexist in the treatment liquid (for example,
It is a substance that does not give a reaction inhibition) and does not impair the original properties (for example, flexibility) of the fiber itself coexisting during the polymerization. Therefore, the electrostatic flocking floc according to the present invention has an advantage that the coating of ultrafine particles such as acidic colloidal silica and the coating of polypyrrole on the fiber surface can be simultaneously advanced in the manufacturing process without any inconvenience. There is. That is, at present, it is believed that the novel flocs of the present invention do not suffer any significant technical disadvantage in their manufacture.
Not only that, the flocs according to the present invention can be produced by simultaneously coating ultrafine particles such as acidic colloidal silica and polypyrrole in one polymerization process (polymerization process of pyrrole). Therefore, this manufacturing method is also very advantageous in terms of floc manufacturing productivity.

The thickness of the ultrafine particle layer of acidic colloidal silica, ultrafine particles of acidic silica and / or alumina sol, and the thickness of the polypyrrole layer, which are coated on the surface of the fiber, are basically arbitrary. But about 0.0
A thickness of 1 μm to about 0.1 μm is suitable. If the thickness is less than 0.01 μm, it becomes difficult to form a polypyrrole layer or the like having a uniform thickness, and as a result, the necessary conductivity cannot be imparted in many cases.
When the thickness is more than m, the fastness to friction of the coating layer is lowered and it is also disadvantageous from the economical aspect. Since it is such an ultrathin film, the presence of the polypyrrole layer or the like does not significantly impair the original texture and flexibility of the fiber. For example, when used as a weather strip for automobile window glass, since the curing of the fiber is extremely small, the original elasticity of the fiber is maintained and a stable sliding resistance value is obtained.

The film thickness of the ultrafine particle layer made of acidic colloidal silica, ultrafine particles of acidic silica and / or alumina sol, and the film thickness of the polypyrrole layer generally vary depending on the polymerization conditions and the like. These coating amounts are adjusted so that the electric leakage resistance value is in the range of 10 ⁵ to 10 ⁸ Ω / cm. If necessary, in order to secure the above-mentioned level of conductivity, a suitable pretreatment may be applied to the fiber surface before coating with polypyrrole or the like.

The acidic colloidal silica used in the present invention is
Silicon dioxide (SiO ₂ ) having OH groups on the surface by hydration in a dispersion medium such as water or alcohol (especially methanol)
Is an acidic (preferably pH 2 to 4) colloidal suspension. Acidic colloidal silica has negative ions on the surface of the colloid, but it does not cause precipitation due to ferric ion, which is a chemical oxidant coexisting in the treatment liquid of the polymerization reaction, and thus may inhibit the polymerization reaction of the pyrrole monomer. There is no such thing. The acidic colloidal silica is more preferably a system made of colloidal silica having a particle size capable of forming a layer having the same thickness as that of polypyrrole on the surface of the fiber. Particularly preferably, the particle size is 0.01 to
It is an acidic colloidal silica in the range of 0.02 μm. For example, acidic colloidal silica having a pH of 2 to 4 and a solid content of about 20% is preferably used in the present invention. As specific commercial products thereof, for example, the trademark name Snowtex (snotex
wtex) colloidal silica products, especially product name MA-ST-
M (dispersion medium methanol), methanol silica sol (dispersion medium methanol), IPA-ST (dispersion medium isopropanol), ST-O (dispersion medium water) (all manufactured by Nissan Chemical Industries, Ltd.) can be mentioned.

The acidic silica ultrafine particles used in the present invention are silicon dioxide (Si 2) in the form of ultrafine particles having a silanol group.
O ₂ ) and is an acidic (preferably pH _{2 to} 4) powder. Similar to acidic colloidal silica, acidic silica ultrafine particles do not cause precipitation due to the ferric ion of the chemical oxidant coexisting in the treatment liquid of the polymerization reaction, so there is no fear of inhibiting the polymerization reaction of the pyrrole monomer. It is a thing.
As the acidic silica ultrafine particles, acidic silica having a particle size comparable to the particle size of the above acidic colloidal silica,
It is more preferable because a layer having a thickness similar to that of polypyrrole can be formed on the surface of the fiber. When the particle size is expressed by the surface area per unit weight, particularly preferable acidic silica ultrafine particles have a surface area of about 300 to 400 m ² / g. However, even if the acidic silica ultrafine particles have a true specific gravity of 2.5 to 2.6, the bulk specific gravity is much smaller than that, so that the acidic silica ultrafine particles having the above-described desired particle diameter are It is relatively difficult to accurately measure and use, and therefore, acidic silica ultrafine particles are acidic colloidal particles that are already in a form dispersed in a non-solvent in terms of accuracy of weighing and easy handling. Inferior to silica. In the present invention, ultrafine particles of acidic silica having a specific gravity of 2 to 3 and a particle diameter of 0.01 to 0.02 μm are very suitably used. Specific examples of commercially available products include Nipsil (manufactured by Nippon Silica Industry Co., Ltd.), Shilton (manufactured by Mizusawa Chemical Co., Ltd.), Hisil (manufactured by PPG Industries Co., Ltd.), Starsil (manufactured by Kajima Chemical Co., Ltd.),
Examples include acidic silica ultrafine particle products such as HGKT40 (manufactured by Wacker Chemical Co.).

The alumina sol used in the present invention is acidic (preferably pH _{2 to 4} ) of aluminum oxide (Al ₂ O ₃ ) having an OH group on the surface by hydration in a dispersion medium such as water or alcohol (particularly methanol). Is a colloidal suspension of. Alumina sol, like the acidic colloidal silica, does not cause precipitation due to the ferric ion of the chemical oxidant coexisting in the treatment liquid for the pyrrole polymerization reaction, so there is no risk of inhibiting the polymerization reaction of the pyrrole monomer. Is. The alumina sol is more preferably a system made of colloidal alumina having a particle size capable of forming a layer having a thickness similar to that of polypyrrole on the surface of the fiber. Particularly preferably, the particle size is 0.01 to 0.0
It is an alumina sol in the range of 2 μm. In the present invention, the specific gravity is 2 to 3 and the particle size is 0.01 to 0.02 μm.
Alumina sol in the range of is very suitably used.
Specific examples of commercially available products include trade names of alumina sol 100, 200, 520 (all manufactured by Nissan Chemical Industries, Ltd.).

The amount of acidic colloidal silica, ultrafine particles of acidic silica and / or ultrafine particles of alumina sol to be used should be appropriately changed depending on the type and properties of the fiber, but the preferred range is silica content. And a range in which the alumina content is converted to an amount of 0.5% by weight to 3.0% by weight based on the weight of the fiber. When the silica content and the alumina content of the ultrafine particles are less than 0.5% by weight,
The fluidity of flocs is not significantly improved. On the other hand, if the silica content and the alumina content exceed 3.0% by weight, the fluidity of the flocs cannot be further improved, and further, the electrical conductivity of the flocs falls below a desired level, which is preferable. Absent. When the silica content and the alumina content are set in the range of 0.5% by weight to 3.0% by weight, the fluidity and classification property of the flocs are satisfactorily improved, and the flame retardancy is also satisfactorily improved. It is more preferable because the phenomenon of spark generation and ignition does not occur under the conditions.

The polypyrrole in the present invention refers to a polymer obtained by polymerizing pyrrole as a monomer (at least as one component of the monomer), and in addition to a homopolymer of pyrrole, pyrrole and a 3,5-substituted pyrrole (3,3).
5-dimethylpyrrole, etc.), 3,4-substituted pyrrole (4
-Methylpyrrole-3-carboxylate, etc.), N-substituted pyrrole (N-methylpyrrole, etc.) or 3-substituted pyrrole (3-methylpyrrole, 3-octylpyrrole, etc.) was used as a monomer for polymerization. Copolymers are also included. Polypyrrole is a particularly preferable material from the viewpoints of adhesive strength with fibers, degree of conductivity, workability, and the like. The most preferred polypyrrole is a homopolymer obtained by polymerizing only pyrrole as a monomer.

The amount of the monomer such as pyrrole used for the fiber varies considerably depending on the type and diameter of the fiber. Generally, the pyrrole monomer is about 0.1 to about 3.0%, more preferably about 0.15 to about 1.0%, by weight of the fiber.
Is added to the treatment liquid at a rate of. For example, when the pyrrole monomer is added in a weight ratio of 0.75% to a polyester fiber (specific gravity 1.34) having a denier of 3 mm and a length of 0.8 mm, the average thickness is about 0.044 (calculated. A polypyrrole layer having a value of μm is formed on the peripheral surface and both end surfaces of the fiber.
The amount of pyrrole monomer used also varies significantly depending on the application of the electrostatically flocked product. In applications where it is sufficient to simply flock the flock of the present invention onto a substrate, the amount of pyrrole monomer used may be small, but sufficiently high conductivity is required for the purpose of removing static electricity. In applications, the amount of pyrrole monomer used is quite high.

However, even if the same amount of pyrrole monomer is used, the thickness of the polypyrrole layer formed on the fiber surface varies depending on the surface shape (roughness) of the fiber, porosity, fiber composition and the like. For example, in the case of a non-permeable fiber such as polyester fiber or aramid fiber, a conductive polypyrrole layer having an average thickness almost equal to the average thickness calculated from the amount of added monomer is formed. In the case of permeable fibers such as 6-nylon fiber and vinylon fiber, a conductive polypyrrole layer having an average thickness slightly smaller than the average thickness calculated from the amount of added monomer is formed. The thickness of the polypyrrole layer also varies depending on the dispersion conditions of the fibers in the treatment liquid described below and the like. A suitable polypyrrole layer thickness is generally 0.01 to 0.0 for permeable fibers such as nylon fibers, vinylon fibers, and cellulose fibers.
It is about 3 μm, and in the case of non-permeable fibers such as polyester fiber, aramid fiber and acrylic fiber, it is generally 0.
It is about 01 to 0.05 μm.

The type of fiber may be natural, regenerated (semi-synthetic) or synthetic fiber. As convenient fibers, aromatic polyamide fibers (trade name: Kevlar, Nomex, Conex, etc.) and other polyamides are used. Fiber (6-nylon, 6,6-nylon, 4,6-nylon, etc.), regular polyester fiber, basic dyeable dyeable polyester fiber, acrylic fiber, vinylon fiber, regenerated cellulose fiber (rayon), wool fiber, Cotton fiber,
Hemp fibers as well as polyethylene, polypropylene and other composite spun fibers and the like. Further, the fibers may be dyed, and so-called so-called fibrous fibers which are colored by mixing a pigment or the like at the spinning stage can be used.

The raw material fibers for the electrostatic flocking flock include denier number; about 1 to 65 d, fiber length; 0.3 to
6.0 mm, and aspect ratio; 1:30 to 1: 100
The above fibers having the properties of are preferable. If the fiber has an aspect ratio of more than 1: 100, uniform electrostatic flocking may not be performed in some cases. The larger the fiber diameter, the larger the aspect ratio fiber can be used, but if the fiber diameter is smaller, the smaller aspect ratio fiber must be selected and used. . Generally, a fiber having a fiber length of 0.3 times the denier number (mm) is said to be most suitable as a raw material fiber for electrostatic flocking.

Further, as described above, in the flocks for electrostatic flocking of the present invention, the polymerization reaction of the pyrrole monomer is caused by fibers (usually short fibers, which may be dyed), acidic colloidal silica and acidic. In a treatment liquid containing at least one kind of ultrafine particles selected from the group consisting of silica ultrafine particles and alumina sol, a chemical oxidant is used as a catalyst and is allowed to proceed with a dopant and / or a surface tension lowering agent optionally added. It is produced by coating the produced polypyrrole with ultrafine particles such as acidic colloidal silica on the surface of the fiber in the treatment liquid. By following the manufacturing method, the obtained floc is
The lengthwise circumferential surface and both front and rear end surfaces of the fiber are substantially covered with both materials of polypyrrole and acidic colloidal silica, acidic silica ultrafine particles and / or ultrafine particles of alumina sol. Generally, the ratio of uncoated part to the total surface of floc is 3%
It is the following.

The monomer and the chemical oxidant are added to the treatment liquid by the procedure of adding them together, or
Alternatively, the monomer may be added first, and then the chemical oxidant may be added. The chemical oxidant for the catalyst may be added all at once, or may be added in several batches.
You may add continuously little by little.

The polymerization reaction of the pyrrole monomer is preferably allowed to proceed as slowly as possible. The temperature condition is preferably low temperature, preferably 2 ° C to 35 ° C, more preferably 2 ° C to 25 ° C. When the polymerization rate is remarkably high, the reaction in the water phase proceeds rapidly (in an instant), the polymer becomes difficult to adhere to the surface of the fiber, and the polymer particles released in the water tank are formed. The polymerization reaction is carried out while stirring or circulating a slurry type treatment liquid containing at least one kind of ultrafine particles selected from the group consisting of acidic colloidal silica, ultrafine particles of acidic silica and alumina sol together with the fibers. When the polymerization of the monomer progresses and the solubility decreases during that period, the produced polypyrrole is deposited or attached on the surface of the fiber together with ultrafine particles such as acidic colloidal silica. This reaction is a quantitative reaction.

Satisfactory flight power, conductivity, fluidity (classification)
In order to achieve flame retardancy, all surfaces including end faces of fibers are substantially covered with both polypyrrole and ultrafine particles of acidic colloidal silica, acidic silica ultrafine particles and / or alumina sol. And it is desirable that the coating be of uniform thickness over the surface. From this viewpoint, it is particularly preferable that the fibers are present in a ratio of 1 part by weight to 5 to 20 parts by weight of the treatment liquid in the treatment liquid in the form of a slurry containing fibers and ultrafine particles of acidic colloidal silica. The stirring speed is not particularly limited, but it is necessary to prevent the flocs from settling, and therefore, for example, the stirring speed in the case of using polyester fibers needs to be higher than that in the case of using polyamide fibers.

As the chemical oxidant for the catalyst, any substance that accelerates the polymerization of the pyrrole monomer may be used.
For example, ferric chloride, ferric perchlorate, ferric nitrate, ferric citrate, ferric p-toluenesulfonate, ferric sulfate, ferric periodate, ammonium ferric sulfate, etc. These are used alone or in appropriate combination of two or more substances. A water-soluble ferric salt is particularly preferable.
The chemical oxidizer is usually about 2 per mole of pyrrole monomer.
It is used in an amount of about 3 to about 3 mol, but when an oxygen radical generating source such as dissolved oxygen in water, oxygen in air, hydrogen peroxide, or ozone is also used as an auxiliary oxidant, it is a chemical oxidant for the pyrrole monomer. The usage of can be reduced accordingly.

Further, the treatment liquid may further contain a surface tension lowering agent in order to make the formation of the polypyrrole film uniform on the fiber surface. Examples of the surface tension reducing agent include a surfactant, an organic solvent, and a silicone-based defoaming agent. Surfactants improve the wettability of the fiber surface, and alcohols can be additionally mixed in order to improve the wettability of the fiber surface by mixing with water. Examples of the above-mentioned surfactant include anionic surfactants such as sodium alkylsulfate, sodium alkylbenzenesulfonate, sodium alkylsulfosuccinate, sodium polyoxyalkylenesulfonate, sodium alkylnaphthalenesulfonate; or polyethylene glycol / polypropylene. Glycol block copolymer,
Examples include nonionic surfactants such as polyethylene glycol alkyl ether and polyethylene glycol alkyl phenyl ether. Examples of the organic solvent include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, n-butanol,
Examples thereof include alcohols such as isobutanol and isoamyl alcohol, dimethylformamide, tetrahydrofuran, dioxane, acetonitrile, cyclohexanone, methyl ethyl ketone, acetone and the like. The addition amount of the surface tension reducing agent is generally a very small amount or a small amount, for example,
In the case of a surfactant, it is about 0.01 based on the total weight of the processing liquid.
An amount in the range of about 2% to about 2% is sufficient, and in the case of alcohols, about 0.1 to about 5.0 with respect to the total weight of the processing liquid.
% Range is sufficient.

If necessary, a dopant may be used together with the polymerization of the pyrrole monomer in order to increase the conductivity of the fiber. This dopant preferably has a pH
It is used under the conditions of 1 to 5, more preferably pH 1 to 3. Suitable dopants include, for example, p-toluenesulfonic acid, benzenesulfonic acid, monochlorobenzenesulfonic acid, dichlorobenzenesulfonic acid, trichlorobenzenesulfonic acid, naphthalenesulfonic acid, isopropylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenedisulfonic acid, Examples thereof include naphthalenetrisulfonic acid, sulfosalicylic acid and other aromatic sulfonic acids; or perchloric acid, hydrochloric acid, sulfuric acid, nitric acid, trifluoromethanesulfonic acid and the like. Particularly, aromatic sulfonic acid or its alkali metal salt is preferable.

After the completion of the polymerization reaction, the coated fiber is washed with water. At this time, if necessary, the entanglement of the flocs can be prevented, and a screw or the like in the supply path from the storage tank in the electrostatic flocking machine can be used. In order to improve the transportability, a small amount of a softening agent or a leveling agent such as stearic acid amide may be added and used. Further, in the case of using an undyed fiber such as polyester as the fiber, before forming the coating layer such as polypyrrole, a surfactant or an oily substance that exudes from the inside of the fiber into the treatment liquid of the polymerization reaction is preliminarily used. It is preferable to wash and remove it.

Further, the simultaneous coating treatment of both materials of the polypyrrole of the present invention and ultrafine particles such as acidic colloidal silica may be carried out after dyeing or before dyeing. However, alkali dyeing of polyester fibers causes de-doping and reduces conductivity, so when performing alkali dyeing, it is necessary to carry out the dyeing before the above coating treatment, and to be sure after dyeing. It is preferable to carry out pickling. Further, the dyeing after the coating treatment needs to be performed under acidic conditions. In addition, the use of raw fiber
Alternatively, by dyeing the fiber, the hue of the dye and the hue of the above-mentioned coating layer are combined to obtain a floc having a variety of color tones. Examples of the dye used include acid dyes, metal complex salt dyes such as chromium complexes, disperse dyes, cationic dyes, and reactive dyes, although they vary depending on the fiber.

Thereafter, the coated fiber is dried,
In order to minimize the entanglement of the flocs, a fluidized-bed drying method, that is, a method of drying the flocs in a slurry state or a state where the flocs are dehydrated by centrifugation by contact with a hot air flow in a fluidized tank is used. Is most preferred. In order to operate more conveniently in this drying method, the temperature is about 120 to about 180 ° C., and the tank residence time is 0.1 to 5
It is advisable to adopt the condition of seconds. When dried under these conditions, the floc of the present invention having a water content of about 1 to 5% can be easily obtained.

The flock for electrostatic flocking of the present invention uses long fibers, to which polypyrrole and both materials of acidic colloidal silica, acidic silica ultrafine particles and / or ultrafine particles of alumina sol are simultaneously coated. It is also produced by performing a treatment and then cutting the treated long fiber into a predetermined size to obtain a short fiber. For example, if a circular tow is incised into a linear shape and then cut to a predetermined size to form a flock, the cut surface, that is, the end surface of the flock, a coating layer such as polypyrrole is not formed, The area of the end face is about 0.3 to 1.2% with respect to the total surface area of the flocs, and does not substantially affect the flight properties of the flocs. Polyamide fiber, vinylon fiber, etc. have the diffusion of pyrrole monomer into the fiber, so even if the process of covering the fiber in the form of tow and then cutting this is taken, the resulting flocs will have There is a tendency for the entire outer peripheral portion or the entire end face to be made conductive, and in this case, the ratio of the non-conductive area becomes smaller.

The flocs of the present invention are manufactured through the processes described above, and as a result, the moisture content thereof is about 1 to 5%.
A dry floc with or near the official moisture regain of is obtained. Since the floc of the present invention is not substantially affected by the humidity of the ambient air, the moisture content of the floc is maintained substantially unchanged.

The flock of the present invention can be used for electrostatic flocking similar to the conventional ones, whereby various kinds of electrostatic flocking products can be manufactured. The method of electrostatic flocking is not particularly limited, and an up-type electrostatic flocking method (where a floc is placed on the lower electrode and the object to be transplanted is provided on the upper electrode, and a voltage is applied between the upper and lower electrodes) Flocking method of flying flock upwards), Down electrostatic flocking method (providing a lower electrode with a transplanted object and using a grid or linear upper electrode, and applying a voltage between the upper and lower electrodes, A flocking method in which the flocs are caused to fly downward by passing through the grid of the upper electrode) or a side-type electrostatic flocking method (where the flocked object is connected to the side of the electric field with an electrode) In the lower part, a flocking method in which the flocs are first allowed to fly downward and laterally from the middle by dropping the flocs into the electric field from the hopper). In addition, a flow tank type electrostatic flocking machine (a type of flocking machine that uses a flow tank having a structure in which a perforated plate is stretched inside the tank and vibration is applied as a floc supply tank, such as an up-down type and a side type. .) May be used to produce electrostatic flocking products such as automobile interior parts from the flock of the present invention.

[0035]

[Function] The coating layer of ultrafine particles of acidic colloidal silica, ultrafine particles of acidic silica and / or alumina sol formed on the surface of the fiber enhances the rigidity of the flocs, and the flocs are more cohesive with respect to the surface characteristics of the flocs. Change to a property that does not. Therefore, in the electrostatic flocking process, the floc aggregate of the present invention is less likely to form lumps and does not flow as lumps, thus improving the fluidity and classifying properties. In addition, acidic colloidal silica, acidic silica ultrafine particles and alumina sol are all inorganic ultrafine particles and are essentially nonflammable high melting point materials, so that the coated fibers are softened and difficult to melt. To make the floc more flame retardant. Therefore, during electrostatic flocking, even if the flock is excessively supplied into the electric field, the frequent occurrence of sparks and the resulting fusion of the flocks, and thus the ignition of the flock fibers do not occur. On the other hand, the polypyrrole coated on the surface of the fiber gives the floc a desired conductivity. In particular, the polypyrrole coating keeps the flocs in a dry state at all times, so that the conductivity of the flocs is not affected by the amount of surrounding moisture. Therefore, in the present invention, the surface of the fiber is respectively coated with both materials of ultrafine particles such as polypyrrole and acidic colloidal silica, so that the resulting flocs work in combination with the properties of both materials. In addition, the high conductivity which is not affected by moisture is satisfactorily achieved, the fluidity and the classifying property are satisfactorily improved, and the flame retardancy is satisfactorily increased. Moreover, the amount of conductive polymer used can be significantly reduced as compared with the case where only polypyrrole is coated.

[0036]

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

Examples 1-6 First, as raw material fibers, cut 6,6-nylon fibers (fineness: 1.5 denier, fiber length: 0.55 mm)
Was dyed with a metal complex dye or an acid dye, if necessary, and then thoroughly washed with water to prepare. Further, from a commercially available product Snowtex ST-O (manufactured by Nissan Chemical Industries, Ltd.), colloid particle diameter: 0.01 to 0.0
2mμ, solid content 20%, pH 3.85 (temperature 12.5 ° C
,) And an acidic colloidal silica having a characteristic of dispersion medium: water was also prepared. Next, the pyrrole monomer was put into an aqueous treatment liquid containing the above 6,6-nylon fiber and acidic colloidal silica, and subsequently, as a dopant,
An amount of 1 mol of sodium anthraquinone disulfonate was added to the treatment liquid per 20 mol of the pyrrole monomer. Then, while stirring the mixed treatment liquid together, the polymerization reaction of pyrrole was carried out at a temperature of 15 ° C. by using ferric paratoluenesulfonate (2 moles per 1 mole of pyrrole monomer) as a catalyst as a catalyst. The resulting polypyrrole and acidic colloidal silica were coated on the surface of 6,6-nylon fiber by advancing for 3.5 hours. After the completion of the polymerization reaction, the obtained flocs were taken out from the treatment liquid, washed thoroughly with water, and then dried until the water content became a predetermined value. As shown in Table 1 below, various amounts of the pyrrole monomer and the acidic colloidal silica used and the amount of water at the time of drying were variously changed to produce the flocks for electrostatic flocking of Examples 1 to 6.

Comparative Example 1-2 Only polypyrrole was obtained by repeating the same procedure as in Example 1-6 except that the acidic colloidal silica was not added to the treatment liquid and the polymerization conditions were the same. Flocks for electrostatic flocking of Comparative Examples 1 and 2 shown in Table 1 below, which were coated on the surface of 6,6-nylon fibers, were produced.

[0039]

[Table 1]

Further, FIGS. 1 to 8 of the drawings show photomicrographs of electrostatic flocking flocs taken by using an electron microscope. Magnification: 10000 times (Figs. 1 and 5), 5000 times (Figs. 2 and 6), 3000 times (Figs. 3 and 7), 1000
Fold (Figure 4, Figure 8). FIGS. 1 to 4 show the flock for electrostatic flocking of Example 1 in which the surface of nylon 6/6 fiber is coated with polypyrrole and acidic colloidal silica, and FIGS. 5 to 8 show only polypyrrole. Is a flock for electrostatic flocking of Comparative Example 1 in which the surface of nylon 6/6 fiber is coated. The length of the white line in the lower right part of these photographs is 5 μm (FIGS. 1 and 5) and 10 μm.
(FIGS. 3 and 7) and 50 μm (FIGS. 4 and 8).

Test Example 1 The surface electric leakage resistance value of each of the obtained flocs was measured by a conventional method. This measured value is shown as "resistance value" in Table 2 below. Next, using a down-type electrostatic flocking machine, the flocs of each of the obtained examples were each used as a base material for a 2/1 weave fabric (polyester / cotton = 65/35, thickness 0.15 mm, adhesive agent). Flocked to the surface of (applied). Applied voltage: 35 kV, distance between electrode and substrate: 10 cm. Then, in the electrostatic flocking process, the flying property and fluidity of the flocs were evaluated according to the following criteria. Furthermore, the flame retardancy of the flocs was also evaluated according to the following criteria by examining the fusion between the flocs and the presence or absence of ignition. -Flying property-A indicates that a sufficient flying force is obtained for the flocs and the electrostatic flocking is uniform and very good. ○ indicates that the required flight force for the flocs was obtained, and the electrostatic flocking was good. -Fluidity and classification-The ◎ indicates that the floc aggregate does not flow as a lump in the flocking machine and that flocs of a certain length can be efficiently classified, resulting in a uniform and highly productive electrostatic charge. Indicates that flocking is possible. In the case of ○, the floc aggregate may partially form a lump and flow as a lump in the flocking machine, and the operation of classifying a flock of a certain length can always be performed smoothly. However, as a result, there are cases in which there is a problem in terms of uniformity of hair transplantation. -Flame Retardancy-⊚ indicates that during electrostatic flocking, phenomena of sparking, flocking of flocs, and ignition do not occur. X indicates that, during electrostatic flocking, the sparks generated may cause flocks to fuse together in the electric field and further progress to cause an ignition phenomenon. The results of these tests are summarized in Table 2 below.

[0042]

[Table 2] From this table, the flocs of Examples 1 to 6 are the same as Comparative Examples 1 and 2.
It can be seen that the fluidity (classification property) and flame retardancy are satisfactorily improved as compared with those of No. Further, regarding conductivity and flight properties, it is understood that the flocs of Examples 1 to 6 maintain the same performance as the flocs of the comparative example.

Test Example 2 The floc for electrostatic flocking produced in the same manner as in the above example was quantitatively analyzed by the following procedure for the coating amount of acidic colloidal silica on the surface thereof. Cut 6,6-nylon fibers (fineness: 1., Not coated with acidic colloidal silica or polypyrrole).
A mixture of 5 denier, fiber length: 0.5 mm) and a known amount of silicon dioxide was used as a standard sample, and several standard samples with different amounts of SiO ₂ were prepared. Then, for these standard samples, the SiKα ray measurement value was obtained according to the fluorescent X-ray analysis method, and the measurement value was used as the X axis, while the amount of silicon dioxide in the sample was used as the Y axis, and the SiKα ray measurement value / silicon dioxide amount. A calibration curve graph of was prepared. Next, each floc sample to be analyzed (Sample N below)
o. 1 to No. 6) 0.5 g was placed in each sample holder, and each analysis sample was subjected to the fluorescent X-ray analysis method in the same manner as above, and the SiKα ray measurement value (measured twice,
cps, average 100 seconds). A blank value was also obtained using a sample holder containing no analytical sample, and the blank value was offset to calculate the amount of acidic colloidal silica coating for each analytical floc sample. The results are shown in Table 3 below.

[0044]

[Table 3] Note) The unit of ^a and ^b = amount is expressed by the fiber weight ratio (%). From this table, the coating amount of acidic colloidal silica on the surface of the flock for electrostatic flocking according to the present invention is about 0.5% to
It is in the range of 0.7%, and it can be seen that it is almost constant. Taking into account the specific gravity of polypyrrole (about 0.9) and the specific gravity of acidic colloidal silica (2.53 to 2.65),
The sample No. 2 to No. It is considered that the flocs of No. 6 have the same volume of silicon dioxide as polypyrrole coated and fixed on the fiber surface. Each of the above results is the result when a fiber having a fineness of 1.5 denier is used, and if the diameter of the fiber is different, the amount of the acidic colloidal silica coating on the flock surface is also increased or decreased accordingly. Conceivable.

Example 7 First, a commercial product of acidic silica (manufactured by Wacker Chemicals, 4
% Aqueous solution, pH 3.6 to 4.3), acidic silica ultrafine particles were prepared. Then, using raw material fibers of the same material as in Example 1 and a treatment liquid of the same composition, and using the same material as in Example 1 as the dopant and the chemical oxidizer, the pyrrole monomer was added to 6,6-nylon. The fiber and the above acidic silica ultrafine particles were added to an aqueous treatment solution, and subsequently, the dopant sodium anthraquinone disulfonate was added to the treatment solution. The amount of pyrrole used in the treatment liquid was 0.25% by weight of the fiber, and the amount of the acidic silica ultrafine particles added was 0.5% by weight of the fiber. The amount of dopant was 1 mol per 20 mol of the pyrrole monomer. Then, while stirring the mixed treatment solution together, the polymerization reaction of pyrrole was carried out by ferric paratoluene sulfonate as a chemical oxidant (2 moles per 1 mole of pyrrole monomer).
The amount of (molar amount) was used as a catalyst and allowed to proceed at a temperature of 15 ° C. for 3.5 hours to coat the produced polypyrrole and acidic silica ultrafine particles on the surface of the 6,6-nylon fiber. After the completion of the polymerization reaction, the obtained flocs were taken out from the treatment liquid, washed thoroughly with water, and then dried until the water content became a predetermined value.

The produced electrostatic flocking flock was measured according to the procedure of Test Example 1 above, and its conductivity, flight property, fluidity and flame retardancy were evaluated. The flock of this example has a surface electric leakage resistance value of 5 × 10 ⁵ Ω /
It was cm, and it was confirmed to have high conductivity. Further, using the down type electrostatic flocking machine, the flocs of Example 7 were applied to the surface of the base material 2/1 weft fabric (polyester / cotton mixed woven fabric, with adhesive applied), applied voltage: 35 kV,
When electrostatic flocking was performed at a distance between the electrode and the base material of 10 cm, sparks, fusion of flocs, and ignition phenomena did not occur at all, and the flocs of this example have satisfactory flame retardancy. It was confirmed to be a thing. Further, during this electrostatic flocking process, it was confirmed that the floc aggregate did not flow as a lump in the flocking machine and did not flow, and desired flight properties and fluidity were obtained.

Example 8 Acidic silica sol in place of the ultrafine particles of acidic silica of Example 7, that is, commercially available DMAC-ST (manufactured by Nissan Chemical Industries, Ltd.), colloidal particle diameter: 0.01 to 0.02 μm
m, solid content 20%, pH 2.5 (at a temperature of 15.0 ° C.), dispersion medium: Other materials, compositions, conditions, etc. were used except that an acidic silica sol having characteristics of dimethylacetamide was used. In the same manner as in Example 7, the pyrrole monomer was introduced into an aqueous treatment liquid containing 6,6-nylon fiber (fineness: 3 denier, length: 0.5 mm) and the above acidic silica sol, and then, , A dopant sodium anthraquinone disulfonate was added to the treatment liquid. The amount of acidic silica sol added to the treatment liquid was 1.0% in terms of fiber weight ratio. Then, while stirring the mixed treatment liquid together, the polymerization reaction of pyrrole
By using ferric p-toluenesulfonate as a chemical oxidant as a catalyst and advancing for 3.5 hours at a temperature of 15 ° C., the produced polypyrrole was coated on the surface of 6,6-nylon fiber together with acidic silica sol. After the completion of the polymerization reaction, the obtained flocs were taken out from the treatment liquid, washed thoroughly with water, and then dried until the water content became a predetermined value.

The produced electrostatic flocking flock was tested in Test Example 2
According to the method according to, the fiber weight ratio is 5.0
% Acidic silica sol layer was found attached to the fiber surface. Further, regarding the floc, the above-mentioned Test Example 1
The flame retardancy was evaluated by the measurement according to the procedure of. Using a down-type electrostatic flocking machine, the flock of Example 8 was applied to the surface of a 2/1 weft woven fabric (polyester / cotton mixed woven, with an adhesive applied) as a base material, an applied voltage: 35 kV, and an electrode. When electrostatic flocking was performed at a distance of 10 cm from the base material, sparks, flocking between flocks, and ignition phenomena did not occur at all, and the flock of this example has satisfactory flame retardancy. It was confirmed that there is. Furthermore, the floc of this example has high conductivity, and during the electrostatic flocking process, the floc aggregate does not flow as a lump in the flocking machine and the desired flight property and fluidity are obtained. It was confirmed.

Example 9 Dye 6,6-nylon fiber of raw material fiber (fineness:
Along with 1.5 denier and fiber length: 0.5 mm, 5.0% by weight of fiber sol of alumina sol (colloid particle size:
0.01 to 0.02 μm, solid content 20%), as a chemical oxidizing agent, 2.3 mol ammonium iron sulfate per mol pyrrole monomer, and 2.0 mol paratoluene per mol pyrrole monomer. Ferric sulfonate and 0.2 mol of sodium anthraquinone disulfonate per mol of the pyrrole monomer were added as a dopant. Subsequently, 0.25% by weight of fiber of pyrrole monomer was added to the above treatment solution, and the polymerization reaction of pyrrole was allowed to proceed at a temperature of 20 ° C. for 5 hours while stirring together. The surface of 6,6-nylon fiber was coated with the produced polypyrrole and alumina sol. After the completion of the polymerization reaction, the obtained flocs were taken out of the treatment liquid, thoroughly washed with water, and then dried at 105 ° C. until a predetermined water content was obtained.

The produced electrostatic flocking flock was measured in accordance with the procedure of Test Example 1 above, and its conductivity, flight property, fluidity and flame retardancy were evaluated. The flock of this example has a surface electric leakage resistance value of 2 × 10 ⁶ Ω /
It was cm, and it was confirmed to have high conductivity. Further, using a down-type electrostatic flocking machine, the flock of Example 9 was applied to the surface of the base 2/1 weave fabric (polyester / cotton mixed woven, with adhesive applied), applied voltage: 35 kV,
When electrostatic flocking was performed at a distance between the electrode and the base material of 10 cm, sparks, fusion of flocs, and ignition phenomena did not occur at all, and the flocs of this example have satisfactory flame retardancy. It was confirmed to be a thing. Also, during this electrostatic flocking process, although the floc aggregate did not flow as a lump in the flocking machine, the flight properties of the flock,
The fluidity was slightly inferior to the case where the acidic colloidal silica was used.

[0051]

As can be seen from the above description, according to the present invention, stable electrostatic flocking can be repeated in a dry environment with satisfactory conductivity and flight properties, and
The flowability is improved, and the electrostatic flocking process does not clump and flow, preventing the generation of inhomogeneous flocking products, and improving the classification property, improving the efficiency of the electrostatic flocking process. Where the flame retardancy is improved, there is no risk of sparking, flocking of flocks and ignition even during electrostatic flocking even under conditions of excessive supply. A flock for electrostatic flocking is provided. In short, according to the present invention, it is possible to obtain a flock for electrostatic flocking which is improved in fluidity, classification property and flame retardancy as well as conductivity and flight property. Moreover, the flock for electrostatic flocking of the present invention can be produced by performing simultaneous coating of polypyrrole and ultrafine particles (acidic colloidal silica, etc.) on the fiber surface during the polymerization process of pyrrole. It also has the advantage that very good flock production is possible.

[Brief description of drawings]

FIG. 1 is a photomicrograph of the flocks for electrostatic flocking of Example 1 in which polypyrrole and acidic colloidal silica are coated on the surface of fibers, taken with an electron microscope (magnification: 10,000 times). The length of the white line in the lower right part of the photograph represents 5 μm.

FIG. 2 is a micrograph of the flocks for electrostatic flocking of Example 1 in which polypyrrole and acidic colloidal silica are coated on the surface of the fibers, taken with an electron microscope (magnification: 5000 times).

FIG. 3 is a photomicrograph of a floc for electrostatic flocking of Example 1 in which polypyrrole and acidic colloidal silica are coated on the surface of the fiber, taken with an electron microscope (magnification: 3000 times). The length of the white line in the lower right part of the photograph represents 10 μm.

FIG. 4 is a micrograph of the flocks for electrostatic flocking of Example 1 in which polypyrrole and acidic colloidal silica were coated on the surface of the fibers, taken with an electron microscope (magnification: 1000 times). The length of the white line in the lower right part of the photograph represents 50 μm.

FIG. 5 is a photomicrograph of the electrostatic flocking floc of Comparative Example 1 in which the surface of the fiber is coated with polypyrrole, taken with an electron microscope (magnification: 10,000 times).
The length of the white line in the lower right part of the photograph represents 5 μm.

FIG. 6 is a photomicrograph of the flock for electrostatic flocking of Comparative Example 1 in which the surface of a fiber is coated with polypyrrole, taken with an electron microscope (magnification: 5000 times).

FIG. 7 is a photomicrograph of the flock for electrostatic flocking of Comparative Example 1 in which the surface of the fiber is coated with polypyrrole, taken with an electron microscope (magnification: 3000 times). The length of the white line in the lower right part of the photograph represents 10 μm.

FIG. 8 is a photomicrograph of the flock for electrostatic flocking of Comparative Example 1 in which the surface of the fiber is coated with polypyrrole, taken with an electron microscope (magnification: 1000 times). The length of the white line in the lower right part of the photograph represents 50 μm.

Claims (3)

[Claims] 1. Electrostatic flocking characterized in that the surface of the fiber is coated with polypyrrole and at least one ultrafine particle selected from the group consisting of acidic colloidal silica, ultrafine particles of acidic silica and alumina sol. Frock. 2. The flock for electrostatic flocking according to claim 1, wherein the ultrafine particles are ultrafine particles having a specific gravity of 2 to 3 and a particle diameter of 0.01 to 0.02 μm. . 3. Pyrrole polymerization reaction with fibers,
In a treatment liquid containing at least one kind of ultrafine particles selected from the group consisting of acidic colloidal silica, ultrafine particles of acidic silica and alumina sol, a chemical oxidant is used as a catalyst to advance the produced polypyrrole together with the ultrafine particles. It is manufactured by coating the surface of the fiber in the treatment liquid.
Flock for electrostatic flocking as described.