JP2009244471A - Conductive flock - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive flock giving a brush which improves flying property and also improve printing durability when the conductive flock is electrostatically flocked. <P>SOLUTION: The conductive flock is polyamide fiber containing 10 to 40% by weight of conductive carbon and 1 to 7% by weight of ash percentage is imparted. It is preferable the conductive flock contains 0.01 to 1% by weight of metal oxides composed of metal with electronegativity which is 1.7 or less for the polyamide fiber containing the conductive carbon. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to conductive flocks and conductive brushes used in electrophotographic recording type dry copying machines, facsimiles, printers, and the like. Specifically, the present invention relates to a conductive flock used for a conductive brush created by electrostatic flocking and a conductive brush using the conductive flock.

Conductive rollers for the charging section of the elements important for the electrostatic latent image format in electrophotographic copying machines, the cleaning section for removing residual toner and charges remaining on the photoreceptor, and the supply section for applying charge to the toner Is often used. However, in recent years, high image quality and color applications are increasing, and toner particles are becoming smaller. When this small-sized toner is used, in a conductive roller made of silicone or polyurethane, the toner enters the bubbles on the surface of the roller to harden the roller surface, or the toner is melted to form a roller by toner filming. There was a problem that the resistance value of the surface was increased. For this reason, Patent Document 1, Patent Document 2, and Patent Document 3 have proposed conductive brushes in which conductive fibers are implanted on the roller surface. However, when a fiber with a conductive polymer such as polypyrrole coated on the fiber is used as the conductive fiber, the conductive polymer film falls off during use and the resistance value of the fiber surface increases. was there. In addition, when electrostatically implanting conductive fibers kneaded with conductive materials as conductive fibers, the resistance value of the flock is lowered due to the inherent resistance value of the conductive fiber and the flying property is deteriorated. It is necessary to make it high (Non-Patent Document 1).
JP 2004-335316 A Japanese Patent Laid-Open No. 10-123821 JP 2004-70006 A “Journal of the Electrostatic Society”, 1992, Vol. 16, No. 5, p. 389-395

  It is an object of the present invention to provide a conductive flock that provides a brush capable of improving flying resistance and improving printing durability when electrostatically flocking the conductive flock.

  The object of the present invention described above is achieved by providing a conductive flock according to the present invention having the following configuration (1).

  (1) It is a conductive flock made of a polyamide fiber containing 10 to 40% by weight of conductive carbon and provided with an electrodeposition treatment agent, and the ash content of the conductive flock is 1 to 7% by weight. Characteristic conductive floc.

  (2) The conductivity according to (1), wherein the polyamide fiber containing conductive carbon contains 0.01 to 1% by weight of a metal oxide composed of a metal having an electronegativity of 1.7 or less. Frock.

  (3) The conductive floc according to either (1) or (2), wherein the electrodeposition treatment agent contains organic silicon.

  (4) The conductive floc according to any one of (1) to (3), wherein the electrodeposition treatment agent applied to the conductive floc is a mixture of colloidal silica and alumina sol.

  (5) A conductive brush produced by electrostatic flocking of the conductive flock according to any one of (1) to (4).

  According to the present invention, as will be described below, a conductive floc having excellent flying property can be obtained.

  Hereinafter, the conductive floc of the present invention will be described in more detail.

  The floc as used in the present invention is a member used for electrostatic flocking and refers to a fiber obtained by subjecting short fibers to electrodeposition treatment.

  The polyamide constituting the present invention is a high molecular weight product in which a so-called hydrocarbon group is connected to the main chain through an amide bond, and is a polyamide mainly composed of polycaproamide or polyhexamethylene adipamide. The term “mainly” as used herein refers to ε-caprolactam units constituting polycaloamide in polycaproamide, and 80 mol% or more as hexamethylene diammonium adipate units constituting polyhexamethylene adipamide in polyhexamethylene adipamide. More preferably, it is 90 mol% or more. Polycaproamide and polyhexamethylene adipamide are particularly preferable. From the viewpoint of dispersibility of the conductive carbon, polycaproamide is particularly preferable.

  The content of conductive carbon in the conductive floc of the present invention is required to be 10 to 40% by weight. When the content of conductive carbon is less than 10% by weight, the specific resistance value of the polyamide fiber becomes high, the conductivity is lost, and no charge can be imparted, so that it does not function as a conductive brush. On the other hand, if the content of the conductive carbon exceeds 40% by weight, the spinnability is lowered in the production of the polyamide fiber, and the production becomes difficult. Preferably it is 15 to 35% by weight.

  The conductive carbon used here is not particularly limited as long as it is a powder having conductivity, such as acetylene black, channel black, and furnace black. However, the furnace carbon is small in that the powder particles are small and relatively uniform. Black is preferred. When the particles are large, it is preferable to use particles having a size of 2 μm or less in consideration of suppression of increase in filtration pressure during spinning, yarn breakage during spinning, and improvement in fiber strength. Alternatively, conductive carbon particles in a dispersion-prepared nylon pellet may already be used by a pigment manufacturer, such as conductive carbon black particle-dispersed nylon pellet “CARBOREX NYRON YT-01” manufactured by Dainippon Ink and Chemicals, Inc.

  Methods for incorporating conductive carbon in polyamide multifilament include blending and melting conductive carbon into polyamide pellets, blending and melting master pellets containing high concentrations of conductive carbon into polyamide pellets, melting Examples thereof include a method of adding conductive carbon to a polyamide in a state and kneading, and a method of kneading a polyamide containing a high concentration of conductive carbon in a molten state to a molten polyamide.

  The conductive floc of the present invention preferably contains a metal oxide composed of a metal having an electronegativity of 1.7 or less in a polyamide fiber containing conductive carbon. The content of the metal oxide is preferably 0.01 to 1% by weight in the polyamide fiber containing conductive carbon.

  In the present invention, by containing a metal oxide composed of a metal having an electronegativity of 1.7 or less, flying property is improved during electrostatic flocking. The reason why the flying property is improved is not clear, but the metal oxide having an electronegativity of 1.7 or less is an ionic bond. Therefore, when a high voltage is applied, the metal oxide easily obtains a charge. It is considered that the conductive floc containing the oxide also easily obtains electric charge and improves flying property. When the added amount of the metal oxide is less than 0.01% by weight, the flying property is not improved because the charge for obtaining the metal oxide is small when a high voltage is applied in electrostatic flocking. When the addition amount of the metal oxide exceeds 1% by weight, the filtration pressure during continuous production in the production of polyamide fibers increases, the exchange cycle of the spin pack becomes faster, and workability decreases.

  Here, the electronegativity is the ability of atoms in the molecule to attract electrons. Specifically, it is assumed that different atoms are chemically bonded. At this time, the charge distribution of electrons in each atom is different from that in the case where the atom is isolated. This is due to the influence of the bonding partner atom, and there is a difference in the strength of attracting electrons depending on the type of atom. The strength of attracting electrons can be determined as a relative value for each atom type. This scale is called electronegativity. Electronegativity is an atom-specific value, and there are various ways to determine the scale, but the value of electronegativity by Pauling ("Chemical Handbook Basic Edition" revised edition, II-589, Maruzen Co., Ltd.) was used. .

  Examples of the metal oxide composed of a metal having an electronegativity of 1.7 or less include magnesium oxide, aluminum oxide, titanium oxide, zinc oxide, manganese oxide, chromium oxide, calcium oxide, scandium oxide, vanadium oxide, and oxidation. Examples thereof include yttrium, zirconium oxide, niobium oxide, cadmium oxide, indium oxide, lanthanum oxide, and hafnium oxide. Of these, magnesium oxide, aluminum oxide, titanium oxide, and zinc oxide are more preferred because they are easy to produce fine particles and have good dispersibility with polyamide fibers.

  The particle diameter of a metal oxide composed of a metal having an electronegativity of 1.7 or less is preferably 5 μm or less from the viewpoint of dispersibility in polyamide fibers. If it exceeds 5 μm, the filtration pressure during continuous production in the production of polyamide fibers will increase, the replacement cycle of the spin pack will be accelerated, and workability will be reduced.

  As a method for incorporating a metal oxide comprising a metal having an electronegativity of 1.7 or less constituting the present invention into a polyamide fiber containing conductive carbon, the metal oxide is added to a polyamide pellet containing conductive carbon. A method of blending and melting, a method of blending and melting master pellets containing a high concentration of metal oxide in polyamide pellets, a method of adding metal oxide to a molten polyamide and kneading, before or during polymerization of polyamide A method of adding a metal oxide to a raw material or a reaction system in a stage can be mentioned, but any method may be used as long as both are uniformly mixed.

Although the manufacturing method of the fiber which comprises the electroconductive floc of this invention is not specifically limited, For example, about the manufacturing method by melt spinning, a two-step method (the method of extending | stretching after winding an undrawn yarn once), one step High speed spinning method (method of spinning the spinning speed as high as 4000 m / min or higher, substantially omitting the stretching step, production of POY), high speed spinning stretching method (method of performing spinning-stretching step continuously), etc. There is. Among them, a two-step method is preferable, and a polyamide resin containing conductive carbon is melted, discharged from a nozzle discharge hole, and after cooling and oiling, a wound undrawn yarn is obtained once at a speed of 1000 m / min or less. The obtained undrawn yarn was wound at a draw ratio of 2.5 to 3.5 and a heat drawing temperature of 100 to 190 ° C., and the specific resistance value (temperature 20 ° C., humidity 30% RH) was 10 ³ to 10 ⁸ Ωcm. A drawn yarn (polyamide long fiber) is obtained. In the above, the specific resistance value is a bundle of 1000 dtex conductive polyamide long fibers, a measurement yarn length of 10 cm, left at a humidity of 65% RH for 18 hours or more, and the electric resistance is measured with a vibration capacity type super insulation meter. The specific resistance value was calculated from the yarn length and yarn weight. The specific resistance value varies depending on the conductive carbon concentration. When the conductive carbon concentration is high, the specific resistance value is low, and when the conductive carbon concentration is low, the specific resistance value is high. After making the obtained polyamide long fiber into a form of tow (convergence of continuous filament), heat treatment is performed with hot water at 80 to 98 ° C. for 30 to 60 minutes, and short fibers are made by a cutting machine such as a guillotine cutter. The hot water treatment during the manufacturing process not only shrinks the polyamide long fibers containing conductive carbon and reduces the variation in electric resistance value, but also changes the resistance value over time after making conductive flock and conductive brush. Has the effect of reducing the size. The cut surface of the short fiber is determined by the cutting machine structure and the relationship between the blade and the fiber. The polyamide fiber containing conductive carbon and the blade are in contact with each other at a right angle and cut at a right angle to the fiber axis. Is preferred. Further, as will be described later, it is preferable that the short fiber as the conductive floc is not twisted or bent from the viewpoint of the flying property of the floc.

  The conductive flock of the present invention is planted using static electricity by applying an adhesive to a substrate. Electrostatic flocking is electrically affected when a minute object is present in an electric field caused by a high voltage. This electrical effect is that the minute object is charged and attracted from one pole to the other. That is, when a DC high voltage is applied to a metal, an electric field (E) is generated therebetween. When the magnitude of this electric field is the voltage (V) and its distance (d), there is a relationship of E = V / d, and the charge (q) of the small object existing in this electric field is the attraction force (F ) = It is pulled by receiving the force given by Eq. Flock refers to this small object. In electrostatic flocking, the positive electrode is called a high-voltage electrode and the negative electrode is called a ground electrode (earth electrode), and the magnitude of the electric field gives a predetermined voltage V by a high-voltage generator. In electrostatic flocking, a base material is placed in parallel between the poles and the pole face, and the flocs pierce the base material on which the adhesive is applied while flying between the poles at right angles to the base material. Therefore, the flying property is determined by the charge (q) of the floc.

  Conductive floc of the present invention An electrodeposition treatment agent is added to the polyamide fiber containing the conductive carbon. The application amount of the electrodeposition treatment agent is required to be 1 to 7% by weight when the ash content of the conductive floc is used as an index. The amount of ash is calculated by the ash method (JIS L 1015 (1999)) of the chemical fiber staple test method defined by JIS.

  An electrodeposition treatment agent is a treatment agent for imparting electric charge to perform electrostatic flocking. Specifically, a treatment in which short fibers electrically act to have a good flying effect in an electric field. It is an agent. When the application amount of the electrodeposition treatment agent is less than 1% by weight, the surface resistance value of the conductive floc is low due to the inherent resistance value of the polyamide fiber containing conductive carbon, and the flying property is deteriorated. If the application of the electrodeposition treatment agent exceeds 7% by weight, crystals will precipitate in the drying process during the electrodeposition treatment, and the crystals will adhere to the wall of the flocking chamber during electrostatic flocking, causing metal corrosion, or gelling of the adhesive Or the problem of extremely reducing the adhesive strength of the conductive floc occurs. Preferably, it is 3 to 5% by weight.

  The electrodeposition treatment agent constituting the conductive floc of the present invention includes, for example, inorganic salts such as tannic acid, sodium chloride, barium chloride, magnesium chloride, magnesium sulfate, sodium nitrate, zirconium carbonate, anion activator, nonionic activator Such as surfactants such as colloidal silica, alumina sol, etc., but when used as a conductive brush, dry copying is possible when using inorganic salts or antistatic surfactants as electrodeposition treatment agents. In a machine, a printer, or the like, the surface treatment agent for the photoreceptor and toner is formed of an organic component, so that depending on the component, the surface may be altered and the print quality may be poor. For this reason, organic silicon and alumina sol are preferable from the viewpoint of not reacting with the surface treatment agent of the photoreceptor or toner, and from the viewpoint of electrical conductivity, dielectric constant, and separability.

  The electrodeposition treatment of the conductive floc of the present invention is not particularly limited. For example, the polyamide short fibers cut into short fibers are immersed in an aqueous solution of an electrodeposition treatment agent diluted with a binder to perform the electrodeposition treatment. Moreover, it is preferable to use 30-100 g / L for the aqueous solution of an electrodeposition processing agent from the viscosity of aqueous solution and the efficiency of an electrodeposition process.

  The electrodeposition treatment agent preferably contains organic silicon, and colloidal silica is particularly preferable. Since colloidal silica is particularly excellent in water dispersibility, uniform electrodeposition treatment on short fibers is easy. In addition, colloidal silica specifically binds to the hydroxyl group of the polyamide, so that it is less likely to fall off due to friction.

The electrodeposition treating agent may be an aqueous solution containing only organic silicon, but more preferably a mixed aqueous solution of colloidal silica and alumina sol. This is because colloidal silica and alumina sol have good mixing properties, and when a high voltage is applied, it is easy to obtain a high charge, and it is possible to obtain a conductive floc excellent in floc separation. In addition, when using a polyamide fiber containing conductive carbon having a specific resistance value of less than 10 ⁶ Ωcm, even if a high voltage is applied, electric current cannot be obtained and the flying property is reduced, but the mixing of colloidal silica and alumina sol By applying the aqueous solution, the resistance value of the floc surface becomes 10 ⁶ to 10 ⁸ Ωcm, and the flying property is improved. The method of mixing the colloidal silica and the alumina sol is preferable to mix the colloidal silica and the alumina sol in an aqueous solution state, since the increase in viscosity is suppressed and uniform dispersion is obtained. The mixing ratio is preferably 6: 1 to 3: 1 for colloidal silica and alumina sol because uniform dispersion can be obtained and the resistance value of the floc surface can be set to the target resistance value.

  The conductive flock subjected to the electrodeposition treatment is dehydrated using a rotary dehydrator, dried at 100 to 130 ° C. for 30 to 60 minutes, and then sieved to make the fiber length uniform.

  The fiber length of the conductive floc of the present invention is preferably 0.1 to 5 mm so that the flock products are not intertwined and can be uniformly charged when used as a conductive brush in a printer.

  The diameter of the conductive floc of the present invention is preferably 10 to 60 μm from the relationship between the conductive floc and the force cast on the adhesive layer applied to the substrate and the flocking density when electrostatic flocking is performed.

  The conductive brush of the present invention is a conductive brush prepared by electrostatic flocking of the conductive flock and is used for removing static electricity, applying charges, removing dust, and the like.

  In the conductive brush of the present invention, the conductive flock is made by electrostatic flocking, so that the resistance value of the circumference of the conductive brush becomes uniform. Particularly, the conductive brush has good performance as a brush for an electrophotographic recording type dry copying machine. Demonstrate. The electrophotographic recording type dry copying machine brush is an application brush that contacts and charges the photosensitive member in place of non-contact corona discharge, a cleaning brush that removes the charge and toner remaining on the photosensitive member, and the toner on the photosensitive member. A toner supply brush for applying charge to the toner in the toner cartridge in order to promote adsorption, and a transfer brush for applying a reverse charge to the print paper in order to transfer the toner supplied to the photosensitive member to the print paper. In either case, an adhesive is applied to a core material that is a cylindrical metal rod, a voltage of 10 to 50 KV is applied, a conductive flock is implanted by electrostatic flocking, drying, depilation and shearing are performed to prepare a brush. The core material, which is a metal rod, is not particularly limited as long as it has conductivity, but stainless steel is preferably used. Although the adhesive is not particularly limited, for example, acrylic resin, polyvinyl acetate, polyurethane, synthetic rubber, natural rubber and the like are the main components, and acrylic is preferably used. In addition, a conductive adhesive such as conductive carbon is preferably contained in the adhesive, and a conductive adhesive is preferable.

Hereinafter, the present invention will be described in detail with reference to examples. In addition, the following method was used for the measuring method in an Example.

A. Addition amount of metal oxide Using a sequential ICP issuance spectroscopic analyzer manufactured by SII Technology, 0.1 g of a sample of polyamide fiber containing conductive carbon (no electrodeposition treatment agent applied) was mixed with nitric acid, sulfuric acid and perchloric acid. The mixture was heated and concentrated until white sulfuric acid smoke was formed, and then dissolved in dilute nitric acid to make a constant volume. About this solution, the metal was measured by ICP emission spectroscopic analysis, and the content in the sample and the oxide conversion value were obtained.

B. Ash content A chemical fiber staple test method defined by JIS, JIS L 1015 (1999), measured by an ash content method, and calculated by the following equation (1).
Dn = M−K (1)
Dn: Ash content (%) as an index of the amount of electrodeposition treatment
M: measured ash content (%)
K: amount of metal derived from metal oxide in the sample measured in A above (%)
C. Flying
Using Flock Motion Tester SPG manufactured by Erich Schenk (up method method: flying distance: 15 cm), when the voltage of 20 KV is applied, the time for all the conductive flocs to fly 5 g is measured. Evaluation was made according to the following criteria.
A: Less than 10 to 20 seconds O: Less than 20 to 30 seconds Δ: Less than 30 to 40 seconds x: 40 seconds or more.

D. Crystal deposition amount of electrodeposition treatment agent 50 g of conductive floc was sieved with a 40-mesh metal wire mesh for 30 minutes, calculated from the following formula (1), and evaluated according to the following criteria.
○: 0 to less than 0.1% Δ: less than 0.1 to 0.5% ×: 0.5% or more
S = (F0−F1) / F0 (1)
F0: conductive flock weight before sieving (g)
F1: Conductive floc weight (g) after sieving.

E. Specific resistance value of polyamide fiber Using a super insulation resistance meter (TERAOHMMETER R-503, manufactured by Kawaguchi Electric Co., Ltd.), a voltage of 100 (V) is applied between 10 cm of polyamide fiber test length, under the conditions of temperature 20 ° C and humidity 30% RH. The electrical resistance value (Ω / cm) was measured and calculated from the following formula (1).
RS = R × D / (10 × L × SG) × 10 ⁻⁵ (2)
RS: Specific resistance (Ωcm)
R: Electric resistance value (Ω)
D: Yarn weight per 10,000 m
L: Test length (cm)
SG: Yarn density (g / cm ³ ).

F. Conductive floc resistance value Using an insulation meter (INSULATION tester manufactured by Toa Electric), press 10 g of the conductive floc sample uniformly into a cylindrical cylinder, and then measure the electrical resistance value (Ω) using ( It was.

G. Polyamide fiber spun yarn melted at 280 ° C., discharged from a round hole cap of one thread per cap, at a discharge rate of about 40 g, cooled and lubricated, and then wound at a speed of 800 m / min. The number of yarn breaks when this was spun for 1 t was evaluated according to the following criteria.
○: Less than 3 times / t Δ: 4 to less than 8 times / t x: 8 times / t or more.

H. Printing durability A test chart issued by the Electrophotographic Society was copied and compared with the printed state (blur, streak) after printing the first and 20000 sheets, and 10 people evaluated the following criteria.
10 points: No difference (no blur or streak)
5 points: Some differences are seen (not noticeable, but there are faint and streaks).
1 point: There is a difference (faint, streaks are clearly observed)
This was classified according to the following criteria based on the total score for 10 people.
A: 75 points or more O: 50 points or more and less than 75 points Δ: 25 points or more and less than 50 points x: Less than 25 points.

I. 98% sulfuric acid relative viscosity (a) A polyamide fiber sample is weighed and dissolved in 98% by weight concentrated sulfuric acid so that the sample concentration (C) is 1 g / 100 ml.
(B) The solution (a) is measured for the number of seconds (T1) dropped at 25 ° C. using an Ostwald viscometer.
(C) The falling seconds (T2) at 25 ° C. of 98 wt% concentrated sulfuric acid in which the sample is not dissolved are measured in the same manner as in the item (2).
(D) The 98% sulfuric acid relative viscosity (ηr) of the sample is calculated by the following equation. The measurement temperature is 25 ° C.
(Ηr) = (T1 / T2) + {1.891 × (1.000−C)}.

J. et al. Average particle diameter Measured from transmission electron microscope images.

K. Conductive brush resistance value A brush (electroconductive flock 1 electrostatically implanted in the core material) is placed on the stainless steel metal plate 4, a weight 3 on one side of 25g is placed on the core material 2, and a resistance meter 5 (SMAK manufactured by TOAKDD Co., Ltd.) 8213) was used to measure the resistance when 10V was applied.

Example 1
Conductive nylon 6 pellets were produced by kneading 98% sulfuric acid relative viscosity of 2.7 nylon 6 with conductive furnace black having an average particle size of 0.035 μm to an addition amount of 20% by weight. Magnesium oxide (MF-30 manufactured by Kyowa Chemical Industry Co., Ltd.) having an electronegativity of 1.2 as a metal oxide is powder blended to 0.04 wt% in conductive nylon 6 and melted at a melting temperature of 280 ° C. After discharging from a round hole cap with a hole diameter of 0.3 mm and cooling, the spinning oil was diluted with water and fed so that the amount of yarn adhered was 0.7%, and undrawn yarn at a take-up speed of 800 m / min. Rolled up. The spun yarn breakage at this time was 1 time / t, and was good. Subsequently, after aging the undrawn yarn for 48 hours in an environment of a temperature of 25 ° C. and an absolute humidity of 16.6 g / m ³ , the supply roller speed of the drawing machine is 200 m / min, the hot plate temperature is 170 ° C., and the drawing roller speed is 500 m / min. Then, a twist of 15 t / m was applied to the conductive nylon 6 long fiber using a down twister to obtain 190 dtex 30 filament conductive nylon 6 long fiber. The specific resistance value of the obtained polyamide long fiber was 10 ¹⁰ Ωcm.

The resulting conductive nylon 6 long fiber is picked up 30,000 times using a 3 m round casserole picker to form a tow, then heat treated with hot water at 98 ° C. for 30 minutes, and a guillotine cutter The fiber length was cut into 1.5 mm short fibers to obtain conductive nylon 6 short fibers.
Colloidal silica (Snowtex-O, manufactured by Nissan Chemical Industries, Ltd.) 50 g / L aqueous solution and alumina sol (Alumina sol-100, manufactured by Nissan Chemical Industries, Ltd.) 50 g / The aqueous solution L was immersed in an aqueous solution at 40 ° C. mixed at a mixing ratio of 6: 1 for 30 minutes to perform electrodeposition. Next, after drying at 120 ° C. for 5 minutes, sieving was performed with a 40-mesh wire mesh to obtain conductive floc (single yarn diameter: 34 μm). The obtained conductive floc had a resistance value of 10 ⁶ Ω and an ash content of 4%. Further, the flying property was 15 seconds and was ◎.

Next, an acrylic resin adhesive containing conductive carbon is applied to the core, which is a cylindrical stainless steel metal rod, a voltage of 20,000 V is applied, electrostatic flocking is performed by a down method, and drying, hair removal, and shearing are performed. The process was obtained and tailored into a brush. The resistance value of the obtained conductive brush was 10 ⁸ Ω. The resulting brush was incorporated into a toner supply brush for an electrophotographic recording type dry copying machine, and 20,000 test charts were copied. As a result, the image quality was ◎.

Example 2
Example 1 except that conductive nylon black having an average particle size of 0.035 μm was kneaded into nylon 6 having a 98% sulfuric acid relative viscosity of 2.7 to give an additive amount of 25% by weight to form conductive nylon 6 pellets. A polyamide long fiber, conductive flock, and brush were prepared in the same manner as described above. The results are shown in Table 1.

Example 3
A polyamide long fiber, a conductive floc, and a brush were prepared in the same manner as in Example 1 except that conductive furnace black was kneaded so as to have an addition amount of 30% by weight to obtain conductive nylon 6 pellets. The results are shown in Table 1.

Example 4
Conductive nylon cut into a polyamide long fiber and a fiber length of 1.5 mm short fiber in the same manner as in Example 1 except that conductive furnace black was kneaded into an additive amount of 25% by weight to make conductive nylon 6 pellets. Six short fibers were obtained.
Electrodeposition processing was performed in the same manner as in Example 1 with an aqueous solution obtained by mixing 30 g / L aqueous colloidal silica solution and 30 g / L aqueous alumina sol at a ratio of 6: 1 as an electrodeposition treatment agent to the obtained conductive nylon 6 short fibers. To make conductive flocks and brushes. The results are shown in Table 1.

  Example 5 A polyamide long fiber and a fiber length of 1.5 mm were cut in the same manner as in Example 1 except that conductive furnace black was kneaded so as to have an addition amount of 25% by weight to form conductive nylon 6 pellets. Conductive nylon 6 short fibers were obtained.

  The obtained conductive nylon 6 short fibers were subjected to electrodeposition treatment in the same manner as in Example 1 with an aqueous solution prepared by mixing colloidal silica 100 g / L aqueous solution and alumina sol 100% in a ratio of 6: 1 as an electrodeposition treatment agent. Conductive flocks and brushes were created. The results are shown in Table 1.

Example 6
Polyamide long fibers, conductive flocs, and brushes were prepared in the same manner as in Example 2 except that the magnesium oxide powder was powder blended to 0.005 wt% in the conductive nylon 6. The results are shown in Table 1.

Example 7
Polyamide long fibers, conductive flocs, and brushes were prepared in the same manner as in Example 2 except that magnesium oxide powder was powder blended to 2% by weight in conductive nylon 6. The results are shown in Table 1.

Example 8
Polyamide long fibers, conductive flocs and brushes were prepared in the same manner as in Example 2 except that zinc oxide powder having an electronegativity of 1.6 as a metal oxide was powder blended to 0.04% by weight in conductive nylon 6. did. The results are shown in Table 1.

Example 9
Polyamide long fibers, conductive flocs and brushes were prepared in the same manner as in Example 2 except that aluminum oxide powder having an electronegativity of 1.5 as a metal oxide was powder blended to 0.04% by weight in conductive nylon 6. did. The results are shown in Table 1.

Example 10
Polyamide long fibers, conductive flocs and brushes were prepared in the same manner as in Example 2 except that calcium oxide powder having an electronegativity of 1 as a metal oxide was powder blended in 0.04 wt% in conductive nylon 6. The results are shown in Table 1.

Example 11
Conductive flocks and brushes as in Example 2 except that the conductive nylon 6 short fibers cut into a short fiber length of 1.5 mm in Example 2 were used as an electrodeposition treatment agent in an aqueous solution of colloidal silica 50 g / L%. It was created. The results are shown in Table 1.

Example 12
Conductive flocks and brushes were used in the same manner as in Example 2 except that the conductive nylon 6 short fibers cut into a short fiber of 1.5 mm in Example 2 were used as an electrodeposition treatment agent in an aqueous solution of alumina sol 50 g / L%. Created. The results are shown in Table 1. Example 14
A polyamide continuous fiber, a conductive floc, and a brush were prepared in the same manner as in Example 2 except that no metal oxide was contained. The results are shown in Table 1.

Example 14
A polyamide long fiber, a conductive floc, and a brush were prepared in the same manner as in Example 2 except that iron oxide powder having an electronegativity of 1.8 as a metal oxide was powder blended to 0.04% by weight in conductive nylon 6. did. The results are shown in Table 2.

Comparative Example 1
Polyamide long fibers, conductive flocs, and brushes were prepared in the same manner as in Example 1 except that conductive furnace black was kneaded so as to have an addition amount of 5% by weight to obtain conductive nylon 6 pellets. The results are shown in Table 2.

Comparative Example 2
A polyamide long fiber, a conductive floc, and a brush were prepared in the same manner as in Example 1 except that conductive furnace black was kneaded so as to have an addition amount of 45% by weight to obtain conductive nylon 6 pellets. The results are shown in Table 2.

Comparative Example 3
An aqueous solution obtained by mixing conductive nylon 6 short fibers cut into a short fiber length of 1.5 mm in Example 2 with an electrodeposition treatment agent in a ratio of 6: 1 colloidal silica aqueous solution 10 g / L and alumina sol aqueous solution 10 g / L. A conductive floc and a brush were prepared in the same manner as in Example 1 except that the above was used. The results are shown in Table 2.

Comparative Example 4
An aqueous solution obtained by mixing the conductive nylon 6 short fiber cut into a short fiber of 1.5 mm fiber length of Example 2 with a colloidal silica aqueous solution 100 g / L and an alumina sol aqueous solution 100 g / L as an electrodeposition treatment agent in a ratio of 6: 1. A conductive floc and a brush were prepared in the same manner as in Example 1 except that the above was used. The results are shown in Table 2.

Comparative Example 5
Conductive flocks and brushes were used in the same manner as in Example 2 except that the conductive nylon 6 short fibers cut into a short fiber of 1.5 mm in Example 2 were used as an electrodeposition treatment agent in an aqueous solution of 50 g / L tannic acid. Created. The results are shown in Table 2.

As shown in Tables 1 and 2, the polyamide long fibers containing 10 to 40% by weight of the conductive carbon of Examples 1 to 14 have a specific resistance value of 10 ⁴ to 10 ¹⁰ Ωcm, and are appropriate resistance as a conductive brush. A value is obtained. Moreover, it turns out that the conductive floc which provided 1-7 weight% of ash content of Examples 1-14 is excellent in flying property, there are few crystal deposition of an electrodeposition processing agent, and it is excellent in electrostatic flocking processing. Moreover, it turns out that the electrically conductive brush of Examples 1-14 is excellent in printing durability.

In contrast, the polyamide long fiber containing 5% by weight of conductive carbon (Comparative Example 1) has a high brush resistance value of 10 ¹⁰ Ω when used as a conductive brush, and therefore cannot supply toner and cannot print. It was. Polyamide long fibers containing 45% by weight of conductive carbon (Comparative Example 2) have low operability of spinning yarn breakage of 30 times / t and cannot withstand production.

The conductive floc using tannic acid as the electrodeposition treatment agent (Comparative Example 5) had a toner surface treatment that was altered by tannic acid, and the printing durability evaluation was x.
In addition, the conductive floc (Example 14) composed of a polyamide long fiber containing conductive carbon using iron oxide having an electronegativity of 1.8 as a metal oxide has a slightly high flying property of 26 seconds. I understand that it is.

  An electrodeposition treatment agent having a low concentration of a mixed liquid composed of colloidal silica and alumina sol (Comparative Example 3) has a high flying property of 45 seconds, takes a long time for electrostatic flocking, and can withstand production. is not. When the concentration of the mixed liquid composed of colloidal silica and alumina sol is high (Comparative Example 4), the amount of crystal deposition of the electrodeposition treatment agent is as high as 0.8%. The printing durability deteriorates.

Furthermore, the colloidal silica simple substance (Example 12) and the alumina sol simple substance (Example 13) have a resistance value of the conductive floc of 10 ⁸ Ω, and the flying property is somewhat slow as 25 to 28 seconds. That is, since the surface resistance value of the conductive floc is high, the amount of charge imparted to the conductive floc is low even when a high voltage is applied, and the flying force is weak and the flying property is deteriorated.

  The present invention relates to a conductive flock used for an electrophotographic recording type dry copying machine, a facsimile, a printer, and the like. Specifically, the present invention relates to a conductive flock used for a conductive brush created by electrostatic flocking.

It is the schematic which shows the measuring method of the electrically conductive brush of this invention.

Explanation of symbols

1 Conductive flock with electrostatic flocking on core material 2 Core material 3 Weight 4 Stainless steel metal plate 5 Resistance meter

Claims (5)

A conductive flock comprising a polyamide fiber containing 10 to 40% by weight of conductive carbon and provided with an electrodeposition treatment agent, wherein the ash content of the conductive flock is 1 to 7% by weight. Conductive flock. The conductive floc according to claim 1, wherein the polyamide fiber containing conductive carbon contains 0.01 to 1% by weight of a metal oxide composed of a metal having an electronegativity of 1.7 or less. 3. The conductive floc according to claim 1, wherein the electrodeposition treatment agent contains organic silicon. 4. The conductive floc according to claim 1, wherein the electrodeposition treatment agent is a mixture of colloidal silica and alumina sol. The electroconductive brush which produced the electroconductive floc in any one of Claims 1-4 by the electrostatic flocking process.

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