JP2008064808A - Electrophotographic printing toner and its printing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic printing toner having good charging characteristics and dispersibility and giving high image density and excellent texture and an electrophotographic printing method using the toner, and to provide an economical electrophotographic printing method by which the work efficiency of printing is enhanced and to which on-demand property is provided. <P>SOLUTION: The electrophotographic printing toner contains a colorant and a resin, wherein the colorant is a dye and a resin (A) having a rate of dissolution in a 10-14C paraffin oil at 25°C being 0-10% and a rate of dissolution in a 10-14C paraffin oil at 100°C being 80-100% is contained as the resin. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a toner used for electrophotographic printing and an electrophotographic printing method using the toner.

The textile printing method is applied to various forms of textiles such as yarns, knitted fabrics, secondary products, etc., and the mainstream is roller printing using an intaglio plate by screen type and mechanical operation, screen using stencil printing, and paper pattern printing. Screen printing includes hand printing, semi-automatic screen printing machine, printing with an automatic traveling screen printing machine, and printing with a flat type and rotary type automatic screen printing machine.
However, roller printing has a complicated process of engraving a pattern on a metal roller and handling of the roller is difficult, and screen printing has problems such as time-consuming screen production and time-consuming printing work. . In addition, rotary screen printing has problems such as the time required for screen production and roller engraving. As described above, since the conventional printing method has a complicated manufacturing process and takes a long time until completion, a simple printing method has been desired.

  In recent years, a printing method using an ink jet that can be manufactured in a short period of time while omitting a conventional engraving plate making process has been proposed (Patent Documents 1 to 5 and the like). However, the ink-jet printing method has drawbacks such as that the density cannot be increased and that the density changes while printing.

  In order to solve these problems, a textile printing method using an electrophotographic method has been recently developed. In this method, an electrostatic latent image is formed on a photoreceptor, toner is attached, the toner is transferred to cloth, and the toner is fixed by heat (Patent Documents 6 to 7, etc.). However, this electrophotographic printing method uses a dry toner, and since the toner layer is thick, it is not soft to the touch, and because it is physically attached to the fiber by a resin, it is resistant to friction and resistance. There were problems such as poor washing characteristics.

Patent Documents 8 to 9 and the like have proposed an electrophotographic printing method using liquid toner. In this method, a liquid toner using a sublimation dye is developed by ion flow, a pattern is printed on a transfer material, and this is superposed on a cloth to perform sublimation heat transfer. This method is a natural and simple method in terms of touch and the like, but in the case of color, there are drawbacks such as difficulty in producing a density superimposed on the second color and inferior washing resistance. Further, it is necessary to carry out double-sided printing without the toner getting into the back of the cloth. In addition, the work is complicated, and there is a problem that paper (transfer material) that is no longer necessary after transfer onto the cloth is wasted.
The difference between normal printing and electrophotographic printing at the stage before the color treatment is that, in the case of normal screen printing, etc., the dye is attached to the cloth in the state of colored glue, whereas In the case of photographic printing, the dye is adhered to the cloth in the form of particles. For this reason, the commonly used coloring method has a problem that the reactivity between the cloth and the reactive dye is insufficient, and the dyeing characteristics such as the coloring density are lowered.

  Patent Document 10 is an invention using a water-soluble or alkali-soluble resin so that a resin component can be removed by a soaping process. Although the resin can be removed by a normal soaping process, there is a limit to the water-soluble resin content because the chargeability is lowered by increasing the water-soluble resin.

Japanese Patent Laid-Open No. 10-195576 Japanese Patent No. 2995135 JP 2003-96340 A JP-A-7-278482 JP-A-8-226083 JP-A-5-027474 Japanese Patent Laid-Open No. 5-033275 Japanese Patent Laid-Open No. 9-73198 JP-A-10-239916 JP 2005-256220 A

  An object of the present invention is to provide an electrophotographic printing toner having good charging characteristics and dispersibility, high image density and excellent texture, and an electrophotographic printing method using the toner. It is another object of the present invention to provide a wasteless electrophotographic printing method that greatly improves the workability of printing and has on-demand characteristics.

The said subject is solved by the following (1)-(13) of this invention.
(1) “A colorant and a resin are contained, the colorant is a dye, and the resin has a solubility of 0 to 10% in a 25 ° C. paraffin oil (C10 to C14), and a 100 ° C. paraffin oil ( An electrophotographic printing toner comprising a resin (A) having a dissolution rate of 80 to 100% in C10 to C14);
(2) “The electrophotographic printing toner according to (1) above, wherein the resin (A) has a number average molecular weight of 500 to 20000 as measured by GPC method”,
(3) “Electrophotographic textile toner according to item (1) or (2), wherein the ratio of the resin (A) to the total resin amount is 50 to 90%”;
(4) The ratio of the resin (A) to the amount of the dye [(resin (A) / dye) × 100%] is 50 to 250%, wherein the items (1) to ( 3) the electrophotographic printing toner according to any one of items
(5) "The electrophotographic printing toner according to any one of (1) to (4) above, wherein the purity of the dye is 80 to 100% by weight";
(6) "The electrophotographic printing toner according to any one of (1) to (5) above, wherein the absolute value of the ζ potential of the toner is 10 to 200 mV";
(7) “Electrophotographic printing toner according to any one of items (1) to (6), wherein the toner has a weight average particle diameter of 0.1 to 5 μm”,
(8) “After using the electrophotographic printing toner according to any one of (1) to (7) to develop an electrostatic latent image on a photoreceptor, pressure is applied by a transfer roller to form an image. An electrophotographic printing method characterized by transferring the "
(9) “Using the electrophotographic printing toner according to any one of (1) to (7), an electrostatic latent image is developed on a photosensitive member, and a toner image is firstly transferred to an intermediate transfer member. An electrophotographic printing method characterized in that after transfer, the image is secondarily transferred to a transfer medium ”,
(10) “The electrophotographic printing method according to item (9), including a step of spraying a solvent onto the intermediate transfer body before the secondary transfer”;
(11) Any of the above-mentioned items (8) to (10), wherein the photoconductor is arranged in a tandem type, the image is transferred to a transfer medium pasted on a belt, and full color printing is performed. Electrophotographic printing method according to
(12) The above-mentioned (8) to (12), wherein the image formed on the transferred material is colored and fixed by a pad steam method at an alkali concentration of 0.1 to 10%. Electrophotographic printing method according to any one of "
(13) Any one of the above items (8) to (12), wherein the resin (A) component is removed from the printed fabric and fiber by dissolving with a paraffinic oil at 80 to 100 ° C. "Electrophotographic printing method according to crab".

  According to the present invention, it is possible to provide an electrophotographic printing toner having good electrical characteristics and dispersibility, high image density and excellent dyeability, and an electrophotographic printing method using the toner. Further, it is possible to provide a wasteless electrophotographic printing method that greatly improves the workability of printing and has on-demand properties. Furthermore, it is possible to provide an electrophotographic printing toner capable of obtaining a high-quality image having a good texture, and to provide an electrophotographic printing method having good transferability to a cloth having poor smoothness.

The present invention will be described in detail below.
The present invention relates to an electrophotographic printing toner used in an electrophotographic printing method in which toner particles in which a colorant is dispersed are printed on a transfer medium such as cloth by an electrophotographic method, and an electrophotographic printing method using the electrophotographic printing toner. The resin contains a resin, and a part of the resin has a dissolution rate of 0 to 10% in a 25 ° C. paraffin oil (C10 to C14) and a dissolution rate in a 100 ° C. paraffin oil (C10 to C14). Is 80 to 100% of the resin (A).

By using such a resin (A), resin removability can be improved without using a resin that adversely affects chargeability such as a water-soluble resin. Since the resin (A) is not soluble at room temperature, the toner particles do not dissolve even when paraffinic oil is used as the dispersion solvent, and the chargeability and development characteristics are not affected. After image formation and dyeing, the resin component can be dissolved and removed by immersion in paraffin oil at 80 to 100 ° C.
In particular, a resin having a number average molecular weight of 500 to 20000 measured by the GPC method has low adhesion to fibers and film strength, and the resin can be removed up to about 70% by a soaping method using normal warm water. Furthermore, if the resin dissolution removal with paraffin oil at 80 to 100 ° C. is used in combination, the resin removal rate becomes 90% or more (see FIG. 6).

  The resin (A) having a solubility in paraffin oil (C10 to C14) at 25 ° C. of 0 to 10% and a solubility in paraffin oil (C10 to C14) of 100 ° C. of 80 to 100% is low molecular weight. Examples include polyethylene resins, low-molecular polypropylene resins, low-molecular ethylene-vinyl acetate copolymers, low-molecular propylene-vinyl acetate copolymers, rosin-modified polyester resins, rosin-modified maleic acid resins, and rosin-modified phenol resins.

Examples of the C10 to C14 paraffin oil include C ₁₀ H ₂₂ , C ₁₁ H ₂₄ , C ₁₂ H ₂₆ , C ₁₃ H ₂₈ , and C ₁₄ H _30, and there are mixtures, linear structures, and branched structures thereof.
Specific product names include Isopar C, Isopar E, Isopar G, Isopar H, Isopar L, Isopar M, Isopar V, Christol J52, Christol J72, Christol J102, Christol J142, Christol J172, Crystal There are Stall J202, Pure Rex 7, Pure Rex 12, Pure Allex 30, Pure Rex 90, and the like.

The dissolution rate in paraffin oil is determined by the following method.
(1) Mix 100 g of paraffin oil and 20 g of resin. (Sufficient stirring and mixing)
(2) Pressure filtration with a 0.1 μm Millipore filter.
(3) Weigh the residue on the filter and measure the dry weight X.
(4) Dissolution rate = ((20−X) / 20) × 100%
In the case of 100 ° C., the filter and the pressure filtration device are also heated to the same level.

In the case of liquid toner, it is preferable to contain a dispersion resin (B1) that enhances dispersion stability as at least a part of the resin (B) other than the resin (A).
Preferred dispersing resins (B1) include a vinyl monomer (b1) represented by the following general formula (1), a vinyl monomer represented by the following general formula (2), vinyl pyridine, vinyl pyrrolidone, ethylene glycol dimethacrylate, styrene, One type each of the monomer (b2) selected from divinylbenzene and vinyltoluene, or several types of copolymers and graft copolymers.

（Ｒ_１はＨまたはＣＨ_３を、ｎは６〜２０の整数を表わす。）

(R ₁ represents H or CH ₃ and n represents an integer of 6 to 20)

（Ｒ_１は、Ｈ又はＣＨ_３、Ｒ_２は、Ｈ又は炭素数が１〜４のアルキル基を表わす。）

(R ₁ represents H or CH ₃ , and R ₂ represents H or an alkyl group having 1 to 4 carbon atoms.)

  The content of the resin (A) having a dissolution rate in a paraffin oil (C10 to C14) of 25 ° C. of 0 to 10% and a dissolution rate of 80 to 100% in a paraffin oil (C10 to C14) of 100 ° C. is The content is desirably 50 to 90% of the resin amount. More preferably, it is 50 to 70%. If it is less than 50%, the resin removability is lowered and the texture is deteriorated. If it exceeds 90%, the proportion occupied by the dispersion resin (B1) decreases, and the dispersion stability decreases.

  The ratio of the resin (A) to the dye ((the resin (A) / dye) × 100%) is desirably 50 to 250%. Furthermore, 80 to 120% is desirable. When it is less than 50%, the dye is easily detached from the toner particles, and the development characteristics are deteriorated. If it exceeds 250%, the coloring power is lowered and the density is lowered.

  Commercially available powder dyes have a dye purity of about 50% by weight and often contain a large amount of salt and sodium sulfate, which adversely affects the resistance and chargeability of the solution. It is preferable to use a dye having a small amount. It is preferable to use a material having a purity of 80% by weight or more because a high-quality image can be obtained.

The purity of the dye is determined by the following dissolution and reprecipitation method.
(1) The dye is extracted using a solvent (N, N-dimethylformamide or the like) that dissolves only the dye without dissolving inorganic salts such as salt and sodium sulfate.
(2) A solvent (such as acetone) that does not dissolve the dye is mixed with the dye solution represented by the above (1) to precipitate the dye.
(3) Purity is calculated as (weight of precipitated dye / weight of initial dye) × 100 (%).

Examples of the dye that can be used in the present invention include acid dyes, reactive dyes, direct dyes, disperse dyes, and cationic dyes.
Examples of direct dyes include direct first yellow R, direct first yellow GC, direct first orange, direct sky blue 5B, direct splat red 3B, coplantin green G, and direct fast black D.
Examples of the acid dye include Acid Brilliant Scarlet 3R, Acid Violet 5B, Alizarin Direct Blue A2G, Acid Syanine 6B, Acid Syanine Green G, and Acid First Black VLG.
Examples of the cationic dye include cationic yellow 3G, cationic golden yellow GL, cationic orange R, cationic brilliant red 4G, and cationic blue 5G.
Examples of disperse dyes include Disperse Fast Yellow-O G, Disperse Blue FFR, Disperse Blue Green B, Disperse Yellow 5G, Disperse Thread FB, and the like.
Examples of reactive dyes include Reactive Orange 2R, Reactive Red 3B, Reactive Blue 3G, Reactive Brilliant Blue R, Reactive Black B, and the like.

It is necessary to use an optimum dye according to the fabric to be printed, such as a disperse dye for polyester fiber, a cationic dye for acrylic fiber, and a reactive dye or direct dye for cotton fiber.
As the carrier liquid, a high-resistance liquid is preferable, and saturated aliphatic hydrocarbons such as isoparaffinic hydrocarbons, silicone oils, and the like are preferable.
Isoparaffinic hydrocarbons include Isopar C, Isopar E, Isopar G, Isopar H, Isopar L, Isopar M, Isopar V, Solvesso 100, Solvesso 150, Solvesso 200, Exor 100/140, Exor D30, Exor D40, Exor D80 , Exol D110, Exol D130 (exxon Mobil, Exxon Chemical), etc., and silicone oils include KF96: 1 to 10000 cst (Shin-Etsu Silicone), SH200, SH344 (Toray Silicone), TSF451 (Toshiba Silicone), etc. .
The boiling point is preferably 100 to 350 ° C. If it is this range, there will be no problem in a coloring process and a high quality image will be obtained. If it is less than 100 ° C., the solvent tends to volatilize before transfer, and the effect of improving transferability is reduced, and it is not preferable for the operator in terms of odor, safety, and volatile solvent vapor. If it exceeds 350 ° C., the solvent is difficult to volatilize, and the solvent cannot be removed in the color development step, causing a problem in the color development characteristics. If it is 350 degrees C or less, it can evaporate at the stage of a heating and steaming of a post process.

In the case of dry printing toner, the volume average particle size is desirably 3 to 20 μm, and if it is less than 3 μm, dust is generated, and if it exceeds 20 μm, the color and resolution are deteriorated.
The particle diameter of the dry printing toner is determined by the Coulter counter method. The Coulter Counter method is a method usually used for measuring the particle size of dry printing toner. The toner is dispersed in the electrolyte solution, and voltage is applied from both sides of the partition wall having small holes. Since the electrolyte solution corresponding to the volume of the particles is eliminated from the small holes, the electrical resistance between the left and right electrodes increases instantaneously, generating a voltage pulse. The particle size distribution is obtained from the number of pulses and the magnitude.

In the case of liquid textile printing toner, the absolute value of ζ potential is preferably 10 to 200 mV. Within this range, a high quality image can be obtained. When the ζ potential is lower than 10 mV, the toner particles aggregate, electrophoretic properties are deteriorated and the background is soiled, and the density is decreased. On the other hand, if the ζ potential is higher than 200 mV, the adhesion amount of the photosensitive member may decrease and the density may decrease.
The weight average particle size of the liquid printing toner is preferably 0.1 to 5 μm. Within this range, a high quality image can be obtained. If the thickness is less than 0.1 μm, sufficient density cannot be obtained or blurring tends to occur, and if it exceeds 5 μm, the color and resolution may be deteriorated.

After development on the photoconductor, transfer is performed with a transfer roller under a pressure of 0.1 to 3 kg / cm ² , so that transferability is improved even on transfer paper or cloth with poor smoothness, and a high-density image can be formed. .
Also, when transferring using an intermediate transfer member, a higher pressure is applied, so transferability to transfer paper or cloth with poor smoothness is improved. However, since the amount of solvent during transfer is smaller than when not using an intermediate transfer body, in the case of textile printing, a solvent such as aliphatic hydrocarbon or silicone oil is sprayed onto the intermediate transfer body before secondary transfer to transfer It is desirable to ensure the amount of solvent necessary for the above. This further improves the transferability. A good spraying amount is about 0.20 to 0.70 mg / cm ² .
In the case of textile printing, in order to improve the density, the amount of developer is increased, or the amount of developer squeezed on the reverse roller after development is reduced, so that the amount of developer on the photoconductor is increased and applied to cloth, etc. Increasing the amount of solvent soaking is effective.
When the transfer voltage is directly transferred onto a cloth or the like, the absolute value is preferably 1000 to 7000 V, and when the intermediate transfer is used, the primary transfer is preferably 100 to 1000 V and the secondary transfer is preferably 300 to 7000 V.

By using the textile printing toner of the present invention, an image transferred to a transfer material such as cloth by electrophotography is developed by a color process using a pad / steam method with an alkali concentration of 0.1 to 10 mol%, thereby providing excellent dyeing properties. can get.
In the case of ordinary reactive dye printing ink that is attached to cloth as a color paste in which the dye is dissolved before the color treatment, the reactive group of the reactive dye reacts with the hydroxyl group of cotton (cellulose) to form a covalent bond. Is generated. For this reason, it is possible to cope with color reactive fixing treatment of general reactive dyes such as alkali shock method and cold batch method (see FIG. 5).
On the other hand, in the case of printing toner, as shown in FIG. 5, the dye is not dissolved in the solvent and is adhered to the cloth in the form of particles, and the resin for controlling the charging property is around the dye. Due to the adhesion, the reactivity between the reactive group of the dye and the hydroxyl group such as cotton cloth (cellulose) becomes insufficient in a normal fixing treatment, and a sufficient dyeing effect cannot be obtained.

It has been found that by performing color treatment by the pad-steam method with an alkali concentration of 0.1 to 10 mol%, it is possible to obtain a dyeing characteristic equivalent to that of a normal textile ink even when an electrophotographic textile toner is used. .
As the alkaline component, a solution in which a hydroxide such as sodium, calcium, barium or the like, sodium carbonate, sodium hydrogen carbonate, ammonium carbonate, sodium phosphate or the like is used in an aqueous solution having a concentration of 0.1 to 10 mol% is used. Although any of these materials can provide the effect, sodium bicarbonate (sodium bicarbonate, NaHCO ₃ ) is particularly preferable.
The concentration of the aqueous alkali solution needs to be 0.1 to 10 mol%. Preferably it is 0.5-5 mol%, More preferably, it is 0.5-2 mol%. When the alkali concentration is lower than 0.1 mol%, the reactivity is lowered, and when the alkali concentration is higher than 10 mol%, the reactive group of the dye itself is hydrolyzed before the reaction with cotton cloth (cellulose) or the like, It may be crushed.
The treatment temperature is 80 to 140 ° C, preferably 95 to 110 ° C. When the treatment temperature is lower than 80 ° C., the resin (resin (A) + (resin (B))) or dye is not sufficiently dissolved and the reactivity is lowered. The dye reactive group may be destroyed before the reaction.
Moreover, it is preferable to carry out by the steaming method using not only temperature but heating steam.

  In the case of disperse dyes, it penetrates through sublimation and is dyed on a polyester cloth by van der Waals force. The problem does not occur. It can be dyed by the usual HP method and HT.

FIG. 1 is a view showing an example of an image forming apparatus used in the electrophotographic textile printing method of the present invention. Charge is applied to the photoreceptor by the charging voltage application member, and the non-image area charge is erased by exposure. As the photoreceptor, a selenium photoreceptor, an organic photoreceptor, or an amorphous silicon photoreceptor can be used. The surface potential of the photoreceptor is good in the range of 400 to 1600V. The latent image with the charge remaining on the photosensitive member is developed with the liquid developer supplied from the developing roller, the excess developer is removed with the reverse roller, and the transfer voltage applying agent is applied to a voltage opposite to the toner charge. To transfer to the printed fabric.
The developing roller rotates in the forward direction with the photoconductor, the reverse roller rotates in the reverse direction, and the linear velocity relative to the photoconductor is 1.2 to 6 times that of the developing roller, and the linear velocity of the reverse roller is 1.2 to 4 times It is effective. Thereby, a high quality image is obtained.
The gap between the roller and the photoconductor is preferably 50 to 250 μm, and the gap between the reverse roller is 30 to 150 μm. The transfer voltage is preferably in the range of 500 to 4000V.
After the toner remaining on the photoconductor without being transferred to the cloth is removed by a cleaning blade and a cleaning roller, the photoconductor is discharged.
Further, an image can be formed in the same manner by a developing method that erases the charge in the image portion and leaves the charge in the non-image portion.

FIG. 2 is an example in which the transfer voltage applying member in FIG. 1 is changed from a charger system to a roller system.
Compared with the charger method, pressure at the time of transfer can be applied, so transferability is good even in the case of a fabric with rough surface and large unevenness. The transfer pressure is preferably 0.1 to 3 kg / cm ² .

FIG. 3 is an example in which an intermediate transfer member is added to the apparatus of FIG. Since a higher transfer pressure than that of the apparatus of FIG. 2 can be applied, the transferability is good even in the case of a cloth with rough surface roughness and large unevenness. The primary transfer pressure is preferably 0.1 to 3 kg / cm ² , and the secondary transfer pressure is preferably 0.1 to 5 kg / cm ² . However, the solvent component in the toner is reduced during the primary transfer to the intermediate transfer member, and the amount of solvent required for the secondary transfer from the intermediate transfer member to the cloth may be reduced. It is effective to add a step of spraying a solvent onto the substrate.

  FIG. 4 shows an example of an apparatus that performs full-color printing by arranging photoconductors in tandem and attaching a cloth on a cloth conveying belt. In this way, high-quality full-color printing can be performed at high speed.

The electrophotographic dry printing toner mixes colorant, resin and charge control agent, kneads in a kneader such as Busconida, and then coarsely pulverizes and finely pulverizes the coarse and fine powders to a predetermined particle size. Obtained.
In electrophotographic liquid textile printing toner, a colorant, resin, and carrier liquid are charged into a dispersing machine such as a ball mill, kitty mill, disk mill, and pin mill, and dispersed to prepare a concentrated toner, which is dispersed in the carrier liquid of the present invention. Can be obtained.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited by these Examples. In the case of reactive dye toner, 200 broad (40 warps / inch, weft 80 / inch) cotton cloth is used for the reactive dye toner, and polyester satin cloth is applied to the paper for the disperse dye toner. Used. In the examples and comparative examples, “parts” are all “parts by weight”, and the mixing ratio of the monomers of the copolymer is a weight ratio.

(Example 1)
The following materials were placed in a pin mill and dispersed for 10 hours. Further, 300 parts of Isopar H was added and dispersed for 1 hour, and this was used as a concentrated printing toner.
Using the developer mixed with 100 g of this concentrated printing toner and 1 L (liter) of Isopar H, electrophotographic printing was performed with the apparatus of FIG.

・ Disperse dye (Sumikaron Red E-FBL) (Sumitomo Chemical Co., Ltd.) (purity 50%) 40 parts and polyethylene resin (A-C629) (Honeywell Co.) 45 parts melt kneaded and pulverized 85 parts ・ Lauryl methacrylate / methyl Methacrylate / methacrylic acid (80/10/10) copolymer Isopar H 20% by weight solution 100 parts Isopar H 180 parts Charge control agent (zirconium naphthenate) 3 parts

(Example 2)
The following materials were kneaded with Busconida, cooled, coarsely pulverized with a pulverizer, pulverized with a jet mill and classified, and 3 parts of silica was added as an external additive to obtain a dry printing toner.
Using this toner, textile printing was performed with a Ricoh dry printer Imagio.
-Disperse dye (Kayalon Polyster Turquoise BlueGL-S) (purification treatment purity 90%) (Nippon Kayaku Co., Ltd.) 25 parts and polyethylene resin (210P) (Mitsui Chemicals Co., Ltd.) 50 parts melt kneaded and pulverized 75 parts-Charge control agent (Metal complex of salicylic acid derivative) 2 parts

(Example 3)
The following materials were placed in a ball mill and dispersed for 24 hours. Further, 250 parts of Isopar H was added and dispersed for 1 hour, and this was used as a concentrated printing toner.
Electrophotographic printing was performed with the apparatus of FIG. 2 using a developer in which 100 g of this concentrated printing toner and Isopar H, 1 L were mixed.
95 parts of melt-kneaded pulverized 60 parts of reactive dye (Cibacron TurquoiseBlueFGF-P) (purification purity 85%) (manufactured by Ciba Chemical) and 35 parts of polyethylene resin (171P) (manufactured by Sanyo Kasei) 95 parts Methacrylate / methacrylic acid (80/10/10) copolymer Isopar H 30 wt% solution 100 parts ・ Isopar H 250 parts ・ Charge control agent (zirconium octoate) 5 parts

Example 4
A concentrated printing toner was prepared in the same manner as in Example 1 except that the disperse dye (Sumikaron Red E-FBL) of Example 1 (purity of 50% by weight) was purified to 90% by weight.
Electrophotographic printing was performed with the apparatus of FIG. 2 using a developer in which 100 g of this concentrated printing toner and Isopar H, 1 L were mixed.

(Example 5)
A concentrated printing toner was prepared in the same manner as in Example 3 except that the dispersion medium in Example 3 was changed from Isopar H to silicone oil (KF-96 2cst).
Electrophotographic printing was performed with the apparatus shown in FIG. 2 using a developer in which 100 g of this concentrated printing toner and 1 L of silicone oil (KF-96 2cst) were mixed.

(Example 6)
The following materials were put into a batch type sand mill and dispersed for 12 hours. Further, 350 parts of Isopar H was added and dispersed for 1 hour to obtain a concentrated printing toner.
Electrophotographic printing was performed with the apparatus of FIG. 2 using a developer in which 100 g of this concentrated printing toner and Isopar M 1 L were mixed.
・ 68 parts of melt-kneaded and pulverized 22 parts of disperse dye (FS-Red 1339) (purity 98%) and 46 parts of ethylene vinyl acetate resin (EV150) (Mitsui DuPont Polychemical Co., Ltd.) ・ 2-ethylhexyl methacrylate / methyl methacrylate / Methacrylic acid (80/10/10) copolymer Isopar H 35 wt% solution 120 parts Isopar H 200 parts Charge control agent (zirconium naphthenate) 2 parts

(Example 7)
The following materials were put into a batch type sand mill and dispersed for 12 hours. Further, 350 parts of Isopar H was added and dispersed for 1 hour to obtain a concentrated printing toner.
Electrophotographic printing was performed with the apparatus of FIG. 2 using a developer in which 100 g of this concentrated printing toner and 1 L of Exol D30 were mixed.
・ Resolved dye (Remazol Black B) (purified to 97% purity) 30 parts and rosin modified maleic resin (MRG-H) (Hitachi Chemical Co., Ltd.) 38 parts melt kneaded and pulverized 68 parts ・ 2-ethylhexyl methacrylate / Methyl methacrylate / Methacrylic acid (80/10/10) Isopar H 20 wt% solution of copolymer 50 parts ・ Isopar H 200 parts ・ Charge control agent (zirconium naphthenate) 2 parts

(Example 8)
The following materials were placed in a ball mill and dispersed for 36 hours. Further, 280 parts of Isopar H was added and dispersed for 1 hour, and this was used as a concentrated printing toner.
Electrophotographic printing was performed with the apparatus of FIG. 2 using a developer in which 100 g of this concentrated printing toner and Isopar H, 1 L were mixed.
・ 50 parts of reactive dye (Cibacron Black FBG-A) (purified to 70% purity) and 30 parts of polyethylene resin (420P) (Mitsui Chemicals) 80 parts ・ Lauryl methacrylate / methyl meta Acrylate / methacrylic acid (80/10/10) Isopar H 15 wt% solution of copolymer 30 parts ・ Isopar H 170 parts ・ Charge control agent (zirconium naphthenate) 2 parts

Example 9
Using a developer in which 100 g of the concentrated printing toner of Example 3 and Isopar H 1 L (liter) were mixed, electrophotographic printing was performed with the apparatus of FIG. 3 to which an intermediate transfer member was attached.

(Example 10)
Electrophotographic printing was performed in the same manner as in Example 9, except that 0.3 mg / cm ² of Isopar H was sprayed before the secondary transfer.

(Comparative Example 1)
The following materials were placed in a pin mill and dispersed for 10 hours. Further, 300 parts of Isopar H was added and dispersed for 1 hour, and this was used as a concentrated printing toner.
Using the developer mixed with 100 g of this concentrated printing toner and 1 L (liter) of Isopar H, electrophotographic printing was performed with the apparatus of FIG.
・ Disperse dye (Sumikaron Red E-FBL) (manufactured by Sumitomo Chemical Co., Ltd.) (purity 50%) 40 parts and epoxy resin (Epicoat 1002) (Japan Epoxy Resin Co., Ltd.) 45 parts kneaded and pulverized 85 parts ・ Lauryl methacrylate / Methyl methacrylate / methacrylic acid (80/10/10) copolymer Isopar H 20% by weight solution 100 parts Isopar H 180 parts Charge control agent (zirconium naphthenate) 3 parts

(Comparative Example 2)
95 parts of melt-kneaded pulverized 45 parts of reactive dye (Cibacron Turquoise BlueFGF-P) (purification purity 55%) (Ciba Chemical Co.) and 50 parts of petroleum resin (Picotex LC) (Hercules Co.) Methyl methacrylate / methacrylic acid (80/10/10) isopar H 30 wt% solution of copolymer 100 parts ・ Isopar H 250 parts ・ Charge control agent (zirconium octoate) 5 parts Resin used in Examples and Comparative Examples, It has the following composition.

In Examples 1, 2, 4, 5, 6, 9, 10 and Comparative Example 1 using a polyester cloth, the printed cloth was steamed at 190 ° C. for 30 minutes, 2 g / L of sodium carbonate, 2 g / L of hydrosulfite. Was then treated with warm water at 80 ° C. for 20 minutes, and further washed with stirring at 100 ° C. Cristol J52 for 15 minutes to prepare a printed sample.
In Examples 3, 7, 8 and Comparative Example 2 using a cotton cloth, a 2% by weight aqueous solution of sodium bicarbonate was applied to a printed cloth, steamed at 100 ° C. for 15 minutes, allowed to stand for 1 hour, washed with water, A printing sample was prepared by carrying out a 5 minute treatment at 80 ° C. with 2 g / L of a surfactant, and then stirring and washing with Isopar M at 100 ° C. for 15 minutes.
The results are shown in Table 2.
As is apparent from the results in Table 2, the electrophotographic printing toner and the electrophotographic printing method of the present invention yielded a printed fabric having high charge control rate, transfer rate, fabric density, high resolution and good texture. .
In Example 4, since the purity of the dye is increased, the image density is higher than that in Example 1. In Example 10, since Isopar H was sprayed on the image on the intermediate transfer roller before the secondary transfer, the transfer rate was increased and the image density was improved as compared with Example 9.
In addition, the textile printing toner of Comparative Example 1 had poor soaping and dissolution cleaning properties and poor texture. In the textile printing toner of Comparative Example 2, the resin was easily dissolved in the toner solvent, the toner characteristics were lowered, and the image quality was poor.

＊画像濃度はＸ−Ｒｉｔｅにより測定。
＊地汚れは地汚れ段階見本布による。評価は５段階（５：最良、１：最悪）
＊風合は風合段階見本布による。評価は５段階
（５：布のみと同程度の柔らかさ、４：柔らかい、３：中程度、２：やや硬い、１：硬い）
＊重量平均粒径は島津製作所ＳＡ−ＣＰ３による。
捺染トナーを積分球式濁度計で透過率１５％程度になるまでアイソパーで希釈し、ＳＡ−ＣＰ３用セルに充填しＡＣＣＥＬ４８０、ＭＯＤＥ：ＣＥＮＴ、３〜１６チャンネルの条件で測定。
＊ζ電位は大塚電子ＥＬＳ−８０００による。
セル：低誘電率セル、電界：５００Ｖ／ｃｍ、６回測定平均モードで測定。
＊解像性は、段階見本による。評価は５段階（５：最良、１：最悪）
＊転写率はテープ剥離法による濃度から算出。
転写率＝〔（転写前感光体上濃度−転写後感光体残濃度）／（転写前感光体上濃度）〕×１００％

* Image density is measured by X-Rite.
* Soil stain is based on the soil stain stage sample cloth. Evaluation is 5 levels (5: best, 1: worst)
* The texture is according to the texture-level sample cloth. Evaluation is 5 grades (5: Softness equivalent to cloth only, 4: Soft, 3: Medium, 2: Slightly hard, 1: Hard)
* Weight average particle diameter is from Shimadzu SA-CP3.
The printing toner is diluted with Isopar until the transmittance is about 15% with an integrating sphere turbidimeter, filled in a cell for SA-CP3, and measured under the conditions of ACCEL480, MODE: CENT, 3 to 16 channels.
* Ζ potential is based on Otsuka Electronics ELS-8000.
Cell: Low dielectric constant cell, electric field: 500 V / cm, measured in 6 measurement average mode.
* Resolution depends on the stage sample. Evaluation is 5 levels (5: best, 1: worst)
* The transfer rate is calculated from the concentration by the tape peeling method.
Transfer rate = [(Concentration on photoconductor before transfer−Remaining photoconductor density after transfer) / (Concentration on photoconductor before transfer)] × 100%

1 is a diagram illustrating an example of an image forming apparatus used in an electrophotographic printing method of the present invention. The figure which shows the example which made the transfer voltage provision member of FIG. 1 the roller system. The figure which shows the example which added the intermediate transfer member to the apparatus of FIG. The figure which shows an example of the apparatus which arrange | positions a photoreceptor to a tandem and sticks a cloth on a cloth conveyance belt, and performs full color printing. It is a figure showing the mode of color fixation processing in textile ink and textile toner. It is a figure explaining soaping and resin dissolution removal.

Claims (13)

It contains a colorant and a resin, and the colorant is a dye. The resin has a solubility in a paraffin oil (C10 to C14) of 25 ° C. of 0 to 10%, and a paraffin oil (C10 to C14) of 100 ° C. An electrophotographic printing toner comprising a resin (A) having a dissolution rate of 80 to 100%. 2. The electrophotographic printing toner according to claim 1, wherein the resin (A) has a number average molecular weight of 500 to 20,000 as measured by GPC method. The electrophotographic printing toner according to claim 1 or 2, wherein a ratio of the resin (A) is 50 to 90% with respect to a total resin amount. The ratio of the resin (A) to the amount of the dye [(resin (A) / dye) x 100%] is 50 to 250%, The electrophotography according to any one of claims 1 to 3 Textile toner. The electrophotographic printing toner according to any one of claims 1 to 4, wherein the purity of the dye is 80 to 100% by weight. 6. The electrophotographic printing toner according to claim 1, wherein an absolute value of the ζ potential of the toner is 10 to 200 mV. 7. The electrophotographic printing toner according to claim 1, wherein the toner has a weight average particle diameter of 0.1 to 5 [mu] m. An electrophotographic textile printing comprising: developing an electrostatic latent image on a photoreceptor using the electrophotographic textile toner according to any one of claims 1 to 7; and applying a pressure with a transfer roller to transfer the image. Method. 8. An electrophotographic printing toner according to claim 1, wherein the electrostatic latent image is developed on a photosensitive member, the toner image is primarily transferred to an intermediate transfer member, and then the image is transferred to the transfer member. An electrophotographic printing method characterized in that it is transferred next. 10. The electrophotographic printing method according to claim 9, further comprising a step of spraying a solvent onto the intermediate transfer member before the secondary transfer. 11. The electrophotographic printing method according to claim 8, wherein a photoconductor is arranged in a tandem type, an image is transferred to a transfer target adhered on a belt, and full color printing is performed. 13. The electrophotographic printing method according to claim 8, wherein the image formed on the transfer material is developed and fixed by a pad-steam method at an alkali concentration of 0.1 to 10%. The electrophotographic printing method according to any one of claims 8 to 12, wherein the resin (A) component is removed from the printed fabric and fiber by dissolving with a paraffinic oil at 80 to 100 ° C.

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