JP2005256220A - Toner for electrophotographic textile printing - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner for electrophotographic textile printing imparting images with fluorescent color, high image density and high resolution, and to provide a method for textile printing, and to provide a method markedly improving workability of the textile printing, having on demand's ability and avoiding waste in textile printing. <P>SOLUTION: The invention relates to the toner used in electrophotography for textile printing in which toner particles comprising coloring agent dispersed in the particles are directly printed on a fabric to be printed by an electrophotographic system, wherein fluorescent pigments are used as the coloring agent. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an electrophotographic printing toner and a printing method thereof.

  The textile printing method is applied to various forms of textiles such as yarn, knitted fabric, secondary products, etc., and the mainstream is roller printing using an intaglio plate by screen type and mechanical operation, screen by 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. 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, the conventional printing method has a complicated manufacturing process and takes a long time until completion, and thus 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 (for example, see Patent Documents 1 and 2) has been proposed. In particular, Patent Documents 3 to 5 have been devised as those using fluorescent dyes. However, the ink-jet printing method has drawbacks such that the density cannot be increased, and the density changes while printing.

  In order to solve these problems, a printing method using an electrophotographic method has been recently developed. In this method, an electrostatic latent image is formed on a photosensitive member, toner is adhered, the toner is transferred to cloth, and the toner is fixed by heat. However, the electrophotographic printing method of Patent Documents 6 and 7 uses a dry toner, and since the toner layer thickness is thick, the touch is not good and the resin is physically attached to the fiber, There were problems such as poor friction fastness and washing resistance.

  Patent Documents 8, 9 and the like are disclosed as electrophotographic printing methods using liquid toner. In this method, a liquid toner using a sublimation dye is developed by an 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 simple method with a natural touch and the like. However, in the case of color, there are drawbacks such as difficulty in producing a density superimposed on the second color and poor washing resistance. Further, the toner does not penetrate to the back side of the cloth, and it is necessary to print on both sides. 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.

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

Accordingly, an object of the present invention is to provide an electrophotographic toner for printing and a printing method therefor, which can obtain a high-resolution image with a fluorescent color and high image density, in view of the above-described conventional technology.
It is another object of the present invention to provide a wasteless printing method that greatly improves the workability of printing and has on-demand properties.

The above-mentioned problem is (1) “printing toner for use in an electrophotographic printing method in which a toner particle in which a colorant is dispersed is printed directly on a printed cloth by an electrophotographic method, and contains a fluorescent dye as a colorant. Electrophotographic textile toner characterized by
(2) “Liquid for use in an electrophotographic printing method in which toner particles in which a colorant is dispersed in a carrier liquid having a high resistance and a low dielectric constant of 10 ⁹ Ω · cm or more are directly printed on a printed fabric by electrophotography. An electrophotographic liquid printing toner characterized in that it is a printing toner and contains a fluorescent dye as a colorant;
(3) “The electrophotographic liquid printing toner according to (2) above, wherein the fluorescent dye is a fluorescent dye and the purity thereof is 80 to 100%”,
(4) “The electrophotographic liquid printing toner according to (2) or (3) above, wherein the carrier liquid is an aliphatic saturated hydrocarbon having a boiling point of 100 to 350 ° C.”,
(5) Any of the above-mentioned (2) to (4), wherein the carrier liquid contains a resin component, and at least a part of the resin is an alkali-soluble resin or a water-soluble resin "Electrophotographic liquid textile printing toner"
(6) "The electrophotographic liquid printing toner according to item (5), wherein the alkali-soluble or water-soluble resin has an acid value of 0 to 2000 mg / KOH";
(7) The items (2) to (2), wherein the fluorescent dye is kneaded or flushed with a water-soluble resin in the presence of humic acid, humic acid salt or humic acid derivative. (6) Electrophotographic liquid textile printing toner according to any one of items
(8) The electrophotographic liquid printing according to any one of (2) to (7), wherein an average particle diameter of toner particles in the liquid toner is 0.1 to 5 μm toner",
(9) “It was formed by developing an electrostatic latent image on a photoreceptor using the electrophotographic toner according to any one of (1) to (8), and then applying pressure with a transfer roller. This is achieved by an “electrophotographic printing method characterized by transferring an image to a material to be printed”.
Further, the above-mentioned problem is characterized in that (10) “the electrostatic latent image on the photosensitive member is developed, the toner image is primarily transferred to the intermediate transfer member, and then the image is secondarily transferred to the printing material. The electrophotographic printing method according to item (9),
(11) “The electrophotographic printing method according to item (10), including a step of spraying a solvent onto the intermediate transfer member before the secondary transfer”;
(12) “A developing roller is used when developing the electrostatic latent image on the photosensitive member, the carrier liquid is a solvent, and the developing roller line for developing with toner against the linear velocity of the photosensitive member. The squeeze roller for removing excess solvent is used at a speed of 1.2 to 6 times, and the linear speed is 1.2 to 4 times the linear speed of the photosensitive member (10) Or the electrophotographic printing method according to item (11) ",
(13) According to any one of (9) to (12), wherein the photoconductor is arranged in a tandem type, and an image is transferred to a cloth attached on a belt and full color printing is performed. This is achieved by the described electrophotographic printing method.

According to the present invention, fluorescent dyes (for example, dyes, pigments, fluorescent resins, etc.) are contained as colorants in the electrophotographic system, so that it is excellent in on-demand, high image density, deep and vivid fluorescent color printing is possible. become.
Toners using fluorescent dyes are well known, but most are used for printing on paper or the like. Further, the fluorescent dye ink used for textile printing is an ink having neither charging characteristics nor toner characteristics. The present invention is used in a process for direct printing by electrophotography, and there has never been a technique capable of solving the hue, on-demand property, texture of printing, and dye dispersibility with a fluorescent dye.
In addition, the density, resolution, and transferability are further improved.
Further, since the fluorescent pigment is a dye and its purity is 80% or more, a high-quality image can be provided.
Further, since the carrier liquid is an aliphatic saturated hydrocarbon having a boiling point of 100 to 350 ° C., there is no problem in the coloring process, and a high-quality image can be provided.
Further, since an alkali-soluble resin or a water-soluble resin is contained in at least a part of the resin, it is possible to provide a high-quality image with a good texture.
Moreover, since the acid value of alkali-soluble resin or water-soluble resin is 0-2000 mg / KOH, a high quality image can be provided.
Further, since the colorant is kneaded or flushed using a polyolefin resin and a water-soluble resin in the presence of humic acid, humic acid salt, or humic acid derivative, a high-quality image can be provided.
Moreover, since an average particle diameter is 0.1-5 micrometers, a high quality image can be provided.
In addition, after the electrostatic latent image is developed on the photosensitive member, pressure is applied by a transfer roller to form an image, so that transferability to paper or cloth with poor smoothness is good.
Further, since the electrostatic latent image is developed on the photosensitive member, the toner image is transferred to the intermediate transfer member, and then the image is formed, the transfer property to paper or cloth having poor smoothness is good.
Further, since the method includes a step of spraying a solvent onto the intermediate transfer body before the secondary transfer, transferability is further improved.
Further, since the linear velocity of the developing roller is 1.2 to 6 times that of the photosensitive member and the linear velocity of the squeeze roller is 1.2 to 4 times, a high quality image can be obtained.
In addition, since the photoconductor is arranged in a tandem type and the image is transferred to the cloth affixed on the belt, high-quality full-color printing can be provided at high speed.

The present invention relates to an electrophotographic printing method characterized in that toner particles in which a colorant is dispersed are directly printed on a printed fabric by an electrophotographic method, wherein the electrophotographic method comprises a fluorescent dye as a colorant It is a printing toner. In particular, high-quality printing can be obtained in a liquid electrophotographic apparatus for printing characterized in that printing is performed by dispersing toner particles in a carrier liquid having a volume resistance of 10 ⁹ Ω · cm or more and a high resistance and a low dielectric constant.

As the fluorescent dye, dyes such as diaminostilbene, fluorescein, thioflavine, eosin, rhodamine B, coumarin derivatives, imidazole derivatives, and pigment types can be used. As the fluorescent dye, a fluorescent whitening dye can be used in addition to a normal fluorescent dye. The fluorescent whitening dye is a dye that absorbs light of 340 to 380 nm and fluoresces the absorption energy in the visible region near 400 to 450 nm to give whiteness.
As the fluorescent pigment, an inorganic fluorescent pigment can be used in addition to a normal daylight fluorescent pigment. Inorganic fluorescent pigments have a luminous property as found in nocturnal paints.

Fluorescent dyes that can be used in the present invention include Solvent Yellow 44, Solvent Orange 5, 55, Solvent Red 49, 149, 150, Solvent Blue 5, Solvent Green 7, Acid Yellow 3, 7, Acid Red 52, 77, 87, 92, Acid Blue 9, Basic Yellow 1, 40, Basic Red 1, 13, Basic Violet 7, 10, 110, Basic Orange 14, 22, Basic Blue 7, Basic Green 1, Bat Red 41, Disperse Yellow 82 121, 124, 184: 1, 186, 199, 216, disperse orange 11, disperse thread 58, 239, 240, 345, 362, 364, disperse blue 7, 56, 183, 155, 354, 365 Disperse Violet 26, 27, 28, 35, 38, 46, 48, 57, 63, 77, 97, Direct Yellow 85, Direct Orange 8, 9, Direct Blue 22, Direct Grain 6, Fluorescent Brightening Agent 54, There are a fluorescent brightening agent 135, a fluorescent brightening agent 162, a fluorescent brightening agent 260, and the like.
In addition to these fluorescent dyes, colorants such as ordinary acid dyes, reactive dyes, direct dyes, disperse dyes, cationic dyes, organic pigments and inorganic pigments can be used in combination.
Both pigments and dyes can be used, but using a dye as a colorant is superior in texture, dyeability and wash fastness.
When using dyes, the dyeability and washing fastness are better when the dye is selected depending on the material of the printed fabric. For example, polyester fibers are disperse dyes, cellulose fibers are reactive dyes, direct dyes, acrylic fibers are cationic. Acid dyes are preferred for dyes, polyamide fibers and wool fibers.
Moreover, when it is desired to suppress the polarity of the functional group with a reactive dye or an acid dye, it is also effective to stabilize the charging performance by wrapping with a resin.
However, if the resin content is increased, the dyeing on the back surface and the texture of the fibers become worse, so it is desirable to suppress the amount to 4 times or less with respect to the colorant.

Commercially available powder dyes have a dye purity of about 50% and often contain a large amount of salt and sodium sulfate, which adversely affects the resistance and chargeability of the solution. It is better to use a dye. A purity of 80% or more is desirable.
When a dye having a purity of about 50% is used, there may be a decrease in chargeability and colorability. It is desirable that the toner has positive or negative charging characteristics. However, the dispersant and the mirabilite, which are impurities in the dye, adversely affect the electrical characteristics. Further, since the substantial dye content is reduced, the colorability may be lowered and the concentration may be lowered. For this reason, it is preferable to increase the purity by using or purifying a dye having a purity of 80% or more. Purification methods include a method using an osmotic membrane and a method of dissolving and recrystallizing.

The carrier liquid used in the liquid developer of the present invention is preferably a high resistance and low dielectric constant material, such as isoparaffin hydrocarbons and silicone oils. Isoparaffin hydrocarbons are 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, Exor D110, Exor D130 (Exxon Mobil Co., Ltd.) (Exxon Chemical) etc. are available. Examples of silicone oils are KF96 1-10000 cst (Shin-Etsu Silicon), SH200, SH344 (Toray Silicon), TSF451 (Toshiba Silicon), etc. is there.
The boiling point is preferably 100 to 350 ° C. When the temperature is 100 ° C. or lower, the solvent is likely to volatilize before transfer, and the effect of improving transferability is reduced. Odor, safety, and volatile solvent vapor are not preferable for the operator. Above 350 ° C., the solvent is difficult to volatilize, and the solvent cannot be removed in the color development step, causing a problem in 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.
Further, as a dispersion resin preferably used in combination with the present invention, the following formula

（Ｒ_１はＨまたはＣＨ_３を、ｎは６〜２０の整数を表わす。）
であらわされるビニルモノマーＡと

(R ₁ represents H or CH ₃ and n represents an integer of 6 to 20)
Vinyl monomer A represented by

（Ｒ₂はＣが１〜４のアルキル基）
で表わされるビニルモノマー及びビニルピリジン、ビニルピロリドン、エチレングリコールジメタクリレート、スチレン、ジビニルベンゼン、ビニルトルエンより選ばれるモノマーＢの各一種ずつもしくは、数種の共重合体、グラフト共重合体が挙げられる。
また、樹脂の一部にはアルカリ可溶性樹脂、水溶性樹脂を含有させると、発色、水洗工程でトナー中の樹脂が溶解し、布から脱離するため、風合の良好な捺染布が得られる。
発色水洗工程では、１００℃前後でスチーミング後、０．１〜２％程度のアルカリで処理する場合があり、アルカリ可溶性樹脂、水溶性樹脂を含有させないと、樹脂分が残り、風合を劣化させる原因となるが、アルカリ可溶性樹脂、水溶性樹脂を含有させることにより、発色水洗工程で樹脂が離脱し、風合の良好な捺染が得られる。
非水溶性樹脂とアルカリ可溶性樹脂又は水溶性樹脂の割合は９／１〜１／９が望ましい。更に望ましくは５／５〜２／８である。非水溶性樹脂分が少ないとトナーの帯電性が低下し、アルカリ可溶性樹脂又は水溶性樹脂分が少ないと風合が低下する。
アルカリ可溶性樹脂又は水溶性樹脂は、水溶性メラミン樹脂、水溶性ロジン変性樹脂、水溶性ポリエステル樹脂、水溶性アクリル樹脂、水溶性エポキシ樹脂、ポリビニルアルコール、ポリビニルピロリドン、ポリエチレンイミン、カルボキシメチルセルロース、アルギン酸ソーダ、コラーゲン、ゼラチン、デンプン、キトサン等がある。
商品としては、クラレ社製ポバール（ＰＶＡ）、イソバン（イソブチレン／マレイン酸樹脂）、ハリマ化成製ネオトール、ハリディプ（アルキッド樹脂、アクリル樹脂）、日本合成化学社製エコアティ（ＰＶＡ）、ナガセケムテックス社製デコナール（エポキシ樹脂）、日本純薬社製ジュリアー（アクリル樹脂）、カブセン（ポリエステル樹脂）などが挙げられる。

(R ₂ is an alkyl group having 1 to 4 carbon atoms)
And vinyl monomers and vinyl pyridine, vinyl pyrrolidone, ethylene glycol dimethacrylate, styrene, divinyl benzene, and vinyl toluene, each of which is one type of monomer B, or several types of copolymers and graft copolymers.
In addition, when an alkali-soluble resin or a water-soluble resin is contained in a part of the resin, the resin in the toner dissolves and is detached from the cloth in the color development and washing steps, so that a printed fabric with a good texture can be obtained. .
In the colored water washing process, after steaming at around 100 ° C., it may be treated with about 0.1 to 2% alkali. If no alkali-soluble resin or water-soluble resin is contained, the resin will remain and the texture will deteriorate. However, when an alkali-soluble resin or a water-soluble resin is contained, the resin is detached in the coloring water washing step, and printing with a good texture can be obtained.
The ratio of the water-insoluble resin to the alkali-soluble resin or the water-soluble resin is preferably 9/1 to 1/9. More desirably, it is 5/5 to 2/8. If the amount of the water-insoluble resin is small, the chargeability of the toner is lowered, and if the content of the alkali-soluble resin or the water-soluble resin is small, the texture is lowered.
Alkali-soluble resin or water-soluble resin is water-soluble melamine resin, water-soluble rosin modified resin, water-soluble polyester resin, water-soluble acrylic resin, water-soluble epoxy resin, polyvinyl alcohol, polyvinylpyrrolidone, polyethyleneimine, carboxymethylcellulose, sodium alginate, There are collagen, gelatin, starch, chitosan and the like.
Products include Poval (PVA) manufactured by Kuraray Co., Ltd., Isoban (isobutylene / maleic acid resin), Neotor made by Harima Kasei, Halidip (alkyd resin, acrylic resin), Eco Coati (PVA) manufactured by Nippon Gosei Kagaku Co., Ltd., Nagase ChemteX Corporation Examples include deconal (epoxy resin), Julia (acrylic resin), Kabsen (polyester resin) manufactured by Nippon Pure Chemical Co., Ltd.

The acid value is preferably from 0 to 2000 mg / KOH, and if it is higher than 2000 mg / KOH, the development characteristics deteriorate.
On the other hand, if it is larger than 2000, there will be a problem in chargeability, and the development characteristics will deteriorate, or the stability with time will deteriorate due to aggregation.

In particular, when an alkali-soluble resin, a water-soluble resin, or a colorant is subjected to a flushing treatment, a developer excellent in image surface can be obtained. Further, although fluorescent dyes and the like are not well dispersible in the resin, by using a flushing treatment, the dye can be uniformly dispersed in the resin, and a high concentration can be obtained. In particular, when humic acid is used in the flushing treatment, the dispersibility is further improved.
In the flushing process, a resin dispersion medium is further added to a water-containing liquid in which a pigment is dissolved in water, and the mixture is mixed well in a kneader called a flasher, and water existing around the pigment is replaced by a resin dispersion medium added later. The process to do.
The water discharged by this operation is discharged, the pigment is dispersed in the resin solution, dried, the solvent is removed, and the resulting mass is pulverized to obtain a colorant powder.
The ratio of the colorant to the resin during the flushing is suitably 10 to 60 parts by weight of the colorant with respect to 100 parts by weight of the resin. The flushing treatment is particularly advantageously carried out in the presence of humic acid, humic acid salts (Na salt, NH ₄ salt etc.) or humic acid derivatives. The amount of these humic acids added is suitably about 0.1 to 30% by weight of the colorant-containing liquid.

  The average particle size of the toner particles in the liquid developer is desirably 0.1 to 5 μm. If the particle size is 0.1 μm or less, a sufficient concentration may not be obtained or blurring may occur easily. , Resolution may be deteriorated. The toner particles in the present invention are composed of a pigment and a resin. Since the average particle size of the wet toner is generally about 0.5 to 3 μm, the average particle size of 0.1 to 5 μm of the present invention is slightly wider than that. Generally smaller than dry toner (about 7 μm).

In the case of the apparatus of FIG. 1, the transfer pressure of the present invention is suitably 0.1 kg / cm ² or less because the transfer is performed with light contact. Since the apparatus of FIG. 2 applies pressure with a transfer roller, 0.1 to 3 kg / cm ² is preferable. If it is 0.1 Kg / cm ² Kg or less, the transferability is lowered, and if it is 3 Kg / cm ² Kg or more, the photoconductor and the photoconductor shaft are burdened and the durability of the apparatus is affected. In the apparatus of FIG. 3, 0.1-20 Kg / cm < ² > is preferable. Since there is an intermediate transfer member, there is a margin in the durability of the apparatus even if the transfer is raised, but since the transfer solvent is reduced, it is necessary to increase the transfer pressure or to spray the solvent.
When development is performed on the photosensitive member and the transfer roller is applied with a pressure of 0.1 to 3 kg / cm ² , the transfer property is improved in the case of transfer paper or textile printing with poor smoothness, and a high-density image can be formed.
Further, when transferring using an intermediate transfer member, transfer performance is improved because a higher pressure is applied. The intermediate transfer member has a volume resistance of 10 ³ to 10 ¹⁰ Ω · cm, preferably 10 ⁵ to 10 ⁷ Ω · cm. If the resistance is too low or too high, the transfer characteristics deteriorate. The material is preferably silicone rubber or hydrin rubber, and preferably has a release layer such as a fluorine coating layer on the surface. However, since the amount of solvent during transfer is less than when no intermediate transfer member is used, in the case of textile printing, a solvent such as aliphatic hydrocarbon or silicone oil is sprayed onto the intermediate transfer member before secondary transfer. It is desirable to secure the necessary amount of solvent.
When the solid content of the toner layer on the intermediate transfer member is 25% or more, transferability is improved by solvent spraying. The solid content can be obtained by a heat loss test method for toner sampled from the intermediate transfer roller.
The same type of solvent as that used for the carrier liquid is preferable.
The spraying method is the best spraying method, but application by a coating roller is also possible.
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 the developer is increased, or the amount of the developer on the photoconductor is increased by decreasing the amount of solvent squeezed on the squeeze roller after development. Increasing the solvent penetration is effective. By squeezing, the solid content of the toner layer on the photoreceptor after squeezing needs to be about 10 to 30%. If the squeeze is too sweet, dripping, background smearing, and image flow tend to occur. When the squeeze is excessive, the toner layer is scraped off to a necessary level and the density is lowered, or the amount of solvent necessary for transfer is reduced and transferability tends to be lowered.
When the linear velocity of the developing roller is 1.2 times or less, a liquid pool necessary for development is not formed, so that a place where development is not performed is formed or liquid sag occurs. If it is 6 times or more, the scraping power of the liquid increases and the image becomes thin. If the linear speed of the squeeze roller is 1.2 times or less, the squeeze effect is small and liquid dripping or background contamination is liable to occur, and if it is 4 times or more, the squeeze effect is too strong, resulting in a decrease in density and poor transfer.
The present invention is also effective for dry toners. The technique described in Japanese Patent Application Laid-Open No. 5-27474 improves the texture by using a flexible resin, but has a limit. In the present invention, by using a water-soluble resin, the original printing texture can be secured by removing the resin itself in the washing step.
In the case of dry toner, the resin used preferably has a softening point of 70 to 170 ° C. from the viewpoint of storage stability. In the case of wet toner, -20 to 120 ° C is desirable.

Hereinafter, it explains in more detail using a drawing.
FIG. 1 shows an example of the image forming 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 400v to 1600v. The latent image with the charge remaining on the photoreceptor is developed with the liquid developer supplied from the developing roller, the excess developer is removed with the squeeze roller, and the transfer voltage applying agent generates a voltage opposite to the charge of the toner. Transfer to swatch fabric.
The developing roller rotates in the forward direction with respect to the photosensitive member, the squeeze roller rotates in the reverse direction, and the linear velocity relative to the photosensitive member is 1.2 to 6 times that of the developing roller, and the linear velocity of the squeeze roller is 1.2 to 4 times. Double is effective.

The gap between the roller and the photosensitive member is preferably 50 to 250 μm, and the gap between the squeeze roller is preferably 30 to 150 μm. The transfer voltage is preferably in the range of 500 to 4000 v.
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 shows 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 shows 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 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 for performing full-color printing by arranging photosensitive members in tandem and attaching a cloth on a cloth conveying belt.
A developer is prepared by adding a colorant, a resin, and a carrier liquid to a dispersing machine such as a ball mill, a kitty mill, a disk mill, and a pin mill, dispersing and kneading to prepare a concentrated toner, and dispersing this in the supporting liquid of the present invention. Can be obtained.
After being transferred to the cloth by the electrophotographic method shown in FIGS. 1, 2, 3, and 4, the drying, steaming process, coloring process, washing process, and processing process can be performed on the line. For example, in printing using disperse dyes, the HP method in which high-pressure dyeing is performed at about 130 ° C. and the HT method in which high-temperature dyeing is performed at about 190 ° C. are usually used in the drying and steaming processes. After dyeing, the resin content is removed and washed by soaping with alkali or surfactant. In the case of conventional plate printing, since excessive printing ink adheres to the cloth, there are many waste liquids in the soaping and cleaning processes, and environmental problems have been serious. In addition, in the case of inkjet textile printing, it is necessary to pre-treat the cloth in advance, and there are problems that the cloth pre-treatment process takes time and the cloth discolors over time. On the other hand, the present invention directly prints the necessary and sufficient dye on the cloth, which not only simplifies the printing process but also has a great environmental advantage.
It is necessary to devise the conveyance of the cloth to be transferred in the apparatus shown in FIGS. 1 to 4 so that the cloth is not deformed such as stretch or wrinkle. The cloth conveyance method most suitable for the present invention is a system in which a cloth is stuck on a cloth conveyance belt and conveyed. The cloth can be attached by pre-coating a pressure sensitive adhesive or the like on the conveyor belt.

(Example 1)
Fluorescent red dye (Solvent Red 63, 50% purity product) 50 parts Laparyl methacrylate / Methyl methacrylate / Methacrylic acid / Glycidyl methacrylate (80/10/5/5) copolymer Isopar H 20% solution
110 parts Polyolefin resin (ethylene / vinyl acetate copolymer resin) (Evaflex)
(Mitsui / DuPont) 60 parts Water-soluble resin Poval (PVA) (Kuraray) 60 parts Isopar H 180 parts Charge control agent (zirconium naphthenate) 3 parts in a ball mill and dispersed for 24 hours, then add 300 parts of Isopar H This was dispersed for 1 hour to obtain a concentrated toner.
Electrophotographic printing was performed with the apparatus shown in FIG. 1 using a developer in which 100 g of this concentrated toner and Isopar H1L were mixed.

(Example 2)
Fluorescent orange dye (solvent orange 5 purity 90% product) 20 parts Polyolefin resin (ethylene / methacrylic acid copolymer resin) (Nucle)
(Mitsui / DuPont) 40 parts Water-soluble resin Kabsen (water-soluble polyester) (Nagase ChemteX) 70 parts Charge control agent (metal complex of salicylic acid derivative) 2 parts are kneaded with busconida, cooled and coarsely pulverized with a pulverizer After pulverization and classification, a dry toner having an average particle size of 7.9 μm was obtained. The cloth was attached to paper, and this toner was used for printing with the Ricoh dry printer Imagio.

(Example 3)
Fluorescent yellow dye (acid yellow 7 purity 80%) 50 parts Polyolefin resin (ethylene / vinyl acetate copolymer resin) (Evaflex)
(Mitsui / DuPont) 20 parts Water-soluble resin Halidive (water-soluble alkyd resin) (Harima Kasei) 80 parts Nitrohumic acid 3 parts kneader and flushing 70 parts of the above flashing kneaded product Lauryl methacrylate / methyl methacrylate / methacrylic acid / Isopar H 20% solution of glycidyl methacrylate (80/10/5/5) copolymer
100 parts Isopar H 250 parts Charge control agent 5 parts was placed in a ball mill and dispersed for 24 hours, and then 250 parts of Isopar H was added and dispersed for 1 hour to obtain a concentrated toner.
Electrophotographic printing was performed with the apparatus shown in FIG. 2 using a developer in which 100 g of this concentrated toner and Isopar H1L were mixed.

Example 4
A concentrated toner was prepared in the same manner as in Example 1 except that the fluorescent red dye of Example 1 (Solvent Red 63, 50% purity product) was used after being purified to 90% purity.
Electrophotographic printing was performed with the apparatus shown in FIG. 2 using a developer in which 100 g of this concentrated toner and Isopar H1L were mixed.

(Example 5)
A concentrated toner was prepared in the same manner as in Example 2 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 of FIG. 2 using a developer in which 100 g of this concentrated toner and silicone oil (KF-96 2cst) were mixed.

(Example 6)
Fluorescent red dye (Basic Red 1 purity 90%) 40 parts Polyolefin resin (ethylene / methacrylic acid copolymer resin) (Nucrel)
(Mitsui / DuPont) 5 parts Water-soluble resin Kabusen (water-soluble polyester) (Nagase ChemteX) 95 parts kneaded and pulverized 90 parts lauryl methacrylate / methyl methacrylate / methacrylic acid / glycidyl methacrylate (80 / 10/5/5) Isopar H20% solution of copolymer
120 parts Isopar H 200 parts Charge control agent (zirconium naphthenate) 2 parts in a ball mill and dispersed for 24 hours, 350 parts of Isopar H was further added and dispersed for 1 hour to obtain a concentrated toner.
Electrophotographic printing was performed with the apparatus shown in FIG. 2 using a developer in which 100 g of this concentrated toner and Isopar M were mixed.

(Example 7)
Fluorescent orange pigment (Sinroich FZ2001 red orange purity 80%)
40 parts Polyolefin resin (ethylene / methacrylic acid copolymer resin ionomer)
(High Milan) (Mitsui / DuPont) 95 parts Water-soluble resin Kabusen (water-soluble polyester) (Nagase ChemteX) 5 parts kneaded and pulverized 90 parts lauryl methacrylate / methyl methacrylate / methacrylic acid / glycidyl methacrylate (80/10/5/5) Copolymer Isopar H20% solution
120 parts Isopar H 200 parts Charge control agent (zirconium naphthenate) 2 parts in a ball mill and dispersed for 24 hours, 350 parts of Isopar H was further added and dispersed for 1 hour to obtain a concentrated toner.

Electrophotographic printing was performed with the apparatus shown in FIG. 2 using a developer in which 100 g of this concentrated toner and Exol D30 were mixed.
The printed fabrics of Examples 1 to 7 were subjected to appropriate post-treatments such as steaming and soaping. The results are shown in Table 1 below.
In addition, Examples 8 and 9 in which printing was performed using the toner of Example 3 with the apparatus of FIG. 1 for charge transfer (transfer pressure of 0.1 kg / cm ² or less) and the apparatus of FIG. Further, Example 10 in which Isopar H was sprayed at 0.3 mg / cm ² or more before secondary transfer was similarly evaluated.

(Example 11)
Fluorescent yellow dye (acid yellow 7 purity 80%) 50 parts Polyolefin resin (ethylene / vinyl acetate copolymer resin) (Evaflex)
(Mitsui / DuPont) 20 parts Water-soluble resin Halidibu (water-soluble alkyd resin) (Harima Kasei) 80 parts Nitrohumic acid 3 parts kneader,
70 parts of the above kneader kneaded product Isopar H 20% solution of lauryl methacrylate / methyl methacrylate / methacrylic acid / glycidyl methacrylate (80/10/5/5) copolymer
100 parts Isopar H 250 parts Charge control agent 5 parts was placed in a ball mill and dispersed for 24 hours, and then 250 parts of Isopar H was added and dispersed for 1 hour to obtain a concentrated toner.
Electrophotographic printing was performed with the apparatus shown in FIG. 2 using a developer in which 100 g of this concentrated toner and Isopar H1L were mixed.

(Comparative Example 1)
Printing was carried out in the same manner as in Example 1 except that the dye of Example 1 was changed to Disper Red 60 purity of 50%.

  As is clear from the above results, a printing fabric having a high transfer rate, a high fabric density and a high resolution was obtained by this image forming method and developer.

*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 ５：最良、１：最悪
*風合は風合段階見本布による
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
*平均粒径は島津製作所ＳＡ−ＣＰ３による
*解像性は、段階見本による 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

* Concentration measured with X-Rite
* Soil stains are based on the soil stain stage sample cloth. 5: Best, 1: Worst
* The texture depends on the textured sample fabric. 5: Softness similar to that of the cloth alone, 4: Soft, 3: Medium, 2: Slightly hard, 1: Hard
* Average particle size is from Shimadzu SA-CP3
* Resolution is based on stage samples 5: Best, 1: Worst
* Transfer rate is calculated from the concentration by tape peeling method

*蛍光特性は目視により評価

* Fluorescence characteristics are evaluated visually

In Example 1, since the resin is adsorbed to the colorant while being dispersed by a ball mill, the concentration is not so high. (Because there is a bare colorant that is not encapsulated in resin, it is not very good in terms of charging). In this respect, Example 3 in which the resin and the colorant are flushed in advance is also excellent in terms of dark chargeability and density. In Example 5, since the dispersion medium is silicone oil, the dispersibility is lowered (the particle size is increased), and the concentration is lower than that of the aliphatic hydrocarbon of Example 3. In Example 6, since the water-soluble resin is 95%, the texture is good, but the concentration is lowered. In Example 7, since the water-soluble resin is as low as 5%, the concentration is high but the texture is lowered.
(Liquid toner that is flushed with a resin blended with a specified amount of water-soluble resin using a high-purity dye and dispersed with an aliphatic hydrocarbon solvent is the best quality)
The ratio of the water-insoluble resin to the water-soluble resin is preferably 9/1 to 1/9, and more preferably 5/5 to 2/8.

It is a figure showing an example of an image forming method of the present invention It is the figure which showed the example which changed the transfer voltage provision member of FIG. 1 from the charger system to the roller system. FIG. 3 is a diagram illustrating an example in which an intermediate transfer member is added to the apparatus of FIG. 2. It is a figure showing an example of an apparatus which arranges a photoconductor in tandem and pastes cloth on a cloth conveyance belt and performs full color printing. It is the figure which showed the textile printing process by the electrophotography in this invention.

Claims (13)

An electrophotographic printing toner for use in an electrophotographic printing method in which toner particles in which a colorant is dispersed are directly printed on a printed fabric by an electrophotographic method, and containing a fluorescent dye as a colorant. A liquid printing toner for use in an electrophotographic printing method in which toner particles in which a colorant is dispersed in a carrier liquid having a high resistivity and a low dielectric constant of 10 ⁹ Ω · cm or more are directly printed on a printed fabric by electrophotography. An electrophotographic liquid printing toner comprising a fluorescent dye as a colorant. The electrophotographic liquid printing toner according to claim 2, wherein the fluorescent pigment is a fluorescent dye and has a purity of 80 to 100%. The electrophotographic liquid printing toner according to claim 2 or 3, wherein the carrier liquid is an aliphatic saturated hydrocarbon having a boiling point of 100 to 350 ° C. 5. The electrophotographic liquid printing toner according to claim 2, wherein the carrier liquid contains a resin component, and at least a part of the resin is an alkali-soluble resin or a water-soluble resin. 6. The electrophotographic liquid printing toner according to claim 5, wherein the alkali-soluble or water-soluble resin has an acid value of 0 to 2000 mg / KOH. 7. The electron according to claim 2, wherein the fluorescent dye is kneaded or flushed with a water-soluble resin in the presence of humic acid, humic acid salt or humic acid derivative. Photographic liquid printing toner. 8. The electrophotographic liquid printing toner according to claim 2, wherein an average particle diameter of toner particles in the liquid toner is 0.1 to 5 [mu] m. An electrostatic latent image is developed on a photoreceptor using the electrophotographic toner according to claim 1, and pressure is applied by a transfer roller to transfer the formed image onto a printing material. And an electrophotographic printing method. 10. The electrophotographic printing method according to claim 9, wherein the electrostatic latent image on the photosensitive member is developed, the toner image is primarily transferred to the intermediate transfer member, and then the image is secondarily transferred to the material to be printed. 11. The electrophotographic printing method according to claim 10, further comprising a step of spraying a solvent onto the intermediate transfer body before the secondary transfer. A developing roller is used for developing the electrostatic latent image on the photosensitive member, the carrier liquid is a solvent, and the linear velocity of the developing roller for developing with toner is 1. 12. The electron according to claim 10, wherein a squeeze roller for removing excess solvent is used at 2 to 6 times, and the linear velocity is 1.2 to 4 times the linear velocity of the photosensitive member. Photo printing method. 13. The electrophotographic printing method according to claim 9, wherein the photosensitive member is arranged in a tandem type, and an image is transferred to a cloth affixed on a belt and full color printing is performed.

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