JP4546908B2 - Toner for electrophotographic printing and electrophotographic printing method using the same - Google Patents

Description

  The present invention relates to a dry printing toner and a liquid printing toner used for electrophotographic printing, and an electrophotographic printing method using them.

  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 machine 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 which can be manufactured in a short period of time while omitting a conventional engraving plate making process is disclosed in JP-A-10-195576, JP-A-2959135, JP-A-2003-96340, JP-A-7. JP-A-278482 and JP-A-8-226083 have been proposed. However, the ink-jet printing method has drawbacks such that the density cannot be increased, and the color characteristics and density change while printing.

  In order to solve these problems, a printing method using an electrophotographic method has recently been developed, and Japanese Patent Application Laid-Open Nos. 2003-12958, 2002-029238, 5-027474, and 5-033275 are disclosed. Proposed in the Gazette. 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 described in these uses a dry toner and is physically attached to the fiber with a resin, so that the original color characteristics of the printing cannot be reproduced, the touch is not good, etc. There was a problem.

  An electrophotographic printing method using a liquid developer has been proposed in JP-A-9-73198, JP-A-10-239916, and the like. In this method, a toner for liquid printing using a sublimation dye is developed by an ion flow, a pattern is printed on a transfer material, and this is superimposed on a cloth and transferred by sublimation heat. This method is natural and easy to touch, but in the case of color, there are disadvantages such as poor secondary color characteristics and difficulty in obtaining high density because it is difficult to obtain the density superimposed on the second color. there were. In addition to these, there is a problem that the work is complicated, and paper (transfer material) that is no longer necessary after transfer onto the cloth is wasted.

JP-A No. 200-110085 (Patent Document 1) describes a magenta liquid printing toner using an anthraquinone colorant.
However, although it has been improved in terms of color characteristics and density, there has been a problem that charging stability is lowered after long-term use, and good dispersibility cannot be maintained.
Further, JP-A-10-254180 (Patent Document 2) proposes a wet developer for textile printing using a dye mixture represented by sorbet yellow 104 and solvent yellow 105 as dyes.
However, since these dyes are sublimation dyes, they could not be printed on cellulosic fabrics such as silk and cotton.

Japanese Patent Laid-Open No. 200-110085 JP 10-254180 A

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

That is, the said subject is solved by following (1)-(14) of this invention.
(1) “In an electrophotographic dry printing toner for printing on a printed fabric by an electrophotographic method using toner particles in which at least a colorant is dispersed in a resin, the following compounds (A), (B ), (E), (F), or a toner for electrophotographic dry textile printing, comprising a dye represented by (G) .

」；
（２）「前記電子写真乾式捺染用トナーにおいて、該トナーの体積平均粒径が３〜２０μｍであることを特徴とする前記（１）に記載の電子写真乾式捺染用トナー」；
（３）「担体液中に分散された、少なくとも着色剤を樹脂に分散させたトナー粒子を用いて、電子写真方式により捺染布に捺染するための電子写真液体捺染用トナーにおいて、前記担体液が、沸点１００〜３５０℃の脂肪族飽和炭化水素であり、該着色剤として下記化合物（Ａ）、（Ｂ）、（Ｅ）、（Ｆ）、または（Ｇ）で表わされる染料を含有することを特徴とする電子写真液体捺染用トナー。

";
(2) “The toner for electrophotographic dry printing according to (1) above, wherein the toner has a volume average particle diameter of 3 to 20 μm in the toner for electrophotographic dry printing”;
(3) "are dispersed in the charge of a body fluid, at least a colorant with toner particles dispersed in a resin, the toner for electrophotography liquid printing for printing the printed fabric by an electrophotographic method, wherein the carrier liquid is An aliphatic saturated hydrocarbon having a boiling point of 100 to 350 ° C. and containing a dye represented by the following compound (A), (B), (E), (F), or (G) as the colorant. A toner for electrophotographic liquid textile printing.

」；
（４）「前記脂肪族飽和炭化水素は、体積抵抗が１０ ^９ Ω・ｃｍ以上であることを特徴とする前記（３）に記載の電子写真液体捺染用トナー」；
（５）「前記樹脂の少なくとも一部にアルカリ可溶性樹脂及び／又は水溶性樹脂を含有することを特徴とする前記（３）又は（４）に記載の電子写真液体捺染用トナー」；
（６）「前記アルカリ可溶性又は水溶性樹脂が、その酸価が０〜２０００ｍｇ／ＫＯＨであることを特徴とする前記（３）〜（５）のいずれかに記載の電子写真液体捺染用トナー」；
（７）「前記電子写真液体捺染用トナーにおいて、該トナーを担体液中に分散させた液体現像剤のζ電位の絶対値が１０〜２００ｍＶであることを特徴とする前記（３）〜（６）のいずれかに記載の電子写真液体捺染トナー」；
（８）「前記トナー粒子の重量平均粒径が０．１〜５μｍであることを特徴とする前記（３）〜（７）のいずれかに記載の電子写真液体捺染用トナー」；
（９）「前記染料の純度が８０〜１００％であることを特徴とする前記（１）〜（８）のいずれかに記載の電子写真乾式または液体捺染用トナー」；
（１０）「電子写真捺染用トナーを用いて静電潜像を感光体上に現像後、転写ローラで圧力をかけ、画像を転写させる電子写真捺染方法において、該電子写真捺染用トナーとして前記（１）〜（９）のいずれかに記載の電子写真乾式または液体捺染用トナーを用いることを特徴とする電子写真捺染方法」；
（１１）「前記静電潜像を感光体上に現像後、中間転写体にトナー像を１次転写し、次いで画像を２次転写させることを特徴とする前記（１０）に記載の電子写真捺染方法」；
（１２）前記２次転写前に中間転写体に溶媒を吹きかける工程を含むことを特徴とする前記（１１）に記載の電子写真捺染方法」；
（１３）「前記現像において感光体の線速に対してトナーを現像するための現像ローラの線速が１．２〜６倍、過剰溶剤を除去するスクイズローラの線速が１．２〜４倍であることを特徴とする前記（１０）〜（１２）のいずれかに記載の電子写真捺染方法」；
（１４）「前記現像においてタンデム型に感光体を配置し、ベルト上に貼りつけた布に画像を転写しフルカラー捺染することを特徴とする前記（１０）〜（１３）のいずれかに記載の電子写真捺染方法」。

";
(4) "The toner for electrophotographic liquid printing according to (3) above, wherein the aliphatic saturated hydrocarbon has a volume resistance of 10 ⁹ Ω · cm or more ";
(5) “Electrophotographic liquid printing toner according to (3) or (4) above, wherein at least a part of the resin contains an alkali-soluble resin and / or a water-soluble resin”;
(6) "The toner for electrophotographic liquid printing according to any of (3) to (5) above, wherein the alkali-soluble or water-soluble resin has an acid value of 0 to 2000 mg / KOH";
(7) “In the electrophotographic liquid printing toner, the absolute value of ζ potential of a liquid developer in which the toner is dispersed in a carrier liquid is 10 to 200 mV. ) Electrophotographic liquid textile printing toner according to any one of
(8) "electrophotographic toner liquid printing according to any one of the weight average particle diameter before Quito toner particles, characterized in that a 0.1 to 5 [mu] m (3) ~ (7)";
(9) "Electrophotographic dry or liquid printing toner according to any one of (1) to (8) above, wherein the purity of the dye is 80 to 100%";
(10) In the electrophotographic printing method in which an electrostatic latent image is developed on a photoreceptor using an electrophotographic printing toner and then an image is transferred by applying pressure with a transfer roller. An electrophotographic printing method comprising using the electrophotographic dry or liquid printing toner according to any one of 1) to (9);
(11) The electrophotographic image described in (10), wherein the electrostatic latent image is developed on a photosensitive member, a toner image is primarily transferred to an intermediate transfer member, and then the image is secondarily transferred. Printing method ";
(12) The electrophotographic printing method according to (11) above, comprising a step of spraying a solvent onto the intermediate transfer body before the secondary transfer ”;
(13) “In the development, the linear velocity of the developing roller for developing the toner is 1.2 to 6 times the linear velocity of the photosensitive member, and the linear velocity of the squeeze roller for removing excess solvent is 1.2 to 4 times. The electrophotographic printing method according to any one of (10) to (12) above, which is doubled;
(14) In the above (10) to (13), the photosensitive member is arranged in a tandem type in the development, the image is transferred to a cloth affixed on a belt, and full color printing is performed. Electrophotographic printing method ".

(1) Operational effect corresponding to claim 1 In the electrophotographic dry printing toner according to claim 1, since the dye represented by the general formula (1) is contained as a colorant in the electrophotographic system, Therefore, it is possible to print with high charge density and high image density.
(2) Operational Effect Corresponding to Claim 2 The electrophotographic dry printing toner according to claim 2 can provide a high-quality image because its volume average particle diameter is 3 to 20 μm.
(3) Operational effect corresponding to claim 3 In the electrophotographic liquid printing toner according to claim 3, the carrier liquid is developed with a liquid developer which is an aliphatic saturated hydrocarbon having a boiling point of 100 to 350 ° C. Therefore, in addition to the effect of the first aspect, the density, resolution, and transferability are further excellent, and there is no problem in the coloring process, and a high-quality image can be provided.
The
(5) Operational effect corresponding to claim 5 In the electrophotographic liquid printing toner according to claim 5, at least a part of the resin contains an alkali-soluble resin and / or a water-soluble resin. Can provide good high-quality images.
(6) Effect corresponding to claim 6 In the electrophotographic liquid printing toner according to claim 6, since the acid value of the alkali-soluble resin or water-soluble resin is 0 to 2000 mg, a high-quality image is provided. it can.
(7) Operational effect corresponding to claim 7 In the toner for electrophotographic liquid printing according to claim 7, the absolute value of the ζ potential of the liquid developer in which the toner is dispersed in a carrier liquid is 10 to 200 mV. Therefore, high quality images can be provided.
(8) The effect corresponding to claim 8 In the toner for electrophotographic liquid textile printing according to claim 8, since the weight average particle diameter is 0.1 to 5 μm, a high-quality image can be provided.
(9) Effect and Action Corresponding to Claim 9 In the electrophotographic printing toner according to claim 9, since the purity of the dye represented by the general formula (1) is 80% or more, the dry or liquid electron When used as a toner for photographic printing, a high-quality image can be provided.
(10) Operational effect corresponding to claim 10 In the electrophotographic printing method according to claim 10, since the electrostatic latent image is developed on a photosensitive member and then pressure is applied by a transfer roller to form an image, smoothness is achieved. Transferability to poor paper and fabric is good.
(11) Operational effect corresponding to claim 11 In the electrophotographic textile printing method according to claim 11, after the electrostatic latent image is developed on the photosensitive member, the toner image is transferred to the intermediate transfer member to obtain an image. Since it is formed, the transferability to paper or cloth having poor smoothness is good.
(12) Operational effect corresponding to claim 12 In the electrophotographic printing method according to claim 12, in addition to the effect of claim 11, the method further includes the step of spraying a solvent onto the intermediate transfer body before the secondary transfer. Good transferability.
(13) Operational effect corresponding to claim 13 In the electrophotographic printing method according to claim 13, the linear velocity of the developing roller is 1.2 to 6 times the linear velocity of the photoreceptor, and the linear velocity of the squeeze roller. Is 1.2 to 4 times, a high-quality image can be obtained.
(14) Operational effect corresponding to claim 14 In the textile printing method according to claim 14, since the photoconductor is arranged in a tandem type and the image is transferred to the cloth affixed on the belt, the high-speed and high-image quality is achieved. Quality full color printing can be provided.

  The present invention relates to an electrophotographic printing toner for printing on a printed fabric by an electrophotographic method using toner particles in which a colorant is dispersed in a resin, and the colorant is represented by the following general formula (1). The present invention relates to a toner for electrophotographic printing characterized by containing a dye.

（式中、Ｒ_１〜Ｒ_１０はそれぞれ独立して、Ｈ、Ｃ_ｎＨ_２ｎ＋１、Ｆ、Ｃｌ、ＯＨ、ＳＯ_３Ｈ、ＮＨＣＯＣＨ_３、ＮＨＣＯＮＨ_２、ＯＣＨ_３、ＮＨＣ_６Ｈ_５、ＮＨ_２、ＮＯ_２から選ばれる基である）

(Wherein R _{1 to} R ₁₀ are each independently H, C _n H _{2n + 1} , F, Cl, OH, SO ₃ H, NHCOCH ₃ , NHCONH ₂ , OCH ₃ , NHC ₆ H ₅ , NH ₂ , NO ₂ is a group selected from ₂ )

The dye represented by the general formula (1) used in the present invention includes a novel compound depending on the type of R _{1 to} R ₁₀ .
The dye skeleton can be synthesized, for example, by heating to about 200 ° C. in the presence of a base such as sodium hydroxide using aromatic nitro compounds and aromatic amines and carrying out a normal azo coupling reaction. .
The reactive group portion of the triazine ring can be synthesized from, for example, the following reaction.

またＲ_１〜Ｒ_１０の官能基は、例えばＦ、Ｃｌ、はＨＦ、Ｃｌ_２等によるハロゲン化反応、ＳＯ_３ＨはＨ_２ＳＯ_４等によるスルホン化反応、ＮＯ_２は硝酸等によるニトロ化反応、ＮＨ_２はＮＯ_２の還元等一般的な方法により得ることができる。

The functional groups of R _{1 to} R ₁₀ are, for example, a halogenation reaction with F, Cl, HF, Cl ₂ , SO ₃ H is a sulfonation reaction with H ₂ SO ₄ , NO ₂ is a nitration reaction with nitric acid, etc. NH ₂ can be obtained by a general method such as reduction of NO ₂ .

The dye represented by the general formula (1) used in the present invention is used as a dye for electrophotographic printing toner of either dry or wet type.
The electrophotographic liquid printing toner in which the dye represented by the general formula (1) is dispersed in a carrier liquid having a volume resistance of 10 ⁹ Ω · cm or more and a high resistance and low dielectric constant is particularly high quality as a red printing toner. Can be obtained.
Cellulosic natural fibers such as cotton and hemp are good reactive dyes that chemically react with functional groups in the fibers and are dyed by covalent bonds. In the present invention, by using the dye represented by the general formula (1), excellent performance in charging characteristics, color characteristics, image density and dyeing property can be obtained. The chemical reaction between the triazine group of the material represented by the general formula (1) and the fiber is represented by the following formula.

In general textile printing ink, the electrical characteristics of the ink are meaningless because an image is created using a plate. However, in the case of electrophotography, charging is performed because an image is formed with positive or negative electrical characteristics. Properties are very important. By using the dye represented by the general formula (1), the charging characteristics are improved. The clear reason is unknown, but it is thought to be due to a delicate balance between the dye skeleton, the electron withdrawing group, and the electron donating group.
Examples of the dye represented by the general formula (1) include those shown in Table 1 below.
In Table 1, the dye A is reactive red 12, the dye B is reactive red 2, and the dye G is reactive red 1.

Also, other red dyes can be mixed and used together with the red dye represented by the general formula (1). When other red dyes are used, 30% by weight or less of the total dye is desirable.
When a full-color image is formed by electrophotography, it is desirable that each color is close to the target reference color, although the four primary colors are mixed. In the printing field, Japan color is used as one of the target standards. When the red dye represented by the general formula (1) is converted into a toner, the color reproducibility is close to the target value and good. The red dye represented by the general formula (1) has a high coloring power, and can produce a high image density even with a small amount of 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 liquid. It is better to use. In the present invention, the dye represented by the general formula (1) preferably has a purity of 80% or more.
Here, the purity of the dye is determined by the following dissolution and reprecipitation method.
<1> Extraction is performed using a solvent (N, N-dimethylformamide or the like) that dissolves only the dye without dissolving inorganic salts such as sodium chloride and mirabilite.
<2> A solvent (such as acetone) that does not dissolve the dye is mixed with the dye solution of <1> to precipitate the dye.
<3> Purity (%) = (Precipitated dye weight / initial dye weight) × 100
To calculate the purity.

The carrier liquid used in the liquid developer using the electrophotographic liquid printing toner of the present invention is preferably a high resistance and low dielectric constant, and is preferably an isoparaffinic hydrocarbon, a silicone oil or the like. 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 carrier liquid preferably has a high resistance and a low dielectric constant having a volume resistance of 10 ⁹ Ω · cm or more.

  The boiling point of the carrier liquid is preferably 100 to 350 ° C. (under normal temperature and normal pressure: 25 ° C., 1 atm). When the temperature is lower than 100 ° C., 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. If the temperature is higher than 350 ° C., the solvent is difficult to volatilize, and the solvent cannot be removed in the coloring process, which causes a problem in coloring characteristics. If it is 350 degrees C or less, it can evaporate at the stage of a heating and steaming of a post process.

  Examples of the resin (binder resin) used in the electrophotographic dry printing toner of the present invention include styrene / acrylic resin, polyester resin, and epoxy resin.

Examples of the resin (dispersing resin) used in the toner for electrophotographic liquid printing of the present invention include acrylic resins, vinyl toluene / acrylic resins, styrene / butadiene resins, and the like.
Further, as a resin (dispersion resin) that is preferably used in the toner for electrophotographic liquid printing of the present invention,

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

(In the formula, R represents H or CH ₃ and n represents an integer of 6 to 20).
Vinyl monomer A represented by

（式中、ＲはＨまたはＣＨ_３を、Ｒ’は炭素数が１〜４のアルキル基又はＨを表わす。）
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の各一種づつ、もしくは、数種の共重合体や、グラフト共重合体が挙げられる。

(In the formula, R represents H or CH ₃ , and R ′ represents an alkyl group having 1 to 4 carbon atoms or H.)
Each of the vinyl monomers represented by the formula (1), each of monomer B selected from vinyl pyridine, vinyl pyrrolidone, ethylene glycol dimethacrylate, styrene, divinyl benzene, and vinyl toluene, or several types of copolymers and graft copolymers. Can be mentioned.

In addition, when an alkali-soluble resin and / or a water-soluble resin is contained in a part of the resin, the resin in the toner dissolves in the color development and washing steps and is detached from the cloth, so that a printed fabric with a good texture can be obtained. It is done.
In the colored water washing process, after steaming at around 100 ° C., it may be treated with about 0.1 to 2% alkali. If an alkali-soluble resin or a water-soluble resin is not included, the resin content remains and the texture deteriorates. 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.

Examples of the alkali-soluble resin or water-soluble resin include water-soluble melamine resin, water-soluble rosin modified resin, water-soluble polyester resin, water-soluble acrylic resin, water-soluble epoxy resin, polyvinyl alcohol, polyvinyl pyrrolidone, polyethyleneimine, carboxymethyl cellulose, sodium alginate , Collagen, gelatin, starch, chitosan and the like.
As products, Kuraray's Poval (PVA), Isoban (isobutylene / maleic acid resin), Harima Kasei Neotor, Halidip (alkyd resin, acrylic resin), Nippon Synthetic Chemicals Ecorety (PVA), Nagase ChemteX Examples include deconal (epoxy resin), Julia (acrylic resin), Kabsen (polyester resin) manufactured by Nippon Pure Chemicals.

  The acid value of the alkali-soluble resin or water-soluble resin is preferably from 0 to 2000 mg / KOH, and if it is higher than 2000 mg / KOH, the development characteristics deteriorate.

The volume average particle size of the toner for electrophotographic dry printing of the present invention is preferably 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 toner for electrophotographic liquid printing of the present invention preferably has a weight average particle diameter of 0.1 to 5 μm. If the weight average particle diameter is less than 0.1 μm, a sufficient concentration may not be obtained or blemishes may occur easily. If it is large, the color and resolution may be deteriorated.
In the case of the electrophotographic liquid printing toner of the present invention, the absolute value of the ζ potential of the liquid developer in which the toner is dispersed in the carrier liquid is preferably 10 to 200 mV. When the absolute value of 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 lowered. On the other hand, if the absolute value of the ζ potential is higher than 200 mV, the adhesion amount of the photosensitive member may decrease and the density may decrease.

In the electrophotographic printing method of the present invention, after development on a photoconductor, transfer is performed with a transfer roller, preferably at a pressure of 0.1 to 3 kg / cm ² , and in the case of printing on transfer paper with poor smoothness, transfer is performed. And the high density image can be formed.
Further, when transferring using an intermediate transfer member, transfer performance is improved because a higher pressure is applied. 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.
The amount of the solvent sprayed is preferably 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 solvent squeeze amount of the reverse roller after development is decreased, so that the amount of the developer on the photosensitive member is increased and applied to the cloth. Increasing the solvent penetration is effective.

FIG. 1 is an example of an electrophotographic printing method using a liquid developer using the electrophotographic liquid printing toner 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, an amorphous silicon photoreceptor, or the like 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 generates a voltage opposite to the toner charge. Transfer to swatch fabric.
The developing roller rotates in the forward direction with the photosensitive member, the reverse 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 reverse roller is 1.2 to 4 times. It is effective.

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 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 primary transfer pressure is 0.1 to 3 Kg / cm ² , and the secondary transfer pressure is 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.

The toner for electrophotographic dry textile printing is mixed with a colorant, resin, charge control agent, etc., kneaded in a kneader such as Busconida, then coarsely pulverized and finely pulverized to obtain coarse particles and fine powders to a predetermined particle size. Can be obtained by cutting.
The toner for electrophotographic liquid textile printing is prepared by adding a colorant, resin, carrier liquid, etc. to a dispersing machine such as a ball mill, kitty mill, disc mill, pin mill, etc. to prepare a concentrated toner. It can be obtained as a developer by dispersing in a liquid.

  The present invention will be specifically described below based on examples. “%” And “parts” are based on weight.

Example 1
Dye A in Table 1 (Purity 50% product) 70 parts Lauryl methacrylate / methyl methacrylate / methacrylic acid (80/10/10)
Copolymer isopar H20% solution 100 parts Rosin modified phenolic resin (Mitsui / DuPont) 60 parts Water soluble resin Poval (PVA) (Kuraray) 55 parts Isopar H 180 parts Charge control agent (zirconium naphthenate) 3 parts to pin mill Then, after 300 hours of dispersion, 300 parts of Isopar H was further added and dispersed for 1 hour to obtain a concentrated toner.
Electrophotographic printing was performed with the apparatus of FIG. 1 using a developer in which 100 g of this concentrated toner and Isopar H1L were mixed.

(Example 2)
Dye B of Table 1 (90% purity product) 30 parts Styrene / acrylic resin (St / acrylic = 60/40) (Mitsubishi Rayon) 40 parts Water-soluble resin Kabusen (water-soluble polyester) (Nagase Chemtex) 75 parts Charge control 2 parts of the agent (metal complex of salicylic acid derivative) were kneaded with Busconida, cooled, coarsely pulverized with a pulverizer, pulverized with a jet mill and classified to obtain a dry toner. The cloth was pasted on paper, and electrophotographic printing was performed with this toner using a Ricoh dry printer Imagio.

Example 3
Dye E of Table 1 (Purity 80%) 50 parts Epoxy-modified resin Epicoat 802 (Japan epoxy resin) 20 parts Water-soluble resin Halidive (water-soluble alkyd resin) (Harima Kasei) 75 parts Stearyl methacrylate / methyl methacrylate /
Methacrylic acid (80/10/10)
Isopar H 20% solution of copolymer 100 parts Isopar H 250 parts Charge control agent (zirconium octoate) 5 parts in a ball mill, dispersed for 24 hours, then further added 250 parts of Isopar H, dispersed for 1 hour, concentrated Toner was used.
Electrophotographic printing was performed with the apparatus of 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 dye A of Example 1 (product having a purity of 50%) was used after being purified to a purity of 90%.
Electrophotographic printing was performed with the apparatus of 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 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 toner and silicone oil (KF-96 2cst) were mixed.

(Example 6)
Dye F of Table 1 (Purity 90%) 40 parts Rosin-modified phenolic resin (Mitsui / DuPont) 5 parts Water-soluble resin Kabusen (water-soluble polyester) (Nagase Chemtex) 95 parts 2-ethylhexyl methacrylate / methyl methacrylate /
Methacrylic acid (80/10/10)
Copolymer isopar H20% solution 120 parts Isopar H 200 parts Charge control agent (zirconium naphthenate) 2 parts in a batch sand mill and dispersed for 12 hours, and then 350 parts of Isopar H is added and dispersed for 1 hour. Was used as a concentrated toner.
Electrophotographic printing was performed with the developer shown in FIG. 2 using a developer in which 100 g of this concentrated toner and Isopar M were mixed.

(Example 7)
Dye G of Table 1 (Purity 80%) 50 parts Rosin-modified phenolic resin (Mitsui / DuPont) 95 parts Water-soluble resin Kabusen (water-soluble polyester) (Nagase Chemtex) 5 parts 2-ethylhexyl methacrylate / methyl methacrylate /
Methacrylic acid (80/10/10)
Copolymer isopar H20% solution 120 parts Isopar H 200 parts Charge control agent (zirconium naphthenate) 2 parts in a batch sand mill and dispersed for 12 hours, and then 350 parts of Isopar H is added and dispersed for 1 hour. Was used as 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. Cotton cloth was used for all transfer cloths.

  After applying sodium silicate (45-48 ° Baume) to the printed fabrics of Examples 1-7, they were left standing for 20 hours, washed with water, and treated with 2 g / l of an anionic surfactant at 80 ° C. for 5 minutes to prepare a printed sample. did. The physical properties and evaluation results of various properties are shown in Table 2.

Further, Examples 8, 9 in which printing was performed using the toner of Example 3 in 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 evaluated in the same manner as in Examples 1-7. Table 2 shows the evaluation results of these characteristics.

(Comparative Example 1)
Printing was carried out in the same manner as in Example 1 except that Reactive Red 4 (purity 50%) represented by the following structural formula was used as the dye of Example 1.

(Comparative Example 2)
Printing was carried out in the same manner as in Example 3 except that Reactive Red 46 (purity 50%) represented by the following structural formula was used as the dye of Example 3.

  In Comparative Examples 1 and 2, the same post-treatment as in Examples 1 and 3 was performed and evaluated in the same manner. Table 2 shows the evaluation results of these physical properties and various properties.

As is apparent from the results in Table 2, the electrophotographic printing toner of the present invention and the electrophotographic printing method using the same provide a high-resolution printed fabric with high charge control rate, transfer rate, and fabric image density. It was.
In Example 4, since the purity of the dye is increased, the image density is higher. Since Example 5 uses a solvent other than the aliphatic hydrocarbon as the dispersion medium, the dispersibility is slightly worse than that of Example 4. In Example 6, since the amount of the water-soluble resin is large, the image density is slightly low. In Example 7, since the amount of the water-soluble resin is small, the texture is slightly low.
In Example 10, since Isopar H was blown onto the image on the intermediate transfer roller before the secondary transfer, the transfer rate was increased and the image density was improved. The toner for electrophotographic textile printing of the comparative example has poor charge controllability and cannot function as a toner.

* Image density is measured by X-Rite. * Stain is 5 levels on the soiled stage sample cloth. 5: Best, 1: Worst * Texture is 5 levels on the textured stage sample cloth. Softness, 4: Soft, 3: Moderate, 2: Slightly hard, 1: Hard * Measure the average particle size by the following method The volume average particle size of the dry printing toner was determined by the Coulter Counter method.
The Coulter Counter method is a method usually used for measuring the particle size of dry 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 was determined from the number of pulses and the magnitude.
The weight average particle diameter of the liquid printing toner was measured by Shimadzu SA-CP3.
The toner is diluted with Isopar until the transmittance becomes about 15% with an integrating sphere turbidimeter, and filled in a cell for SA-CP3. The measurement conditions were ACCEL480, MODE: CENT, 3-16 channels.
* Zeta potential was measured by Otsuka Electronics ELS-8000. Cell: Low dielectric constant cell, electric field: 500 V / cm, measured in 6 measurement average mode.
* Resolution is evaluated in 5 stages using a stage sample. 5: Best, 1: Worst * Transfer rate is calculated by the following formula from density by tape peeling method. Transfer rate (%) =
{(Concentration on photoconductor before transfer−Remaining photoconductor density after transfer) / (Concentration on photoconductor before transfer)} × 100
* The charge control rate was calculated by the electrodeposition method. The distance between electrodes was 1 cm, the electrode area was 2 cm × 2 cm, and the electrodeposition time was 100 seconds.
* ΔE is calculated by X-Rite and the color difference from Japan color.

It is a figure which shows an example of the electrophotographic textile printing method in this invention. It is a figure which shows 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 which shows an example of the apparatus which arrange | positions a photoreceptor to a tandem and affixes a cloth on a cloth conveyance belt and performs full color printing.

Claims (14)

In an electrophotographic dry printing toner for printing on a printed fabric by electrophotography using at least toner particles in which a colorant is dispersed in a resin, the following compounds (A), (B), (E ), (F), or (G) , and a toner for electrophotographic dry printing, which comprises a dye represented by (G) .

  2. The electrophotographic dry printing toner according to claim 1, wherein the toner has a volume average particle size of 3 to 20 [mu] m. Dispersed in responsible body fluids, at least a colorant with toner particles dispersed in a resin, the toner for electrophotography liquid printing for printing the printed fabric by an electrophotographic method, wherein the carrier liquid, boiling point 100 An electron which is an aliphatic saturated hydrocarbon at 350 ° C. and contains a dye represented by the following compound (A), (B), (E), (F), or (G) as the colorant Toner for photographic liquid textile printing.

The toner for electrophotographic liquid printing according to claim 3, wherein the aliphatic saturated hydrocarbon has a volume resistance of 10 ⁹ Ω · cm or more .   The toner for electrophotographic liquid printing according to claim 3 or 4, wherein an alkali-soluble resin and / or a water-soluble resin is contained in at least a part of the resin.   The toner for electrophotographic liquid printing according to claim 3, wherein the alkali-soluble or water-soluble resin has an acid value of 0 to 2000 mg / KOH.   7. The electrophotographic liquid printing toner according to claim 3, wherein the absolute value of the ζ potential of the liquid developer in which the toner is dispersed in a carrier liquid is 10 to 200 mV. Electrophotographic liquid textile toner. Electrophotographic toner liquid printing according to any one of claims 3-7, wherein the weight-average particle diameter before Quito toner particles is 0.1 to 5 [mu] m.   The toner for electrophotographic dry or liquid printing according to any one of claims 1 to 8, wherein the purity of the dye is 80 to 100%.   An electrophotographic printing method in which an electrostatic latent image is developed on a photoreceptor using an electrophotographic printing toner, and then an image is transferred by applying pressure with a transfer roller. An electrophotographic printing method using the electrophotographic dry or liquid printing toner according to any one of the above.   11. The electrophotographic printing method according to claim 10, wherein after developing the electrostatic latent image on a photosensitive member, the toner image is primarily transferred to an intermediate transfer member, and then the image is secondarily transferred.   The electrophotographic printing method according to claim 11, further comprising a step of spraying a solvent onto the intermediate transfer body before the secondary transfer.   In the development, the linear speed of the developing roller for developing the toner is 1.2 to 6 times the linear speed of the photosensitive member, and the linear speed of the squeeze roller for removing excess solvent is 1.2 to 4 times. The electrophotographic printing method according to any one of claims 10 to 12.   14. The electrophotographic printing method according to claim 10, wherein in the development, a photoconductor is arranged in a tandem type, an image is transferred to a cloth affixed on a belt, and full color printing is performed.

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