JP2008225291A - Liquid toner for electrophotographic textile printing and textile printing method of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid toner for electrophotographic textile printing having preferable image quality, high printing density and excellent texture, and to provide a method for electrophotographic textile printing using the toner, and a method for electrophotographic textile printing significantly improving the efficiency of workability of textile printing, having on-demand ability and avoiding waste. <P>SOLUTION: The liquid toner for electrophotographic textile printing contains a colorant, a resin (A) and a dispersion medium, wherein the dispersion medium contains triglyceride having a viscosity of 0.5 to 100 mPa s (at 25°C) and a resistance of 10<SP>10</SP>to 10<SP>16</SP>Ω cm. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a liquid 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. This method forms an electrostatic latent image on a photoconductor, attaches toner, transfers the toner onto cloth, and fixes the toner by heat (Patent Documents 6 to 7 and the like). 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 colorant is attached to the cloth in the state of a dissolved color paste, In the case of printing by electrophotography, the colorant 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.

  The idea of using fatty acid esters for printing inks and inkjet inks has been made for some time. The reason why it is used for printing ink and ink-jet ink is used for the purpose of preventing deterioration of machine members and improving the stability of printing quality. A device to be used as a dispersion medium for electrophotographic liquid toner has been proposed in Patent Document 11 and the like. These proposals are positioned as alternative carriers for isoparaffin and silicone oil, are used for printing on paper, and are different from the object of the present invention.

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 JP 2002-278169 A

  An object of the present invention is to provide an electrophotographic printing liquid toner having good image quality, high printing 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)-(15) of this invention.
(1) “Colorant, resin (A) and dispersion medium are contained, the dispersion medium has a viscosity of 0.5 to 100 mPa · s (25 ° C.), and the resistance is 10 ¹⁰ Ω · cm to 10 ¹⁶ Ω · cm. An electrophotographic printing liquid toner comprising a fatty acid triglyceride represented by the following general formula (I):

」、
（２）「前記脂肪酸トリグリセリドが植物を原料として得られたものであることを特徴とする前記第（１）項に記載の電子写真捺染液体トナー」、
（３）「前記脂肪酸トリグリセリドがＲ：ｎ＝７及び９のいずれかを含むことを特徴とする前記第（１）項又は第（２）項に記載の電子写真捺染液体トナー」、
（４）「前記着色剤が染料であることを特徴とする前記第（１）項乃至第（３）項のいずれかに記載の電子写真捺染液体トナー」、
（５）「前記染料の純度が８０〜１００重量％であることを特徴とする前記第（１）項乃至第（４）項のいずれかに記載の電子写真捺染液体トナー」、
（６）「前記樹脂（Ａ）がＧＰＣ法で測定した数平均分子量５００〜２００００の樹脂（Ａ１）を含有することを特徴とする前記第（１）項乃至第（５）項のいずれかに記載の電子写真捺染液体トナー」、
（７）「全樹脂（Ａ）量に対して前記樹脂（Ａ１）の割合が５０〜９０％であることを特徴とする前記第（６）項に記載の電子写真捺染液体トナー」、
（８）「染料量に対して前記樹脂（Ａ）の割合〔（樹脂（Ａ）／染料）×１００％〕が５０〜２５０％であることを特徴とする前記第（１）項乃至第（７）項のいずれかに記載の電子写真捺染液体トナー」、
（９）（＝新規請求項）「前記樹脂（Ａ）が前記着色剤により着色されたトナー粒子、及び/又は、前記樹脂（Ａ）中に前記着色剤を包含するトナー粒子が前記分散媒に分散されてなることを特徴とする前記第（１）項乃至第（８）項のいずれかに記載の電子写真捺染液体トナー」、
（１０）「前記トナー粒子のζ電位の絶対値が１０〜２００ｍＶであることを特徴とする前記第（９）項に記載の電子写真捺染液体トナー」、
（１１）「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第（９）項又は第（１０）項に記載の電子写真捺染液体トナー」、
（１２）「前記第（１）項乃至第（１１）項のいずれかに記載の電子写真捺染トナーを用い、感光体上の静電潜像を現像した後、転写ローラで圧力及び静電力により画像を転写させることを特徴とする電子写真捺染方法」、
（１３）「前記第（１）項乃至第（１１）項のいずれかに記載の電子写真捺染トナーを用い、感光体上の静電潜像を現像し、中間転写体にトナー像を１次転写した後、画像を被転写体に２次転写させることを特徴とする電子写真捺染方法」、
（１４）「２次転写前に中間転写体に溶媒を吹き付ける工程を含むことを特徴とする前記第（１２）項又は第（１３）項に記載の電子写真捺染方法」、
（１５）「タンデム型に感光体を配置し、ベルト上に貼り付けた被転写体に画像を転写し、フルカラー捺染することを特徴とする前記第（１２）項乃至第（１４）項のいずれかに記載の電子写真捺染方法」。

"
(2) “The electrophotographic printing liquid toner according to (1) above, wherein the fatty acid triglyceride is obtained from a plant as a raw material”,
(3) “The electrophotographic textile printing liquid toner according to (1) or (2) above, wherein the fatty acid triglyceride contains any one of R: n = 7 and 9”,
(4) “Electrophotographic textile printing liquid toner according to any one of items (1) to (3), wherein the colorant is a dye”,
(5) “Electrophotographic textile printing liquid toner according to any one of (1) to (4) above, wherein the purity of the dye is 80 to 100% by weight”;
(6) "Any one of the above items (1) to (5), wherein the resin (A) contains a resin (A1) having a number average molecular weight of 500 to 20000 as measured by GPC method" Electrophotographic textile printing liquid toner ",
(7) “Electrophotographic textile printing liquid toner according to item (6), wherein the ratio of the resin (A1) to the total resin (A) is 50 to 90%”,
(8) The ratio of the resin (A) to the amount of the dye [(resin (A) / dye) × 100%] is 50 to 250%, the items (1) to ( 7) Electrophotographic textile printing liquid toner according to any one of items
(9) (= New Claim) “Toner particles in which the resin (A) is colored with the colorant and / or toner particles containing the colorant in the resin (A) are used as the dispersion medium. The electrophotographic printing liquid toner according to any one of (1) to (8) above, wherein the toner is dispersed,
(10) "Electrophotographic textile printing liquid toner according to item (9), wherein the absolute value of the zeta potential of the toner particles is 10 to 200 mV",
(11) “The electrophotographic printing liquid toner according to (9) or (10) above, wherein the toner particles have a weight average particle diameter of 0.1 to 5 μm”,
(12) “After developing the electrostatic latent image on the photoreceptor using the electrophotographic printing toner according to any one of the above items (1) to (11), a transfer roller is used to apply pressure and electrostatic force. An electrophotographic printing method characterized by transferring an image ",
(13) “Using the electrophotographic printing toner according to any one of (1) to (11), an electrostatic latent image on a photosensitive member is developed, 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 ”,
(14) "The electrophotographic printing method according to item (12) or (13), including a step of spraying a solvent onto the intermediate transfer member before secondary transfer",
(15) Any one of the above items (12) to (14), 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 crab".

  According to the present invention, it is possible to provide an electrophotographic printing liquid toner having good image quality, high printing density and excellent dyeing property, 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 liquid 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.

Hereinafter, the present invention will be described in detail.
The present invention relates to an electrophotographic printing toner for use in an electrophotographic printing method comprising resin toner particles in which a colorant is dispersed in a dispersion medium and printing on a transfer medium such as cloth by an electrophotographic method, and the electrophotographic printing toner The dispersion medium has a viscosity of 0.5 to 100 mPa · s, the resistance is 10 ¹⁰ Ω · cm to 10 ¹⁶ Ω · cm, and is represented by the following general formula (I). It is characterized by being a fatty acid triglyceride derived from plants. Here, it is not indispensable that all the colorants are integrated with the resin, and it is not very easy as a practical matter, but it is preferable that they are integrated as much as possible.

It has been found that the printing density and texture can be improved by using the dispersion medium of the present invention in an electrophotographic printing liquid toner. In textile printing, it is necessary to fix the dye on the cloth by applying a coloring process (steaming, high pressure, high temperature, alkali treatment, etc.) after the dye is attached to the cloth. If the fixation is insufficient in the color treatment, the dye that is not fixed is removed during soaping, and a sufficient concentration cannot be obtained. By using the dispersion medium of the present invention, it is considered that the dye fixing effect is enhanced and the printing density is improved. In the electrophotographic printing liquid toner of the present invention, preferably, toner particles in which the resin (A) is colored with a colorant and / or toner particles containing the colorant in the resin (A) are dispersed in a dispersion medium. The toner particles are typically in a softened state in the dispersion medium. The particle size of the toner particles in the present invention is a particle size measured in a dispersion medium. For the particle size measurement, a toner particle diluted with the same dispersion medium was used to avoid the overlapping of the projected images of the toner particles and to obtain a projected image for each individual particle.
The reason why the fixing effect is increased is that the dye contained in the resin (A) in the color treatment is easily transferred to the cloth through the present dispersion medium because of the affinity, and the dye remaining in the resin (A) This is considered to be almost eliminated (see FIG. 6 after the coloring process).

The texture depends on the amount of residual resin after the soaping process, and if the resin remains much after the soaping, the texture tends to deteriorate.
The dispersion medium of the present invention has an effect of promoting the detachability of the resin (A) from the cloth or making the specific resin (A) brittle during steaming by being present at the interface between the cloth and the resin (A). It is considered that there is a resin removal property in soaping. (See Fig. 6 after soaping)

The dispersion medium of the present invention needs to have a viscosity of 0.5 to 100 mPa · s. When the viscosity is lower than 0.5 mPa · s, the dispersion medium is easily absorbed by the cloth immediately after the transfer, so that the dispersion medium is less likely to be present at the interface between the resin and the cloth, or the transferability is lowered. When the viscosity is higher than 100 mPa · s, the toner particle migration is lowered, and the printing density is lowered.
The resistance needs to be 10 ¹⁰ Ω · cm to 10 ¹⁶ Ω · cm. When it is lower than 10 ¹⁰ Ω · cm, the developability is deteriorated, and background staining and density decrease occur. If it is higher than 10 ¹⁶ Ω · cm, image blur may occur.
In general formula (I), n needs to be 3-17. When n is larger than 17, the effect of drawing and fixing the dye from the resin to the fiber and the effect of making the resin (A) brittle and improving the texture are reduced. When n is smaller than 3, the odor is too strong or the transferability is lowered.

The fatty acid glycerides of the present invention are from plant of palm oil, palm oil, palm kernel oil, corn oil, cottonseed oil, khair oil, guava oil, grapefruit oil, peanut seed oil, babassu kernel oil, soybean oil, etc. It can be separated and purified.
If it uses a plant as a raw material, it is preferable in terms of the environment in terms of carbon neutrality. Examples of the fatty acid triglyceride of the present invention include the following.

またこれらを数種混合させたものでもかまわない。
本発明の脂肪酸グリセリドの中で、Ｒのｎ＝７、９のものが特に好ましい。またこの中で、ｎ＝７が６０〜８０％、ｎ＝９が４０〜２０％のものが更に好ましい。

Also, a mixture of several of these may be used.
Among the fatty acid glycerides of the present invention, those with R n = 7, 9 are particularly preferred. Of these, those in which n = 7 is 60 to 80% and n = 9 is 40 to 20% are more preferable.

The colorant of the present invention is preferably a dye. In the case of a pigment, since it does not dye on a fiber, it is necessary to make it adhere with resin, and resin for making it adhere will reduce a feel.
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.

  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 (%).

The resin (A1) used in the present invention preferably has a number average molecular weight of 500 to 20000 as measured by GPC method.
Resin (A1) in this molecular weight range has weak adhesion to fibers and film strength, and when combined with the dispersion medium of the present invention, 95% or more of the resin can be removed by soaping treatment.
Particularly preferred types of the resin (A1) include rosin-modified polyester resin, rosin-modified maleic resin, rosin-modified phenol resin, low molecular polyethylene resin, and low molecular polypropylene resin.

In addition to these resins (A1), it is preferable to contain a dispersion resin (A2) that enhances dispersion stability.
Preferred dispersing resins (A2) include vinyl monomer A represented by the following general formula (1), vinyl monomer represented by the following general formula (2), vinyl pyridine, vinyl pyrrolidone, ethylene glycol dimethacrylate, styrene, divinylbenzene. , Each one of monomers B selected from 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.)

Specifically, the preferred acrylic resin of the present invention can be synthesized, for example, as follows.
500 g of Isopar H was charged into a 3 L flask equipped with a stirrer, thermometer, condenser, and dropping funnel, heated to 90 ° C. and stirred, 100 g of lauryl methacrylate (Acrylic ester L manufactured by Mitsubishi Rayon Co.), glycidyl methacrylate (acrylic) A monomer solution consisting of 20 g of ester G), 15 g of methacrylic acid (manufactured by Mitsubishi Rayon Co., Ltd.) and 1 g of azbisisobutyronitrile is added dropwise over 2 hours. Thereafter, polymerization is carried out for 5 hours while maintaining the temperature at 95 ° C.
Thereafter, a monomer solution composed of 30 g of methyl methacrylate (Acryester M manufactured by Mitsubishi Rayon Co., Ltd.) and 0.2 g of azbisisobutyronitrile is added dropwise over 2 hours, and polymerization is carried out for 1 hour while maintaining at 85 ° C. The synthesized acrylic resin preferably has a polymerization rate of 95% or more, a molecular weight Mn of about 8000 to about 50000, and an Mw of about 10,000 to about 80000.

In combination with the dispersion medium of the present invention, a paraffinic solvent and a naphthenic solvent having a high resistance and a low dielectric constant can be used.
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.

  For example, Isopar C, Isopar E, Isopar G, Isopar H, Isopar L, Isopar M, Isopar V, Exor 100/140, Exor D30, Exor D40, Exor D80, Exor D110, Exor D130 (manufactured by ExxonMobil) There is.

  The ratio of the resin (A) to the dye ((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.

  In the present invention, the toner particles in which the resin (A) is colored with a colorant and / or the toner particles containing the colorant in the resin (A) are dispersed in a dispersion medium. The absolute value of the ζ potential in the dispersion medium of such toner particles 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 liquid printing toner preferably has a weight average particle diameter of 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 less 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 secure the necessary amount of solvent. 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.
The transfer voltage is preferably 1000 to 7000 V in absolute value when directly transferred onto a cloth or the like, and 100 to 1000 V for primary transfer and 300 to 7000 V for secondary transfer when using intermediate transfer.

When the dye is a reactive dye, excellent dyeability can be obtained by subjecting an image transferred to an object to be transferred such as cloth by an electrophotographic method to color development by a pad steam method with an alkali concentration of 0.1 to 10 mol%. 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 and dye are not sufficiently dissolved and the reactivity is lowered. When the treatment temperature is higher than 140 ° C., the dye reactive group may be crushed before the reaction with a cloth or the like.
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.

  In the electrophotographic liquid printing liquid toner of the present invention, a colorant, a resin, and a carrier liquid are charged into a dispersing machine such as a ball mill, a kitty mill, a disk mill, a pin mill, and dispersed, and the resin (A) is colored with the colorant. A concentrated toner containing toner particles and / or toner particles containing a colorant in the resin (A) can be prepared and further dispersed in a support liquid.

  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 liquid toner, 200 broad (warp 120 / inch, weft 80 / inch) cotton cloth is used for textile printing, and polyester satin cloth is used for paper for disperse dye liquid toner. Used by pasting. 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 put in a pin mill and dispersed for 10 hours. Further, 300 parts of fatty acid triglyceride A shown in Table 1 was added and dispersed for 1 hour to obtain a concentrated printing toner.
Using the developer obtained by mixing 100 g of this concentrated printing toner, 0.3 L (liter) of fatty acid triglyceride B shown in Table 1 and 0.7 L (liter) of Isopar H, electrophotographic printing was performed using the apparatus shown in FIG. Table 1 shows the number average molecular weight in terms of polystyrene of the resin (A1) used, the absolute value of the ζ potential of the colored toner particles in the liquid toner, and the weight average particle diameter.

・ 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 100 parts of a fatty acid triglyceride B solution of Table 1 of a methacrylate / methacrylic acid (80/10/10) copolymer 100 parts Fatty acid triglyceride A 180 parts of Table 1 Charge control agent (zirconium naphthenate) 3 parts

(Example 2)
The following materials were placed in a ball mill and dispersed for 72 hours. Further, 250 parts of fatty acid triglyceride B shown in Table 1 was added and dispersed for 1 hour, and this was used as a concentrated printing toner.
Using the developer of 100 g of this concentrated printing toner, 0.4 L of fatty acid triglyceride B of Table 1 and ISOPAR L, 0.6 L, electrophotographic printing was performed with the apparatus of FIG.
Disperse dye (Kayalon Polyster Turquoise Blue GL-S) (purification treatment purity 90%) (manufactured by Nippon Kayaku Co., Ltd.) 25 parts and polyethylene resin (210P) (manufactured by Mitsui Chemicals Co., Ltd.) 50 parts melt kneaded and ground 80 parts stearyl methacrylate / 105 parts of a fatty acid triglyceride B 20% by weight solution of Table 1 of methyl methacrylate / methacrylic acid (80/10/10) copolymer 185 parts of fatty acid triglyceride B of Table 1 Charge control agent (zirconium naphthenate) 3 parts

(Example 3)
The following materials were placed in a ball mill and dispersed for 48 hours. Further, 250 parts of fatty acid triglyceride C shown in Table 1 was added and dispersed for 1 hour to obtain a concentrated printing toner.
Using this concentrated printing toner 100 g, a developer in which 0.2 L of fatty acid triglyceride C shown in Table 1 and Isopar H, 0.8 L were mixed, electrophotographic printing was performed with the apparatus shown in FIG.

95 parts by melting and kneading and pulverizing 60 parts of reactive dye (Cibacron TurquoiseBlueFGF-P) (purification purity 85%) (manufactured by Ciba Chemical Co., Ltd.) and 35 parts of polyethylene resin (171P) (manufactured by Sanyo Kasei Co., Ltd.) 2 ethylhexyl methacrylate / 100 parts of fatty acid triglyceride C solution of Table 1 of methyl methacrylate / methacrylic acid (80/10/10) copolymer 100 parts Fatty acid triglyceride C 250 parts of Table 1 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.
Using this concentrated printing toner 100 g, a developer in which 0.3 L of fatty acid triglyceride D shown in Table 1 and Isopar H, 0.7 L were mixed, electrophotographic printing was performed with the apparatus shown in FIG.

(Example 5)
Electrophotographic printing was performed with the apparatus shown in FIG. 2 using a developer in which 100 g of the concentrated toner of Example 3 and 1 L of fatty acid triglyceride D shown in Table 1 were mixed.

(Example 6)
The following materials were placed in a batch sand mill and dispersed for 12 hours. Further, 350 parts of the fatty acid triglyceride F shown in Table 1 was added and dispersed for 1 hour to obtain a concentrated printing toner.
Using the developer obtained by mixing 100 g of this concentrated printing toner, 0.6 L of fatty acid triglyceride C shown in Table 1 and 0.4 L of Exol D40, electrophotographic printing was performed with the apparatus shown in FIG.

・ 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 / 120 parts of fatty acid triglyceride F in Table 1 of methacrylic acid (80/10/10) copolymer 120 parts 200 parts of fatty acid triglyceride F in Table 1 Charge control agent (zirconium naphthenate) 2 parts

(Example 7)
The following materials were placed in a batch sand mill and dispersed for 12 hours. Further, 350 parts of the fatty acid triglyceride F shown in Table 1 was added and dispersed for 1 hour to obtain a concentrated printing toner.
Using a developer in which 100 g of this concentrated printing toner and 1 L of fatty acid triglyceride E shown in Table 1 were mixed, electrophotographic printing was performed with the apparatus shown in FIG.

・ 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) copolymer fatty acid triglyceride C 20 wt% solution of Table 1 50 parts ・ Table 1 fatty acid triglyceride C 100 parts ・ Table 1 fatty acid triglyceride D 100 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 fatty acid triglyceride G shown in Table 1 was added and dispersed for 1 hour, and this was used as a concentrated printing toner.
Using the developer in which 100 g of this concentrated printing toner and fatty acid triglyceride G 0.5 L (liter), Isopar H, 0.5 L (liter) of Table 1 were mixed, electrophotographic printing was performed with the apparatus of FIG.

・ 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 30 parts by weight of a 15% by weight fatty acid triglyceride G of Table 1 of an acrylate / methacrylic acid (80/10/10) copolymer. 170 parts of a fatty acid triglyceride G of Table 1. Charge control agent (zirconium naphthenate) 2 parts

Example 9
The apparatus shown in FIG. 3 was mounted with an intermediate transfer member using a developer obtained by mixing 100 g of the concentrated printing toner of Example 3 with 0.3 L (liter) of fatty acid triglyceride B of Table 1 and Isopar M 0.7 L (liter). Photo printing was performed.

(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) (Sumitomo Chemical Co., Ltd.) (purity 50%) 40 parts and epoxy resin (Epicoat 1002) (Japan Epoxy Resin Co., Ltd.) 35 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

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) copolymer Isopar H 30% by weight solution 100 parts Isopar H 250 parts Charge control agent (zirconium octoate) 5 parts

In Examples 1, 2, 4, 5, 6, 9, 10 and Comparative Example 1 using a polyester cloth, the printing cloth was steamed at 175 ° C. for 30 minutes, 2 g / L of sodium carbonate, 2 g / L of hydrosulfite. For 20 minutes with 80 ° C. warm water.
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, The system surfactant was treated with 2 g / L at 80 ° C. for 5 minutes.
The results are shown in Table 2.
As is apparent from the results in Table 2, the electrophotographic printing liquid toner of the present invention and the electrophotographic printing method yielded a printed fabric having a high printing 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.
Further, the printing liquid toners of Comparative Examples 1 and 2 did not use the dispersion medium or resin of the present invention, so the printing density was low and the texture was poor.

Image density is measured by X-Rite.
Stain is due to a soiled stage sample cloth. Evaluation is 5 levels (5: best, 1: worst)
The bleed rate was calculated from the line width before and after the color fixing treatment.
Bleed rate = (line width after color fixation treatment / line width before color fixation treatment) x 100%
The texture is according to the texture-level sample cloth. Evaluation is 5 levels (5: softness similar to cloth only, 4: soft, 3: moderate, 2: slightly hard, 1: hard)
The weight average particle diameter is according to 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.
The 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.
The resolution and density uniformity depend on the stage sample. Evaluation is 5 levels (5: best, 1: worst)
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%

It is a figure which shows an example of the image forming apparatus used for the electrophotographic textile printing method of this invention. It is a figure which shows the example which made the transfer voltage provision member of FIG. 1 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. It is a figure showing the mode of color fixation processing in textile ink and textile toner. It is a figure which illustrates typically the fixation aspect to the cloth of the toner particle in the textile printing method of this invention.

Claims (15)

It contains a colorant, a resin (A), a dispersion medium, the dispersion medium has a viscosity of 0.5 to 100 mPa · s (25 ° C.), a resistance of 10 ¹⁰ Ω · cm to 10 ¹⁶ Ω · cm, and An electrophotographic printing liquid toner comprising a fatty acid triglyceride represented by the general formula (I).

2. The electrophotographic printing liquid toner according to claim 1, wherein the fatty acid triglyceride is obtained using a plant as a raw material. 3. The electrophotographic printing liquid toner according to claim 1, wherein the fatty acid triglyceride contains any one of R: n = 7 and 9. 4. The electrophotographic printing liquid toner according to claim 1, wherein the colorant is a dye. 5. The electrophotographic printing liquid toner according to claim 1, wherein the purity of the dye is 80 to 100% by weight. 6. The electrophotographic printing liquid toner according to claim 1, wherein the resin (A) contains a resin (A1) having a number average molecular weight of 500 to 20000 measured by GPC method. The electrophotographic printing liquid toner according to claim 6, wherein the ratio of the resin (A1) to the total resin (A) is 50 to 90%. 8. The electrophotography according to claim 1, wherein the ratio of the resin (A) to the amount of the dye [(resin (A) / dye) × 100%] is 50 to 250%. Textile liquid toner. The toner particles in which the resin (A) is colored with the colorant and / or toner particles including the colorant in the resin (A) are dispersed in the dispersion medium. Item 9. The electrophotographic printing liquid toner according to any one of Items 1 to 8. The electrophotographic textile liquid toner according to claim 9, wherein an absolute value of the ζ potential of the toner particles is 10 to 200 mV. 11. The electrophotographic printing liquid toner according to claim 9, wherein the toner particles have a weight average particle diameter of 0.1 to 5 μm. 12. An electrophotographic method comprising: developing an electrostatic latent image on a photosensitive member using the electrophotographic printing toner according to claim 1; and transferring an image with a transfer roller by pressure and electrostatic force. Printing method. An electrostatic latent image on a photosensitive member is developed using the electrophotographic printing toner according to any one of claims 1 to 11, and 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. The electrophotographic printing method according to claim 12 or 13, further comprising a step of spraying a solvent onto the intermediate transfer body before the secondary transfer. 15. The electrophotographic printing method according to claim 12, wherein a photoconductor is arranged in a tandem type, an image is transferred to a transfer medium attached on a belt, and full color printing is performed.

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