JPH0533275A - Treating agent for electrophotographically printed fabric and method for printing - Google Patents

Abstract

PURPOSE:To print a web into durable, deep and brilliant multi-colors without requiring a steaming treatment by electrostatically transferring a colored polyam ide toner to a web, etc., by an electrostatic electrophotography method and subsequently treating the web, etc., with a treating solution containing a cationic color-deepening agent. CONSTITUTION:A colored polyamide toner produced by coloring a polyamide resin with a dye such as an acidic dye, metal complex dye or acidic mordant dye and subsequently adjusting the electric charge of the dyed polyamide resin is electrostatically transferred to a web comprising natural, regenerated or synthetic fibers and subsequently thermally fixed. The treated web is treated with a treating solution containing a cationic color-deepening agent produced by emulsion-polymerizing a (meth)acrylic ester, (meth)acrylic ester having a perfluoro group, etc., in the presence of a cationic protecting colloid such as cationic starch or a water-soluble cationic modified urethane resin, thereby permitting to print the web into durable, deep and brilliant multi-colors impossible by conventional methods without requiring a steaming treatment, a dry heating treatment, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic printing cloth treating agent and a printing method using the treating agent.
More specifically, the present invention relates to an electrophotographic printing cloth treating agent and a printing method in which the durability of the electrophotographic printing cloth is improved, and the color depth and sharpness are improved.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
Examples of the printing method for cloth and the like include a screen printing method, a roller printing method, a rotary screen printing method, a thermal transfer printing method, and a recent inkjet printer printing method. However, these printing methods have the following drawbacks. The screen printing method has a drawback in that it takes time to manufacture the screen, it takes a lot of space to store the screen, and since the work is an intermittent process, the production speed of the printing is slow, and the roller printing method, which has a high production speed, is a metal. It is difficult to handle because the process of engraving the pattern on the roll is complicated and the roller is heavy, and the rotary screen printing method combines the features of the roller printing method and the screen printing method.This rotary screen is lightweight and can be replaced. It is easy, but in any printing, it takes time to make a screen to create a new pattern, roller engraving, adjustment of color paste, printing after printing is done by means of steaming or dry heat treatment. There is a wide variety of fixing, washing, and drying processes, and it takes a long time from the design to the production of the printing cloth. There is a drawback such as facing a make pooled or bad stock because they are forced to measure and forecast production. Especially when fashion becomes diversified or individualized like these days, we cannot keep up with it from the aspect of delivery date.
The disadvantages such as the difficulty of profitability in processing a wide variety of small quantities are becoming a problem.

Under such circumstances, the thermal transfer printing method was conceived as a printing method in which the design pattern screen production, roller engraving, color paste adjustment and cleaning after printing, and the drying process were improved under such circumstances. is there. Although this method has considerably improved the above-mentioned drawbacks and disadvantages, a sheet-like material printed with a sublimation dye is adhered to a cloth and heated to sublimate the dye to dye the cloth, but a fiber which can be printed by this method Are limited to polyester fibers or pre-treated fabrics that can be dyed with sublimation dyes, and pattern changes are limited to transfer master paper supplied by printing makers, which is suitable for mass production but has inefficiency. However, the transfer paper is uneconomical and has the same drawbacks as the above regarding the processing step.

Further, in recent years, in the textile printing industry, in addition to the production of various kinds in a small amount and the demand for shortening the delivery time, the engraving plate making step, which is the biggest problem of the above-mentioned textile printing method, is omitted and a computer is used. An interlocking inkjet printer (JP-A-2-47377, JP-A-2-47378, JP-A-2-53976) has been partially introduced, engraving rolls and screens are not required, and production is possible immediately after receiving an order. The design and color are easy to change, the design is easy to store and retrieve, and the degree of freedom is higher than that of the conventional printing method.However, this method requires a large amount of money and specialized skills. There is a difficulty that requires knowledge.

On the other hand, a method of drawing a pattern using an electrostatographic copying machine to which an electrophotographic technique is applied, that is, an electrostatic latent image is formed on the surface of a photosensitive drum in an electrostatic copying machine, and a toner containing a colorant is included. Has been developed in recent years. A method has been developed in recent years, in which a toner development is formed by causing the toner to fly by electrostatic force, the toner development is transferred to a cloth or the like at a transfer portion, and the toner is heat-melted and fixed to the cloth or the like at a fixing portion. Is. For example, in the method of directly developing and printing cloths by electronic printing (Japanese Patent Laid-Open No. 51-56313), the color is developed by steaming, followed by washing and resin removal with trichlene,
Electrostatic printing method (JP-A-52-18985, JP-A-52)
-148285, JP-A-53-6692, JP-A-5
No. 3-81783, JP-A No. 53-130385, and JP-A No. 60-213978), there is a method of dyeing a cloth with a dye by steam fixing, and then washing and removing the binder resin in the toner with a solvent or the like. Although proposed, this solvent or the like leads to environmental pollution, and it is difficult to wash the binder resin. Further, a sublimation printing method using a sublimable or vaporizable dye (JP-A-52-60627, JP-A-56-30143, JP-A-58-87378, JP-A-60-118852).
No. 6-113299), these target fibers are polyester fibers, or in the case other than polyester fibers, it is necessary to pretreat them with a compound capable of dyeing a sublimable dye in a pretreatment step. However, there are problems in that the process of pretreatment is complicated and the target fibers are limited.

Regarding the relationship between fibers and dyes, toners containing disperse dyes are polyester fibers, toners containing reactive dyes and direct dyes are cellulose fibers, toners containing cationic dyes are acrylic fibers, toners containing acid dyes are polyamide fibers or There is an absurdity that it is necessary to use a toner containing a dye suitable for a fiber to be printed such as a wool fiber, and a friction fastness test of clothes, a washing durability test,
Dry cleaning durability test (hereinafter, in the present invention,
Although the consumption performance durability is not evaluated, or even if it is evaluated (Japanese Patent Laid-Open No. 53-130385), the resin removal after steaming has a problem because it is washed with a solvent.

Under the present circumstances, the electrophotographic method is excellent in electronic transfer printing when paper is used as an imprinted object and is industrially widely used. However, when a cloth is used as the imprinted object. Has a poor fixing property of the electronic transfer printing, and has hardly been put to practical use. That is, the toner conventionally used for electronic copying has a remarkably poor consumption performance durability after being fixed on a cloth, and lacks color depth and vividness and cannot be put to practical use. Further, in the method of directly developing and printing a toner on a cloth or the like by an electrophotographic method, it is difficult to develop the color by steaming, and further it is difficult to remove the resin with a solvent such as trichlene, and the target fiber is limited in the sublimation printing method. I will end up. An object of the present invention is to provide a treatment agent and a printing method for obtaining a printing cloth by an electrostatic electrophotographic method, which has flexibility and consumption performance durability, good color depth and vividness. .

[0008]

In order to solve the above problems, the inventors of the present invention have conducted diligent research on printing of fabrics, etc., and as a result, have improved the durability of electrophotographic printing fabrics and The present invention has been completed by finding a processing agent capable of improving the depth and sharpness of That is, the present invention is
A processing agent used for a printing cloth obtained by directly transferring and fixing a colored polyamide toner onto a cloth or the like by an electrostatic electrophotographic method, which is characterized by containing a cationic darkening agent. The present invention provides a printing cloth treating agent according to (1) and a printing method using the treating agent.

In the printing method using the electrostatic electrophotographic method of the present invention, an original image is passed through a photolytic filter (blue filter, green filter, red filter) to form a latent image on the photosensitive drum, which is colored in the developing section. Polyamide toner is made to fly to the latent image by electrostatic force, and the toner development of these toners is transferred to the cloth or the like by electrostatic attraction at the transfer section, improving the durability of the printing cloth fixed at the fixing section and increasing the depth of color. And, to improve sharpness, treat with a cationic darkening agent.

The electrostatic electrophotographic method of the present invention is a known color electrophotographic process, in which the surface of the photosensitive drum is uniformly exposed to light by a corona discharge of a corotron in a dark place. Through a photolysis filter to form a latent image on the surface of the photosensitive drum, and the electrostatic latent image on the surface of the photosensitive drum is selectively electrostatically adhered to the latent electrostatic image on the surface of the photosensitive drum by using electrostatically charged powder (toner) to make it visible. Developing step, the cloth is brought into close contact with the photosensitive drum, the transfer corona charge is applied from the opposite side to transfer the toner to the cloth, and then the cloth is separated from the photosensitive drum, the transfer separation step, the transferred toner image on the cloth is made into a permanent image. In order to fix with heat and pressure, a cleaning step to remove the toner remaining on the surface of the photosensitive drum, and a residual charge on the surface of the photosensitive drum with light or a roller. Erased by discharge is a device consisting of neutralizing step of the initial state.

The cloth and the like used in the present invention include cotton, wool, hemp, silk, rayon, di- or triacetate, acrylic, nylon, polyester, polypropylene, polyethylene and other natural fibers or synthetic fiber materials, either alone or mixed, It is a heat-like material such as a woven fabric, a knitted fabric, a non-woven fabric, a synthetic leather, or a natural leather produced by mixed fibers, and in addition, a woven fabric, a knitted fabric, or a non-woven fabric made of an inorganic fiber such as glass fiber can be used.

The colored polyamide toner of the present invention may be a powder of an original colored resin obtained by adding a colorant such as yellow, magenta or cyan to a polyamide resin, or the surface of the polyamide resin powder may be dyed even if treated with the colorant. A colored polyamide resin may be used, and the obtained colored polyamide powder has an average particle size of 5 to 50 μm, preferably 5 to 20 μm. A charge control agent may be added to adjust the charge capacity of these particles, or Add a fluidity improver to improve fluidity,
An offset preventive agent may be added to prevent the offset property on the surface of the heat roll during heat fixing.

As the polyamide resin constituting the colored polyamide toner of the present invention, a thermoplastic polyamide resin having a softening point of 80 to 160 ° C. is preferable, and a melt viscosity measured at a temperature 10 ° C. higher than the softening point is 10 ³ to 10 ° C. A resin having 10 ⁸ CPS is preferable, and a resin having 10 ³ to 10 ⁴ CPS is more preferable. Incidentally, the softening point in the present invention is JIS K28
5 ° C / min in silicone oil by ring and ball method according to 17
It is a value measured at the temperature rising rate of.

When the colored polyamide toner of the present invention is electrostatically transferred to a cloth or the like and melt-pressed with a heat roll, it is necessary for the colored polyamide toner to properly permeate into the cloth in order to enhance the adhesive force and the durability of the consumption performance. is there. If the melt viscosity is lower than the above range, the permeability to the fabric is too large, the clarity and reproducibility of the printed fabric are poor, and not only the appearance is impaired, but the texture tends to become hard, and the heat fixing roll surface Transfer of the molten toner to the toner is remarkable, which is not preferable. On the other hand, if the melt viscosity is higher than the above range, the permeability of the melted toner into the cloth or the like is deteriorated, sufficient fixing cannot be obtained, and the durability of the consumption performance is deteriorated, which is not preferable. On the other hand, if the softening point is higher than the above range, it is necessary to raise the temperature at the time of heat fixing to a cloth or the like, which causes heat shrinkage or damage of the cloth, which is not preferable. If the softening point is lower than the above range, the storage stability of the powder deteriorates, which is not preferable.

As the polyamide resin having the fluidity characteristics exhibiting the heat melting characteristics as described above and having the fixability to a cloth or the like, a polyamide resin having at least one amide bond or ester bond in the molecular chain is used. It is suitable.
As such a polyamide resin, a copolyamide resin obtained by polymerizing various dicarboxylic acids, diamines and lactams is used, and as a raw material of the dicarboxylic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid are used. , Nonanedicarboxylic acid, decanedicarboxylic acid,
Aliphatic dicarboxylic acids having 6 to 12 carbon atoms such as dodecanedicarboxylic acid, dimer acid mainly containing dicarboxylic acid having 36 carbon atoms, terminal carboxylated 1,2-polybutadiene, terminal carboxylated hydrogenated 1,2-polybutadiene, etc. Aromatic dicarboxylic acids such as terminal carboxylated liquid rubber, isophthalic acid, phthalic acid, and terephthalic acid are used.
Dodecenyl succinic acid, n-octyl succinic acid and the like and their acid anhydrides can also be used. Also, the molecular weight is 400-4,00.
It is also possible to use carboxylated polyethylene glycol having both ends of 0. As the raw material of the diamine, ethylenediamine, propylenediamine, 1,2-diaminopropane,
Tetramethylenediamine, piperazine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, both terminal amino acids with a molecular weight of 300 to 2,000. Aliphatic and alicyclic diamines such as modified polyethylene glycol diamine can be used. Examples of the lactam raw material include ε-caprolactam, ω-laurolactam, and other lactams having 6 to 12 carbon atoms, or ring-opened ω-
Amino acids can be used.

As the colorant for the colored polyamide toner of the present invention, known acid dyes, metal complex hydrochloric acid dyes, acid mordant dyes (chromium dyes) and the like can be used. For example, Suminol Fast Yellow R (Sumitomo Chemical Co., Ltd.), Direct Fast Yellow R (Mitsubishi Kasei Co., Ltd.), Kayanol Milling Yellow O (Nippon Kayaku Co., Ltd.), Mitsui Nylon Fast Yellow G
(Mitsui Toatsu Dyestuff Co., Ltd.), Suminol Fast Red G (Sumitomo Chemical Co., Ltd.), Direct Supra Red 3B (Mitsubishi Kasei Co., Ltd.), Kayanol Milling Red BW (Nippon Kayaku Co., Ltd. Ltd.), Mitsui Nylon
Fast Red G (Mitsui Toatsu Dyestuffs Co., Ltd.), Suminol Fast Navy Blue R (Sumitomo Chemical Co., Ltd.), Kayanol Cyanine G (Nippon Kayaku Co., Ltd.), Mitsui Nylon Fast Sky Blue B (Mitsui Toatsu Dye Co., Ltd.), Mitsui Chrome Yellow M (Mitsui Toatsu Dye Co., Ltd.), Mitsui Alizarin Red S (Mitsui Toatsu Dye Co., Ltd.), Mitsui Chrome Examples thereof include dyes such as Pure Blue BX (Mitsui Toatsu Dyes Co., Ltd.), white pigments such as titanium white and zinc white, and black pigments such as carbon black and aniline black. The method of coloring the polyamide resin with these dyes or pigments may be a known method, for example, a deposition method of adding to the molten polymer, a dyeing method of dyeing the resin powder, a surface treatment method of adhering the resin powder to the surface, etc. However, the dyeing method and the dyeing method are more preferable.

The treating agent of the present invention contains a cationic darkening agent and is treated on the printing cloth obtained as described above.
The cationic darkening agent used in the present invention has already been disclosed in JP-B-60-30796 and JP-A-62-28.
The aqueous resin compositions proposed in 9685, JP 62-289686 A, JP 62-289687 A, etc. are used. That is, an aqueous resin composition obtained by polymerizing a monomer having an unsaturated bond capable of being polymerized in the presence of a cationic surfactant or a cationic protective colloid, or an unpolymerizable monomer in the presence of an emulsifying dispersant. Those comprising an aqueous resin composition obtained by adding a cationic protective colloid to an aqueous resin composition obtained by polymerizing a monomer having a saturated bond are preferably used, and further, the glass transition point of the dry film of the aqueous resin composition ( Tg) is in the range of 20 to 110 ° C., its refractive index is 1.50 or less, and the aqueous resin composition emulsion has a zeta (ζ) potential of +5 to +
An aqueous resin composition in the range of 80 mV (measurement condition: ionic strength 10 ⁻³ , pH = 7) is preferably used.

As a particularly preferable color-deepening agent, a monomer comprising a monomer having a polymerizable unsaturated bond and a monomer having a polymerizable unsaturated bond and a crosslinking reactive group is polymerized. The main component obtained is a polymer having a molecular weight of 1000 or more, the dry film has a refractive index of 1.50 or less, and the high molecular weight substance is emulsified in water, or the surface zeta of emulsion-polymerized particles. The potential is +5 mV or more, and the maximum particle size is 50 μm or less. Specific examples include those obtained by emulsifying amino-modified polysiloxane with a nonionic activator, (meth) acrylic acid ester, (meth) acrylic acid ester having a perfluoro group, vinyl alkyl ether, and the like. Cation emulsion-polymerized by a conventional method in the presence of a cationic protective colloid such as starch, cationic cellulose or water-soluble cation-modified urethane resin, or a cationic surfactant such as stearyltrimethylammonium chloride or stearylethylimidazoliniumethylsulfate. Emulsion emulsion polymerization.

The electrophotographic printing fabric of the treatment agent of the present invention may be treated by any of a spraying method, a dipping method and a kiss roll method, but it is important to treat it uniformly. The amount of the cationic darkening agent according to the present invention attached to the printing cloth is 0.05 to 1%, preferably 0.1 to 0.3%.
Is.

[0020]

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The parts and% in the examples are based on weight unless otherwise specified, and various measuring methods were in accordance with the following methods. (A) Dry rubbing fastness (abbreviated as friction) According to JIS L0849, rubbing fastness tester I type was used to rub 100 times with a dry white cotton cloth for rubbing. Five panelists conducted a 5-level visual evaluation, and the average value of the evaluation values of the 5 persons was adopted. The five-level evaluation criteria are as follows. 1: Almost disappeared pattern 2: Thin pattern 3: Part of the pattern disappeared 4: Slightly thin pattern 5: Pattern does not change (b) Washing resistance (abbreviated as washing) JIS L1089 F-1 method After washing in a household washing machine according to
Dehydrated and air dried. Five panelists conducted a 5-level visual evaluation, and the average value of the evaluation values of the 5 persons was adopted. The five-level evaluation criteria are as follows. 1: Most of the pattern is removed 2: Part of the pattern is removed 3: Part of the pattern is lost 4: Pattern is slightly thin 5: Pattern does not change (c) Dry cleaning resistance (abbreviated as DC) According to JIS L0860 Dry cleaning was performed. Five panelists conducted a 5-level visual evaluation, and the average value of the evaluation values of the 5 persons was adopted. The five-level evaluation criteria are as follows. 1: Almost all patterns are missing 2: Part of the patterns is missing 3: Part of the patterns disappears 4: The pattern is slightly faint 5: The patterns do not change (d) Visual judgment regarding sharpness Visually by 5 panelists Three-level evaluation was performed and the average value of the evaluation values of 5 people was adopted.

The three-level evaluation criteria are as follows.

1: Vividness did not change 2: Somewhat sharpness 3: Remarkably vivid Example 1 Polyamide resin having a melt viscosity of 1000 CPS (Nippon Rilsan Co., Ltd., Pratamide H106, average particle size: 40-) 50μ)
Was colored under the following conditions, dried (50 ° C., under vacuum), classified (MDS separator: Nippon Pneumatic Mfg. Co., Ltd.), and subjected to charge control by surface treatment (Aerosil) to obtain a colored polyamide. Using a toner, under the following electronic copying conditions, electronic copying was performed on a PET tropical cloth, and heat fixing was performed to obtain a printing cloth. A diluted liquid of the cationized darkening agent A shown below was prepared on the obtained printing cloth, and sprayed uniformly from above so as to change the amount of adhesion. The relationship between the amount of the cationized darkening agent attached and the durability at that time was investigated. The results are shown in Table 1. <Polyamide dyeing conditions> Dyeing temperature: 80 ° C Dyeing time: 60 minutes Particle size of powder: 50μ or less Dye: Suminol Fast Yellow R Dye concentration: 3% owf <Copying conditions by electronic copying machine> Electronic copying machine: SHARP SF8600 Carrier: 1070 g Colored polyamide toner: 30 g <Cationic darkening agent A> Emulsion in which butyl methacrylate and N-methylol acrylamide are copolymerized with cation-modified polyurethane emulsion as a protective colloid, solid content 15%

[0023]

[Table 1]

From this result, the amount of the thickening agent attached was 0.1%.
It turns out that the above is sufficient.

Example 2 In the same manner as in Example 1, a textile fabric which was electronically copied and heat-fixed using a colored polyamide toner on a PET tropical fabric was used.
Immersion in various treatment agent solutions shown below, the adhesion amount is 0.3
The durability of the cloth obtained by treating the cloth so that the resulting cloth was treated so as to be 100% and drying was obtained. The results are shown in Table 2.

<Treatment> Comparative product 1: Urethane emulsion (SOFTEX U-1
00: manufactured by Kao Co., Ltd. Comparative product 2: polyethylene oxide emulsion (Softex K-111) Invention product A: the product used in Example 1 Invention product B: cationic surfactant (stearyl trimethyl ammonium chloride, Emulsion polymerized by emulsion polymerization of trifluoroisopropyl methacrylate, ethyl acrylate and glycidyl methacrylate in the presence of Kotamine 86P Conc., Kao Corporation, solid content 15% Inventive product C: amino-modified polysiloxane (Toray Silicone, SF- 8417) Emulsified with 11.5 parts of branched alkyl ethylene oxide adduct 3.5 parts and 0.6 part of 30% acetic acid and having a particle zeta potential of +45 mV, solid content 15% 50:50 of the products D: A and C of the present invention ( Weight ratio) Mixed product

[0027]

[Table 2]

Example 3 In the same manner as in Example 2, a printing cloth which was electronically copied and heat-fixed using a colored polyamide toner on a PET tropical cloth was used.
The sharpness of the cloth obtained by treating with the same treating agent as in Example 2 was evaluated. The results are shown in Table 3.

[0029]

[Table 3]

[0030]

EFFECTS OF THE INVENTION By treating an electrophotographic printing cloth with the treatment agent of the present invention, it is possible to improve the durability, which has heretofore been considered impossible, and to improve the color depth and sharpness. It enables multi-color printing on fabrics made of fibers, its industrial value is extremely large, and in today's society that demands sensitivity, it draws original designs by itself, and it can be used to create T-shirts, ties of any kind. By printing on handkerchiefs, handkerchiefs, cutting cloths, etc. instantly, you can enjoy fashion. In the apparel industry, you can deliver a small amount of a wide variety of products in a short time after receiving an order, so you have a bad inventory. Will be eliminated and effective use of funds will be achieved. Further, the electrostatic electrophotographic printing method of the present invention is the same as the conventional method for producing a design, but a plate making step, an engraving step, and a color paste are not required.
The processes such as steaming and dry heat treatment, which are indispensable for dyeing processing, are not necessary, water and heat energy can be extremely omitted, and there is no concern about environmental pollution.

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Claims (5)

[Claims] 1. A processing agent used for a printing cloth obtained by directly transferring and fixing a colored polyamide toner onto a cloth or the like by an electrostatic electrophotographic method, which contains a cationic darkening agent. An electrophotographic printing cloth treating agent. 2. An aqueous resin composition obtained by polymerizing a monomer having a polymerizable unsaturated bond in the presence of a cationic surfactant or a cationic protective colloid, or a cationic darkening agent, or 2. An aqueous resin composition obtained by adding a cationic protective colloid to an aqueous resin composition obtained by polymerizing a monomer having a polymerizable unsaturated bond in the presence of an emulsifying dispersant. The treatment agent for textile printing cloth described. 3. The glass transition point (Tg) of the dry coating of the aqueous resin composition is in the range of 20 to 110 ° C., and its refractive index is
1.50 or less, and the ζ-potential of the aqueous resin composition emulsion is +5 to +80 mV (measurement conditions: ionic strength 10 ⁻³ , pH
= 7). The treatment agent for textile printing cloth according to claim 2, wherein 4. The textile printing cloth according to claim 2, wherein a part of the monomer having a polymerizable unsaturated bond is a monomer having a polymerizable unsaturated bond and a cross-linking reactive group. Processing agent. 5. A printing cloth obtained by directly transferring and fixing a colored polyamide toner onto a cloth or the like by an electrostatic electrophotographic method is treated with the treatment agent according to any one of claims 1 to 4. A printing method characterized by: