JP2000226781A - Fabric for ink jet printing and ink jet printing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a fabric for ink jet printing affording water resistance and color clearness in the area of ink jet dyeing technology using pigment ink. SOLUTION: This fabric for ink jet printing is such one as to have a cationic resin-contg. ink-receiving layer on the surface; wherein the cationic resin is 1,000-10,000 in molecular weight and 0.5-10.0 mS/cm in electrical conductivity in the form of a 1% aqueous solution. This fabric has high water resistance; and when put to ink printing, the fabric has effect of preventing the pigment ink from bleeding together with water, therefore affording clear and deep colored prints.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cloth for recording a pigment ink by an ink jet method, and a recording method thereof.

[0002]

2. Description of the Related Art Conventionally, there has been developed a technique for recording on a fabric by using an ink jet method by using a coloring material.
Dyes and pigments are commonly used as coloring materials. Ink-jet recording methods using these coloring materials (that is, ink-jet dyeing methods) include various methods for improving the quality of fabrics as products. Improvements have been made. Originally, when ink-jet dyeing is performed using a dye or a pigment, a “bleeding” phenomenon occurs on a fabric surface, and such blurring was a major factor in lowering the quality of a product.

[0003] Therefore, many improvements have been made to solve the "bleeding" phenomenon. At present, the fabric surface is treated with an ink holding agent, that is, an ink receiving agent, before ink-jet dyeing the fabric. Is the mainstream. For example, Japanese Patent Publication No. 50234/1990 and Japanese Patent Publication No.
No. 45359 discloses a dyeing method in which a fiber structure is treated in advance with a cationic substance as an ink receiving agent when performing ink jet dyeing.

Japanese Patent Application Laid-Open No. 7-119047 discloses a water-soluble metal salt or a cationic compound as an ink receiving agent.
There is disclosed an inkjet dyeing method which provides a treatment liquid containing a nonionic water-soluble polymer and a nonionic or amphoteric surfactant and has an excellent bleeding suppressing effect. However, in the case of inkjet dyeing using the above-described treatment liquid containing an ink receiving agent, there is a problem in that the water resistance varies depending on the type of the cationic compound. Further, when a dye ink is used, a washing step is necessarily required to improve the fastness, and there are problems such as an increase in the number of steps and an indispensable waste liquid treatment.

On the other hand, when the pigment ink is used, the pigment required for recording is fixed by the binder, so that such a washing step is not required. For this reason, ink-jet dyeing with pigment inks has recently been focused on. However, pigment inks are generally inferior in sharpness and the like as compared with dye inks, but because of their excellent water resistance, for example,
It is suitable for use as an advertising cloth posted outdoors, specifically, as an advertising sheet such as a hanging banner, a banner, or a cloth signboard.

For this reason, stronger water resistance and sharpness are desired. However, when a treatment liquid comprising a cationic resin is applied, a certain effect can be surely obtained with respect to bleeding.
With respect to water resistance, it was difficult to say that there was any effect, and this was a problem.

[0007]

SUMMARY OF THE INVENTION The present invention has such a technical background and has been made to solve those problems. That is, an object of the present invention is to provide a fabric for inkjet recording excellent in water resistance and sharpness in an inkjet dyeing technique using a pigment ink, and an inkjet recording method thereof.

[0008]

Means for Solving the Problems In order to solve such a problem, the present inventors initially focused on the degree of cationization used as a general index for cationic resins. However, the measurement of the degree of cationization is complicated and time-consuming, and it takes a long time to obtain a result. Therefore, when the electric conductivity was measured as a substitute value, the water resistance and the sharpness were controlled as long as the molecular weight was controlled. It has been found that there is a significant difference between the present invention and the cationic resin, and based on this finding, the present invention has been completed.

That is, according to the present invention, there is provided (1) an ink jet recording cloth having an ink receiving layer containing a cationic resin on a surface thereof, wherein the cationic resin has a molecular weight of 1,000.
And 1 to 10,000 mS / cm in an aqueous 1% aqueous solution.

(2) The ink receiving layer is divalent to trivalent
(1) The ink-jet recording fabric containing a valent metal ion.

(3) In the method of ink-jet recording a fabric using a pigment ink, the fabric has a molecular weight of 1,000 to 10,000 and an electric conductivity of 0.5 mS / cm to 10.0 mS in a 1% aqueous solution. / Cm, a treatment liquid containing a cationic resin is applied to a fabric, and then a pigment ink is printed on the fabric.

(4) In the method of ink-jet recording a fabric using a pigment ink, the fabric has a molecular weight of 1,000 to 10,000 and an electric conductivity of 0.5 mS / cm to 10.0 mS in a 1% aqueous solution. / Cm and a treatment liquid containing a divalent to trivalent metal ion to a cloth, and thereafter, a pigment ink is printed on the cloth.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention relates to a recording material which is excellent in water resistance and sharpness and is used for printing by an ink jet system using a pigment as a coloring material, and a recording method therefor. In the present invention, in order to improve water resistance and sharpness, a treatment liquid (ink receiving material) containing a cationic resin having an electric conductivity and a molecular weight in a specific numerical range is pretreated on the surface of the fabric. Thus, an ink receiving layer is formed on the surface of the cloth pre-processed with the processing liquid. And
After the ink receiving layer is formed by the pre-processing, the pigment ink is inkjet-recorded on the fabric.

That is, the electric conductivity of the cationic resin contained in the treatment liquid to be pretreated is in the range of 0.5 mS / cm to 10.0 mS / cm in the state of a 1% aqueous solution. Generally, the pigment ink used in the ink jet method contains an ionic polymer to enhance the dispersing effect of the pigment, and the dispersing effect is enhanced by an electric repulsion. By using a cloth provided with a resin material having a different ionic property from the ink, the bonding force between the ink molecules and the resin molecules in the portion where an image is formed is increased.

The present invention makes use of the fact that the electrical conductivity affects this binding force. If the electric conductivity is less than 0.5 mS / cm, the amount of unfixed pigment on the fabric increases due to the lack of ionic components on the fabric that can be combined with the pigment, and the water resistance is reduced. In addition, the aggregation of the pigment is small and the sharpness and the density cannot be increased. When the electric conductivity is more than 10.0 mS / cm, the bonding force between the pigment molecules and the resin increases and the concentration increases, but unreacted resin remains on the surface of the fabric, and as a result, the water resistance decreases. Further, it has an adverse effect on hue.

Here, the molecular weight of the cationic resin is 10
A range from 00 to 10000 is employed. The molecular weight of the cationic resin must be substantially in the above range in order to uniformly apply the resin to the fabric, and one or two or more types of the resin are used at the time of application. No problem. Examples of the cationic resin used for the recording fabric of the present invention include substances such as polymers and oligomers such as acrylamide, vinylamine, allylamine, ethyleneimine and dicyandiamide.

The electric conductivity is measured according to the following method. That is, a 1% aqueous solution is prepared by dissolving a cationic resin in pure water, and this aqueous solution is measured using a conductivity meter CM-20S (manufactured by Toa Denpa Kogyo Co., Ltd.). In order to coagulate the pigment while maintaining the fine dispersion, it is preferable that a divalent or higher valent metal is mixed in the treatment liquid composed of the cationic resin, because a further effect can be seen.

As the divalent metal, Cu, Zn, Ca, S
Examples of the trivalent metal include n and Ba, such as Al and Fe. These metal ions also have the effect of lowering the refractive index of light and improving sharpness. In addition, in order to obtain the same effect as the above-mentioned divalent or higher-valent metal, alumina hydrate, colloidal silica, inorganic substances such as metal oxide, water-insoluble collagen fine particles, oil emulsion, polysulfonic acid ether, wax emulsion, Organic substances such as polyhydric alcohol aliphatic esters, polyethylene glycol fatty acid esters, and stearic acid esters may be added.

In particular, as the inorganic substance, a refractive index of 1.2 to 1.7 and a specific surface area of 100 to 50 for improving sharpness.
It is preferable that the particle size is 0 m ² / g and the particle size is fine.
Further, at the time of printing, a component having an effect of exhibiting ink absorption performance and having an effect of preventing penetration and diffusion of the ink into the fabric layer may be contained in the treatment liquid.

The substance which can be expected to have the above effects can be selected from synthetic resins such as polyurethane, polystyrene and polyacryl, latexes such as urethane rubber and butadiene rubber, and mixtures thereof. It is necessary to select the color material appropriately depending on the configuration and molecular weight.

If necessary, a penetrant, a pH adjuster and the like may be used in combination with the above-mentioned treating solution without any problem. Examples of the penetrant include alcohols such as octyl alcohol and isopropyl alcohol, and general surfactants. The pH adjuster can be arbitrarily selected from common ones such as acetic acid, ammonium acetate, sodium carbonate, and ammonium sulfate, and combinations thereof.

The method of applying the treatment liquid comprising the cationic resin of the present invention includes a method of directly applying the treatment liquid to a cloth and a method of forming the above treatment liquid into a film and laminating the same. Examples of the method of direct application include a gravure method, a coating method, and a mangle pad method. As means for forming and laminating a film,
A lamination method and the like can be mentioned. The ink receiving layer is formed on the fabric surface by performing processing (application processing) with the above-described processing liquid. Printing is performed on the surface of the fabric on which the ink receiving layer is formed by an inkjet method.

As the ink jet recording method of the pigment ink, a charge modulation method, a micro dot method, a charge jet control method, a continuous method such as an ink mist method, a stem method (two liquid chamber type), a pulse jet method (one liquid chamber type). ), An on-demand method such as a bubble jet method and an electrostatic suction method, and the like.

After printing by the ink jet method, a heat treatment is performed to fix the pigment. The heat treatment here can employ either dry heat or wet heat, but is preferably 110 to 200 ° C., particularly preferably
120-180 ° C. Such heat treatment further improves the durability of the ink receiving layer.

The recording fabric for ink-jet printing includes any fabric structure irrespective of a woven fabric, a knitted fabric, or a non-woven fabric. Preferably, a woven or knitted fabric is used. Further, as a material of the fabric, natural fibers such as cotton, hemp, silk, wool, regenerated fibers such as rayon, semi-synthetic fibers such as acetate and triacetate, synthetic fibers such as polyester, nylon and acrylic,
Also included are those in which one or more of them are used in the form of mixed spinning and weaving.

In the ink jet recording fabric of the present invention, it goes without saying that it is necessary to select the most suitable cationic resin in order to improve the water resistance in accordance with the type of the fabric and the pigment. Hereinafter, examples will be further described, but the present invention is not necessarily limited to the examples.

[0027]

EXAMPLES Example 1 Fabric: 100% polyester plain fabric Treatment liquid (ink receiving material): Neofix E-117 10 parts [Polyethylene polyamine resin, electric conductivity: 2.2 mS / cm, molecular weight : 2500 (manufactured by Nikka Chemical Co., Ltd.)]-10 parts of alumina sol [alumina (manufactured by Nissan Chemical Co., Ltd.)]-10 parts of aquaprene WS-11A [polyether urethane (manufactured by Meisei Chemical Co., Ltd.)]-70 parts of water Was applied by a mangle pad method so as to have a pickup rate of 75%, and dried at 100 ° C. for 1 minute. The ink jet recording fabric prepared by the above method was subjected to printing by an ink jet method using an ink containing a pigment. The following pigments were used. Ink formula ・ Pigment (one of the following) C.I. I. Pigment Yellow 151 (P.Y.151) C.I. I. Pigment Red 122 (P.R122) C.I. I. Pigment Blue 15: 3 (P.B.15: 3) C.I. I. Pigment Black 7 (P.Bl.7)-Additives Surfactants, preservatives, binders, wetting agents, defoamers-Solvent Water Inkjet printing conditions were as follows. Printing conditions Nozzle diameter: 100 μm Driving voltage: 100 V Frequency: 5 KHz Resolution: 360 dpi Subsequently, a dry heat treatment was performed at 150 ° C. for 1 minute. Table 1 shows the results.

[Example 2] Fabric: 100% cotton sheet-knitted fabric Treatment solution: 10 parts of Neofix E-117 [polyethylene polyamine resin, electric conductivity: 2.2 mS / cm, molecular weight: 2500 (Nichika Chemical) 90 parts of water was applied to a mangle pad system so as to have a pickup ratio of 80%, and dried at 100 ° C. for 1 minute. Printing was performed on the ink jet recording fabric prepared by the above method using the ink containing the pigment under the same ink and ink jet printing conditions as in Example 1. Subsequently, a dry heat treatment was performed at 140 ° C. for 2 minutes. Table 1 shows the results
Shown in

Example 3 Fabric: Same as in Example 2 Treatment liquid: 10 parts of Fix Oil R737 [polyamine resin, electric conductivity: 1.88 mS / cm, molecular weight: 2000 (manufactured by Meisei Chemical Co., Ltd.)]・ Aquaprene WS-11A 10 parts (Polyether-based urethane: manufactured by Meisei Chemical Co., Ltd.) ・ 80 parts of water 80% pickup rate by mangle pad method
After the application, drying was performed at 100 ° C. for 1 minute.
Printing was performed by the ink jet method under the same pigment and printing conditions as in Example 1. Subsequently, a dry heat treatment was performed at 140 ° C. for 2 minutes. Table 1 shows the results.

Example 4 Fabric: 100% nylon plain woven fabric Treatment liquid: 10 parts of Neofix RD-5 [amine composition, electric conductivity: 2.6 mS / cm, molecular weight: 1500 (Nichika Chemical)・ Aquaprene WS-11A 10 parts [Polyether-based urethane (manufactured by Meisei Chemical Co., Ltd.)] ・ 80 parts of water is applied to a mangle pad method so as to have a pickup rate of 70%, and then 100 ° C. and 1 part. Drying for minutes was performed.
Ink-jet printing was performed on the ink-jet recording fabric prepared by the above method using an ink containing a pigment in the same manner as in Example 1. Then, at 150 ° C, 2
For 10 minutes. Table 1 shows the results.

Example 5 Fabric: Same as in Example 1 Treatment liquid: 10 parts of Neofix R-800 [quaternary ammonium salt compound, electric conductivity: 1.0 mS / cm, molecular weight: 5000 (Nichika)・ Aquaprene WS-11A 10 parts (polyether urethane: manufactured by Meisei Chemical Co., Ltd.) ・ CLA-530 10 parts (silica hydrate: manufactured by Kyoeisha Chemical Co., Ltd.) ・ 70 parts of water to mangle It was applied by a pad method so as to have a pickup rate of 75%, and was dried at 100 ° C. for 1 minute. Printing was performed by the ink jet method under the same pigment and printing conditions as in Example 1. Subsequently, a dry heat treatment was performed at 150 ° C. for 1 minute. Table 1 shows the results.

Comparative Example 1 The following treatment liquid was applied without using the cationic resin of the present invention. Fabric: Same as in Example 1 Treatment liquid: ・ 10 parts of alumina sol 520 (alumina: manufactured by Nissan Chemical Co., Ltd.) ・ 10 parts of aquaprene WS-11A (polyether urethane: manufactured by Meisei Chemical Co., Ltd.) ・ 80 parts of water to mangle 75% pickup rate by pad method
After the application, drying was performed at 100 ° C. for 1 minute.
Printing was performed by the ink jet method under the same pigment and printing conditions as in Example 1. Subsequently, a dry heat treatment was performed at 150 ° C. for 1 minute. Table 1 shows the results.

Comparative Example 2 The cationic resin was changed to the next chemical having an electric conductivity of less than 0.5. Fabric: Same as in Example 1 Treatment liquid: 10 parts of Tortoise 604T [polyamide polyamine compound, electric conductivity: 0.43 mS / cm, molecular weight: 3000, (manufactured by Nichika Chemical Co., Ltd.)] ・ Aquaprene WS-11A 10 Part (polyether-based urethane: manufactured by Meisei Chemical Co., Ltd.) ・ 80% water pick-up rate of 80% by mangle pad
And dried at 100 ° C. for 1 minute.
Printing was performed by an ink jet method under the same pigment and printing conditions as in Example 1. Subsequently, a dry heat treatment was performed at 140 ° C. for 2 minutes. Table 1 shows the results.

Comparative Example 3 The cationic resin was changed to the next chemical having an electric conductivity of 10 or more. Fabric: same as in Example 2 Treatment liquid: 10 parts of Neofix RP-90C (amide-based copper-containing type, electric conductivity: 11.5 mS / cm, molecular weight: 3000 (manufactured by Nikka Chemical Co., Ltd.)) Water 90 The part was applied with a mangle pad method so as to have a pickup ratio of 80%, and dried for 1 minute at 100 ° C. The ink-jet recording fabric prepared by the above method was applied using an ink containing a pigment. Printing was performed under the same ink and inkjet printing conditions as in Example 1. Subsequently, dry heat treatment was performed at 140 ° C. for 2 minutes.
Shown in

Comparative Example 4 A cationic resin having a molecular weight of 1
Changed to 0000 or more. Fabric: Same as in Example 2 Treatment liquid: 10 parts of Neofix CF-3 (polyvinylamine-based compound, electric conductivity: 2.1 mS / cm, molecular weight: 25000 (manufactured by Nika Chemical Co., Ltd.)) 90 parts of water 80% pickup rate using mangle pad method
And dried at 100 ° C. for 1 minute. Printing was performed on the ink jet recording fabric prepared by the above method using the ink containing the pigment under the same ink and ink jet printing conditions as in Example 1. Subsequently, a dry heat treatment was performed at 140 ° C. for 2 minutes. Table 1 shows the results
Shown in

[0036]

[Table 1]

[Density]: Density was measured using a reflection densitometer (Macbeth RD918;
(The higher the numerical value, the better the concentration). [Water resistance]: The water resistance was measured by immersing a black ink-printed cloth in water for 10 minutes and measuring the residual ratio. Residual ratio = reflection density after immersion treatment / reflection density before immersion treatment × 100 Here, the reflection density was measured using a reflection densitometer (Macbeth RD918; manufactured by Macbeth). [Sharpness]: The sharpness was determined by printing a full-color image and visually determining the sharpness of the image. ：: Image is clear Δ: Image lacks sharpness ×: Image is not clear

[0038]

As described above, the recording fabric obtained according to the present invention is excellent in water resistance and has the effect of preventing the pigment from bleeding with water when printing ink on the fabric. Clear and high density can be obtained.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Ayumi Yamazaki 1-10-1 Kiya, Fukui City, Fukui Prefecture F-term (reference) 4H057 AA01 AA02 BA15 CA03 CC01 DA01 DA34 GA06 GA26 HA22 HA90

Claims (4)

[Claims] 1. An ink jet recording fabric having an ink receiving layer containing a cationic resin on the surface thereof, wherein the cationic resin has a molecular weight of 1,000 to 10,000 and an electric conductivity of 0.5 mS / cm in a 1% aqueous solution. ~ 1
An ink jet recording cloth having a flow rate of 0.0 mS / cm. 2. The ink jet recording fabric according to claim 1, wherein the ink receiving layer contains divalent to trivalent metal ions. 3. A method for inkjet recording a fabric using a pigment ink, wherein the molecular weight is 1000 to 1000.
0 and the electric conductivity is 0.5 mS in the state of a 1% aqueous solution.
An ink jet recording method, comprising: applying a treatment liquid containing a cationic resin having a density of from about 0.1 mS / cm to 10.0 mS / cm to a cloth, and printing a pigment ink on the cloth. 4. A method for inkjet recording a fabric using a pigment ink, wherein the molecular weight is 1000 to 1000.
0 and the electric conductivity is 0.5 mS in the state of a 1% aqueous solution.
/ Cm to 10.0 mS / cm of a cationic resin;
An ink jet recording method comprising applying a treatment liquid containing divalent to trivalent metal ions to a fabric, and then printing a pigment ink on the fabric.