JP3410026B2 - Leather for inkjet printing and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to natural or synthetic leather suitable for ink-jet printing and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, leather products made of natural leather or synthetic leather take advantage of the texture thereof, in addition to footwear such as shoes, clothing such as clothes, gloves, belts, bags, purses, etc. It is widely used in our daily lives such as furniture and industrial products.

However, in order to impart a pattern to the surface of a leather product, embossing or the like has been the mainstream in natural leather, and no full-scale printed product such as that seen in clothing has been known. Even when performing printing by a known method such as screen printing, since natural leather has poor resistance to high temperatures and chemicals, particularly alkaline chemicals, it contains an alkaline agent and a reactive dye, such as a cellulosic fiber cloth. It is practically impossible to use a method such as applying moist heat treatment after applying the printing paste, and further, the paste component contained in the printing paste is washed and removed in order to hold the dye stably. At that time, there is a problem that the texture of the leather is hardened due to the alteration of the protein component.

Further, although synthetic leather is subjected to methods such as gravure roll printing, screen printing and transfer printing, the printing method involves coloring when the pattern plate and the leather to be printed are in contact with each other. However, in the case of multi-color printing, plates and processes are required for the number of colors, which not only inevitably raises the cost and lowers the productivity, but also has the problem that the design change cannot be dealt with promptly. There is a problem that it is difficult to homogenize the surface state due to the change.

Further, the above-mentioned problems of reduced productivity and inability to promptly deal with design changes are the same not only with leather but also with fabrics. No. 61-75871, a textile printing apparatus provided with a cloth transporting means, a printing liquid jetting means, and a printing fluid supply means with a liquid jetting control valve, that is, an inkjet textile printing device is used. As described in Japanese Unexamined Patent Publication No. 61-6347, there is disclosed a method of obtaining a fiber cloth in which a blended color is expressed by an aggregate of dots of different colors.

As a method of applying the printing method using the above-mentioned ink jet printing apparatus to natural leather, Japanese Patent Application Laid-Open No. 7-331585 discloses starch, casein, gelatin, maleic anhydride resin, melamine resin, urea resin. , Styrene-butadiene rubber, PVA, polyvinylpyrrolidone, hydroxycellulose, polyethylene oxide,
Resins that are soluble in liquid inks such as acrylamide, and dispersions of inorganic fine particles such as colloidal silica and alumina sol, styrene-acrylic copolymers, vinyl acetate resins, vinyl acetate-acrylic copolymers, vinyl acetate
Affinity for the above liquid inks such as Veova copolymer, vinyl acetate / maleate copolymer, vinyl acetate / ethylene copolymer, vinyl acetate / ethylene / vinyl chloride copolymer, emulsion obtained by emulsifying epoxy resin, etc. Disclosed is a method of providing an aggregate of particles having a functional group having a.

Further, in JP-A-8-113881, water-soluble resins such as PVA and polyvinylpyrrolidone before printing, or styrene / acryl copolymers, vinyl acetate resins, vinyl acetate / acryl copolymers, vinyl acetate.・ Veova copolymer, vinyl acetate / maleate copolymer, vinyl acetate / ethylene copolymer, vinyl acetate / ethylene / vinyl chloride copolymer, emulsion obtained by emulsifying epoxy resin, inorganic fine particles such as colloidal silica and alumina sol A natural leather is provided with a dispersant such as to form an ink receiving layer on the surface thereof, and then color is added by an inkjet method, or at the same time as or after that, polyallylamine salt, polyallylsulfone, dimethyldiallylammonium chloride, polyamine Sulfone salt, polyvinylamine salt, chitosan acetic acid Etc., molecular weight 2,0 a water-soluble
A cationic polymer having a number of 00 or more and 200,000 or less, and a compound of a primary to tertiary amine salt type, a compound of a quaternary ammonium salt type, a compound of a pyridinium salt type, an imidazoline type cationic compound, a higher alkylamine A method for providing a coloring material fixing material containing a cationic low molecular weight substance having a molecular weight of 1,000 or less, such as an ethylene oxide adduct, an amino acid type amphoteric surfactant and a carboxylic acid type amphoteric surfactant is disclosed.

However, the above-mentioned Japanese Unexamined Patent Publication No. 7-33158.
As described in JP-A No. 5 and JP-A-8-113881, a resin soluble in a dye solvent (generally a water-soluble resin)
And a method using a particle aggregate, the surface direction of the leather by the particle aggregate, that is, while suppressing the penetration in the two-dimensional spreading direction, and yet in the leather thickness direction of the dye in the printing ink by the water-soluble resin. Since it promotes permeation, fineness of the image can be obtained, but when the moisture absorption state of the leather itself fluctuates with the fluctuation of humidity due to changes in the environment and climate, the above-mentioned water solubility in the high humidity region Due to the action of the resin, the image obtained by efficiently permeating the dye has a high density, and on the contrary, the density is lower in the low humidity region than that in the high humidity region, resulting in uneven density between the printing surface or each lot. It had a problem that it would occur.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and even when the temperature or humidity is changed during processing or use, the leather surface or each An object of the present invention is to provide a natural or synthetic leather in which the printing density between lots does not vary, and a method for producing the same.

[0010]

In order to achieve the above object, the present invention has the following constitution.

The first aspect of the invention is an ink jet characterized in that it has a permeation adjusting layer containing a water repellent agent and a binder resin and a color forming adjusting layer containing a cationic substance and a binder resin on the leather surface. It is a leather for printing.

A second aspect of the present invention is to include a water repellent agent comprising at least one compound selected from the group consisting of paraffin compounds, aluminum compounds, zirconium compounds, and ethylene urea compounds on the surface of leather. And a color-developing control layer containing a cationic substance and a binder resin, the leather for inkjet printing.

The third invention is the first and second inventions.
In the second invention, the binder resin contained in the permeation adjusting layer or the color adjusting layer is at least one resin selected from the group consisting of acrylic resin, urethane resin, or acrylic / urethane copolymer. It is characterized by consisting of.

A fourth aspect of the invention is the same as the first to third aspects of the invention, wherein the leather surface is permeated and has a water repellency of 50 points according to the JIS L-1092 method. As described above, the number of points is less than 80.

The fifth aspect of the invention is to apply a permeation adjusting treatment liquid containing a water repellent agent and a binder resin to the surface of the leather and allow it to dry, and then develop a color containing the cationic substance and the binder resin. A method for producing a leather for inkjet printing, which comprises applying an adjustment treatment liquid and drying the leather.

Further, a sixth aspect of the invention is that the surface of the leather is
After applying a permeation-adjusting treatment liquid containing a water repellent comprising at least one compound selected from the group of paraffinic compounds, aluminum compounds, zirconium compounds, or ethyleneurea compounds, and drying it, the cation is then added. A method for producing a leather for inkjet printing, which comprises applying a color-developing treatment solution containing a functional substance and a binder resin and drying the solution.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The ink-jet printing leather of the present invention has a water repellent agent, a cationic substance and a binder resin on the leather surface. The permeation control layer containing the agent and the color formation control layer containing the cationic substance are located on the outer side of the permeation control layer.

As the leather in the present invention, natural leather which has undergone the usual tanning process, polycarbonate type polyurethane, polytetramethylene ether glycol type polyurethane, polyester ether type polyurethane,
Polybutylene adipate polyurethane, polymethylpentane adipate polyurethane, polynonanediol adipate / polyoctane adipate polyurethane,
Polyurethane resin such as polymethylpentane adipate polyurethane, polyurea, polyurethane polyurea,
Used for synthetic leather having a synthetic resin layer containing styrene-butadiene rubber, acrylonitrile-butadiene rubber, vinyl chloride, acrylate-styrene copolymer, styrene-butadiene copolymer, urethane-vinyl chloride copolymer, etc. as a main component. To be Particularly, in the case of synthetic leather, it is more preferable that the synthetic resin layer is porous.

In order to obtain the ink-jet printing leather of the present invention having the above-mentioned constitution, a permeation adjusting treatment liquid containing a water repellent is applied to the leather surface and dried to form a permeation adjusting layer, and then the permeation adjusting layer is formed. A color formation adjusting treatment liquid containing a cationic substance and a binder resin is applied and dried to form a color forming adjustment layer.

Here, as the water repellent in the permeation adjusting layer, paraffin compounds, aluminum compounds,
It is also possible to use a water repellent composed of at least one compound selected from the group consisting of zirconium compounds and ethyleneurea compounds, or a widely used fluorine water repellent. At least one selected from the group consisting of the above-mentioned paraffin compounds, aluminum compounds, zirconium compounds, and ethyleneurea compounds, which do not require high-temperature heat treatment to be applied to leather, because they require high-temperature heat treatment to adhere to leather. A water repellent composed of the above compounds is preferable.

It is preferable that the leather surface is permeated and adjusted by such a water repellent, and the water repellency according to JIS L-1092 method is 50 points or more and less than 80 points. When the water repellency of the leather surface is 80 points or more, the permeation adjusting layer has too high water repellency, so that the dye does not sufficiently permeate, and the desired concentration cannot be obtained. Is low, that is, the hygroscopicity is high, so that it is easily affected by a change in humidity of the outside air, which causes density unevenness. The water repellency of the leather surface is more preferably 50 to 70 points.

As the water repellent, the water repellency of the leather surface is 5
A fluorine-based water repellent agent can be used as long as it can adjust the permeation to 0 point or more and less than 80 points. In this case,
Since heat treatment cannot be performed, it is important to include a binder resin in the permeation adjusting treatment liquid. Further, even when a water repellent composed of any of paraffin compounds, aluminum compounds, zirconium compounds, and ethylene urea compounds other than the fluorine water repellent is used, the permeation adjusting treatment liquid contains a binder resin. Exercising is effective.

In the above case, if the binder resin is made of at least one resin selected from the group consisting of acrylic resins, urethane resins, or acrylic / urethane copolymers, it is compatible with leather. It is preferred because it has high properties, and it is more preferred that the molecular weight is less than 5,000.

Further, in order to apply the above-mentioned permeation control treatment liquid to the leather surface, 0.1 to 70 g / m ² is applied to the surface to be imprinted by a spray drying method, a coating method or the like. When the permeation adjusting treatment liquid contains a binder, it is preferable to mix them in such a manner that the weight ratio of the water repellent agent to the binder (solid component conversion) is in the range of 10: 100 to 100: 100, and 30: 100 to. 60:10
0 is more preferable.

Next, the color adjusting layer has a pair of ionicity and a property of the dye in the printing ink so that the dye contained in the printing ink used in the printing step is fixed to the color adjusting layer by ionic bond. In general, the dye contains an anionic property such as an acid dye, a direct dye, a metal complex salt dye, and a reactive dye. Therefore, a cationic substance should be included in the dye. . Therefore, unless the anionic dye is used as the dye in the printing ink used in the subsequent step, the effect of adjusting color development is not exhibited.

The cationic substance may be a dye fixing agent such as a polyamine derivative or a quaternary ammonium salt, or a water-soluble agent such as aluminum sulfate, aluminum hydroxide, sodium aluminate, polyaluminum chloride or polyacrylamide polymer flocculant. Examples of the organic polymer.

The dye applied to the color forming adjustment layer is intended to migrate to the leather after that, but as described above, the permeation adjusting layer containing the water repellent is provided between the color forming adjustment layer and the leather. Therefore, the leather is adjusted by the permeation adjusting layer so as to exhibit uniform water repellency, that is, in other words, it exhibits uniform hygroscopicity (water absorption). Therefore, even if the outside air is high in humidity, the absorption of water into the leather is adjusted to a constant value, and the dye is uniformly transferred to the leather, so that uneven density is suppressed.

The color adjusting treatment liquid for forming the color adjusting layer is the same as in the case of the permeation adjusting treatment liquid.
It is preferable that the resin composition contains a binder resin, and the binder resin is made of at least one resin selected from the group consisting of acrylic resins, urethane resins, and acrylic / urethane copolymers. , 0.1 to the coated surface by the coating method, etc.
It is applied at 60 g / m ² and then dried.

The leather thus provided with the permeation adjusting layer and the color forming adjusting layer on the surface is applied with a dye ink by an ink jet printing method and then gradually dried with warm air of 40 to 60 ° C., and then used. A finishing treatment can be applied according to the above.

As the ink jet printing method, the heating resistance element is embedded in the nozzle, the ink is boiled by the heat generation, and the ink is ejected by the pressure of the bubble. An electric signal is applied to the piezoelectric element. Pulse jet method that causes the volume change of the ink chamber to be ejected to eject ink particles, and ink is continuously jetted under pressure from a nozzle that is vibrating ultrasonically to make particles, and the particles are controlled to a charged amount During constant electrolysis Deflect through
An example is a charge control method in which recording and non-recording particles are recorded separately.

[0031]

[Example] <Example 1: Fluorine-based water repellent / binder resin + cationic substance / binder resin> Asahi Guard A was used as a solvent for sheep leather that had undergone the usual tanning process.
A permeation adjusting treatment liquid containing 20 g / l of G-710 (manufactured by Meisei Chemical Industry Co., Ltd .; fluorine-based water repellent) and 20 g / l of liquidine AW2560 (manufactured by Sankyo Chemical Co., Ltd .; acrylic binder) was sprayed. After applying 50 g / m ² and drying at 80 ° C. for 1 minute, using water as a solvent, Danfix 505RE (manufactured by Nitto Boseki Co., Ltd .; chlorine-resistant quaternary ammonium salt type polycationic fixing agent) 5
40 g / m ^{2 of} a color adjusting treatment solution containing g / l and N8-120X (manufactured by Takamatsu Yushi Co., Ltd .; cationic polyurethane resin) was applied by a spraying method at 40 g / m ² and then dried at 60 ° C. for 3 minutes to obtain JIS L- Leather having a water repellency of 70 by the 1092 method was obtained. Then, a desired print pattern was printed with a bubble jet type inkjet printing apparatus using a dye ink containing an acidic dye, and a product of Example 1 was obtained.

<Example 2; Ethyleneurea-based water repellent + cationic substance / binder resin> Octep EM (manufactured by Hodogaya Chemical Co., Ltd .; ethyleneurea-based water repellent) was applied to sheep leather that had been subjected to the usual tanning process. 10g /
30 g / m ^{2 of} the permeation adjusting treatment liquid prepared as 1 by the spray method
After application and drying at 60 ° C. for 3 minutes, 40 g / m ² of a color-developing treatment solution having the same formulation as in Example 1 was applied by a spray method, followed by drying at 60 ° C. for 3 minutes to obtain JIS L-10.
A leather having a water repellency of Method 92 of 50 was obtained. continue,
The product of Example 2 was obtained by printing a desired print pattern using a bubble jet type inkjet printing apparatus using a dye ink containing an acid dye.

<Comparative Example 1; Fluorine-based water repellent + cationic substance / binder resin> Asahi Guard AG-710 (manufactured by Meisei Chemical Industry Co., Ltd.) was used as a solvent for sheep leather that had been subjected to a normal tanning process. Fluorine-based water repellent) 20 g / l of permeation adjusting treatment liquid was sprayed to 50 g / m ²
After applying and drying for 3 minutes at 60 ° C., 40 g / m ² of a color development adjusting treatment solution having the same formulation as in Example 1 was applied by a spray method, and then dried for 3 minutes at 60 ° C. As a result, the water repellency of the leather surface according to JIS L-1092 method was 90 points. Then, a desired print pattern was printed with a bubble jet type inkjet printing apparatus using a dye ink containing an acid dye to obtain a product of Comparative Example 1.

<Comparative Example 2: Cationic substance + binder resin (particle aggregate)> Sheep leather which has been subjected to a normal tanning process, water as a solvent, and Danfix 505RE (manufactured by Nitto Boseki Co., Ltd. Quaternary ammonium salt type polycationic fixing agent) 5 g / l and N8-120X
(Takamatsu Oil & Fat Co., Ltd .; cationic polyurethane resin) is applied by a spray method at 40 g / m ² and then dried at 60 ° C. for 3 minutes, and a bubble jet method using a dye ink containing an acid dye is used. A desired print pattern was printed with an inkjet printing device to obtain a product of Comparative Example 2.

Examples 1, 2 obtained as described above
When the print particle diameters (diameter of the dye ink dyed on the printing surface) and the print densities of the products of Comparative Examples 1 and 2 were compared, it was found that the products of Example 1 and Example 2 had two products. Was obtained, a print particle size of an appropriate size and a sufficient and uniform density were obtained. However, in the products of Comparative Example 1 and Comparative Example 2, density unevenness occurred and sufficient uniformity was not obtained. In Comparative Example 1, since the water repellency was high, bleeding and stains occurred due to migration when the dye ink was dried.

[0036]

Industrial Applicability As described in detail above, the leather and the method for producing the same obtained by the present invention have the effects that high-quality printed leather can be obtained without uneven printing, and in the case of the method of the present invention. Unlike screen printing, since no printing paste is used, a washing step is unnecessary, and it is possible to prevent deterioration of texture and quality.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-8-113881 (JP, A) JP-A-8-209553 (JP, A) JP-A-9-59700 (JP, A) JP-A-7- 331585 (JP, A) JP-A-9-324372 (JP, A) JP-A-1-192884 (JP, A) JP-A-11-158782 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) D06P 3/32 D06P 5/00 C14B 1/56 D06N 3/00

Claims (6)

(57) [Claims] 1. A leather for inkjet printing, comprising a permeation adjusting layer containing a water repellent agent and a binder resin, and a color forming adjusting layer containing a cationic substance and a binder resin on the surface of the leather. 2. A permeation control layer containing, on the leather surface, a water repellent agent comprising at least one compound selected from the group consisting of paraffin compounds, aluminum compounds, zirconium compounds, and ethylene urea compounds. A leather for inkjet printing, comprising: a color-developing adjustment layer containing a cationic substance and a binder resin. 3. The binder resin according to claim 1, wherein the binder resin comprises at least one resin selected from the group consisting of acrylic resins, urethane resins, and acrylic / urethane copolymers. The ink-jet printing leather according to 1. 4. The surface of the leather is adjusted in permeation, and the water repellency according to JIS L-1092 method is 50 points or more and less than 80 points. The leather for inkjet printing according to any one of 3 above. 5. A leather surface is provided with a permeation adjusting treatment liquid containing a water repellent and a binder resin and dried, and then a color developing treatment liquid containing a cationic substance and a binder resin is applied and dried. A method for producing a leather for inkjet printing, which is characterized by the above. 6. A permeation adjusting treatment liquid containing, on the leather surface, a water repellent agent comprising at least one compound selected from the group consisting of paraffin compounds, aluminum compounds, zirconium compounds and ethylene urea compounds. A method for producing a leather for inkjet printing, which comprises applying and drying, and then applying and drying a color forming treatment solution containing a cationic substance and a binder resin.