KR20020080693A - A solution for coating of leather and coated leather with multifunctional property - Google Patents

Abstract

PURPOSE: Provided are a solution which shows effects for permanently removing malodor and inhibiting the attachment of contaminants in shoe, garment, sheet, and so on, by oxidizing and dissolving the contaminants adsorbed to three-dimensional fiber structure. CONSTITUTION: The solution comprises (a) 0.0001-5 parts by weight of porous molecular sieve, (b) 0.001-3 parts by weight of photoactive material selected from oxides represented by formula 1: AaTibOx, titanium dioxide, zinc dioxide, and zirconium dioxide, and (c) 0.5-5 parts by weight of binder resins. In the formula 1, A represents at least one element selected from zinc, tungsten, iron, tin, vanadium, zirconium, chromium, silicon, copper, cobalt, nickel, niobium, silver, molybdenum, palladium, platinum, gold, aluminum, arsenic, bismuth, antimony, cadmium, boron, cesium, cerium, magnesium, calcium, sodium, potassium, titanium, phosphorus, and manganese; each of a and b represents a molar ratio of the each components, a=1=b, b is 0.001-1, and x is a value which is chosen so as to adjust an atomic value.

Description

A solution for coating of leather and coated leather with multifunctional property}

The present invention relates to a solution for processing a leather fabric and a treated multifunctional leather fabric, and more particularly, by treating the surface of the leather fabric with a solution containing a specific molecular having a porous molecular sieve and photoactivity, antibacterial, deodorizing, breathable Leather that maintains and emits far infrared rays or decomposes organic substances adsorbed on the surface of leather fabrics.It is used for clothing, shoes, car seats and furniture sofa fabrics that create a pleasant indoor atmosphere. The present invention relates to a fabric treatment solution and a treated multifunctional leather fabric.

Currently used natural leather has a fiber structure composed mainly of collagen with a unique three-dimensional solid structure, and has a wider absorbing area per unit area than the general fiber structure, better breathability, and has excellent solar absorption and thermal insulation. Used for sofas, seats, handbags, etc. Such natural leather temporarily adsorbs odor and maintains breathability due to its characteristic three-dimensional network collagen, but loses its function over time. That is, after a certain time, the various sweat and contaminants are adsorbed, and when the supersaturated state becomes saturation, not only the odor due to the inherent odors caused by the decay of the accumulated contaminants, but also the dirt gets on the surface.

The porous molecular sieve is a material having pores of several hundreds to several hundreds of microns or more, and examples thereof include zeolite, silica gel, elvan, jade, activated carbon and M41S. In particular, zeolite (pore size 13Å or less) has been developed and used as a material in many chemical processes, but macromolecules do not pass, so steric hindrance occurs and diffusion disturbance occurs during adsorption. In contrast, mesoporous molecular sieves (15 to 500 mm 3) and micropore molecular sieves (500 mm or more) have a relatively large pore size, which causes little diffusion disturbance and is applicable to the reaction of larger molecules. The size of has the advantage that it can be adjusted according to the manufacturing method. Since the publication of papers and patents on Mobil's Composite of Matter (MCM-41) called Mesoporous molecular sieve by Beck et al. In 1992, numerous papers and patents have been reported.

Since the late 1980s, advanced countries have been actively studying the oxidation reaction using photocatalyst and oxidant, which is a kind of advanced oxidation treatment technology. Here, the term 'high oxidation treatment technology' refers to a more advanced treatment technology for oxidizing organic substances, which are pollutants, by generating hydroxy radicals (.OH) as intermediates. The main advantage of the photocatalytic oxidation reaction is that it is possible to obtain a sufficient organic pollutant treatment effect by simply supplying oxygen without adding an oxidant such as hydrogen peroxide and ozone. In the case of administration of hydrogen peroxide, the oxidizing power and bactericidal effect are further enhanced.

'Photocatalyst' refers to a substance that absorbs light in a wavelength range and helps chemical reactions occur. The photocatalyst completely oxidizes toxic substances into carbon dioxide and water using oxygen or water as an oxidant under light irradiation. This is a relatively inexpensive, renewable energy source and chemically useful material compared to other processes, as well as being recognized as a new method that can be applied to the oxidative decomposition reaction of hardly decomposable organics. This photocatalytic reaction process is used to convert various inorganic compounds into less dangerous substances for easier disposal and regeneration, and to completely decompose toxic organic compounds.

The origin of the photocatalytic reaction begins with Becquerel's discovery of voltage and current in 1839 when the silver chloride (AgCl) electrode was immersed in an electrolyte solution and then connected to a counter electrode. However, it was not until 1955 that Brattin and Garret explained the phenomenon, and since then, there have been reports of organic decomposition reactions using semiconductors such as zinc oxide as photocatalysts. It was. There are many kinds of semiconductor materials used for the oxidation / reduction reaction, but there are very few semiconductor materials that can be used for the photocatalytic reaction, and the following requirements must be satisfied. First, it must be optically active and stable without photocorrosion. Second, it must be biologically and chemically inert, and must be economically inexpensive as well as be able to use visible or ultraviolet light. According to the general results, the activity for the photocatalytic reaction of the oxide semiconductor is known in the order of titanium oxide> zinc oxide> zirconium oxide> tin oxide> vanadium oxide.

Various methods have been proposed as a method of immobilizing an oxide exhibiting activity in a photocatalytic reaction. Most of oxides are mainly used in powder form, and recovery of these particles and photoblocking by the particles are pointed out as problems. Therefore, a method of effectively fixing the photocatalyst without lowering the efficiency of the photocatalyst is required. The most common method of immobilizing an oxide semiconductor is to coat a solid support. The technique of fixing titanium oxide etc. to heat-resistant materials, such as glass, a metal, and ceramics, has been known for a long time, and it is practically used as a glass or a tile. At this time, the precursors used are titanium alkoxide, titanium chelate, titanium oxide, titanyl nitrate, titanyl sulfate, titanium tetrachloride, and the like, and coating methods mainly used include deposition coating, screen printing, spin coating, spray coating, and the like. These are known to vary greatly in photocatalytic activity depending on the materials and ranges used.

Accordingly, the present invention is a natural leather is coated with a porous molecular sieve, a specific oxide having a photoactive activity on the leather surface layer or reticular layer in view of the absorption of ultraviolet rays and visible light, etc. generated from sunlight is superior to other materials By increasing the adsorption capacity of the 3D fiber structure and oxidizing and decomposing the pollutants adsorbed on the 3D fiber structure, it provides a functional leather fabric having the effect of removing odorous substances and suppressing the attachment of pollutants in shoes, clothes, and sheets. Its purpose is to. That is, as shown in Figure 2 by coating a material having a photocatalytic activity capable of adsorbing and decomposing harmful substances with far-infrared emission on the natural leather of the three-dimensional structure before coating as shown in Figure 1 It is intended to have a function of leather, such as antibacterial, deodorant, breathable.

1 is a cross-sectional view of a natural leather having a three-dimensional structure before treatment.

2 is a cross-sectional view of a natural leather coated with a solution of the present invention.

3 is a graph showing the ultraviolet absorbance of the leather prepared in Example 1, Example 7, Example 12 and Comparative Example 1.

[Description of Symbols for Main Parts of Drawing]

1: porous molecular sieve

2: photoactive material

The present invention comprises a) 0.0001 to 5 parts by weight of a porous molecular sieve, b) 0.001 to 3 parts by weight of a photoactive material selected from oxides, titanium dioxide, zinc dioxide and zirconium represented by the following formula (1), and c) binder water It is characterized by a leather fabric treatment solution containing 0.5 to 5 parts by weight of the feeder.

Formula 1

A _a Ti _b O _x

In Formula 1 above:

A is zinc, tungsten, iron, tin, vanadium, zirconium, chromium, silicon, copper, cobalt, nickel, niobium, silver, molybdenum, palladium, platinum, gold, aluminum, arsenic, bismuth, antimony, cadmium, boron, cesium, At least one element selected from cerium, magnesium, calcium, sodium, potassium, titanium, phosphorus and manganese; a and b represent the molar ratio of each component element, and a = 1-b, where b is in the range of 0.001 to 1; x is a value determined to fit the valence.

In addition, the present invention 100 parts by weight of the leather fabric a) 0.0001 to 5 parts by weight of the porous molecular sieve, b) 0.001 to 3 parts by weight of the photoactive material selected from the oxide, titanium dioxide, zinc dioxide and zirconium dioxide represented by the following formula (1) And c) treating with a solution containing 0.5 to 5 parts by weight of the binder resin; And

Reprocessing the treated leather with 0.1 to 3 parts by weight of cationic fixing agent; characterized by another method of manufacturing a leather fabric comprising a.

The raw material of the leather fabric treatment solution according to the present invention includes a porous molecular sieve, a photoactive material, resins for binders and other additives.

The porous molecular sieve is selected from zeolite, silica gel, elvan, jade, activated carbon and M41S, and has a pore size of 5 to 1,000 mm 3. The porous molecular sieve is added in an amount of 0.0001 to 5 parts by weight, more preferably 0.01 to 1 part by weight based on 100 parts by weight of leather. At this time, the purpose of using the porous molecular sieve is to increase the adsorption capacity of the leather as well as to give the effect of excellent breathability. In general, the natural leather itself can maintain significantly better breathability than the leather coated a lot when not coated at all. The excellent air permeability is due to the three-dimensional leather structure and the air permeability according to the solution in the present invention is natural leather dyed paper〉 [resin + porous molecular sieve + photoactive material]〉 [resin + photoactive material]〉 to be. In addition, there are various flaws in natural leather, such as cotton rupture, mite marks, scratches by wire mesh, etc. In order to eliminate this, the conventional coating method requires excessive use of synthetic resins such as urethane resin and acrylic resin, which makes the film thick and breathable. The disadvantage is that it decreases. In the present invention, by using a porous porous sieve having large pores in order to compensate for such a problem, it is possible to produce a leather having excellent breathability while compensating for various scratches.

The photoactive material is added in an amount of 0.001 to 3 parts by weight, more preferably 0.01 to 1 part by weight, based on 100 parts by weight of the leather fabric. As the photoactive material of the present invention, one selected from oxide, titanium dioxide, zinc oxide, and zirconium oxide represented by Chemical Formula 1 is used. These photoactive materials have photocatalytic activity and decompose odors and contaminants adsorbed to the pores of the porous molecular sieve. In this case, the addition method of the photoactive material may be added in the state impregnated in the porous molecular sieve, in addition to the method of adding itself, which is based on the invention [Korean Patent Application No. 2001-2063] filed by the present inventors. According to the manufacturing method.

The binder resins are selected from acrylic resins, urethane resins and fluorine resins, and are added in an amount of 0.5 to 5 parts by weight based on 100 parts by weight of the leather fabric. These resins penetrate into the leather and cotton layers by penetration when applied to the surface treatment of the leather, and combine with the amine groups of the leather, so that the porous molecular sieve and the photoactive material are attached to the three-dimensional network structure as shown in FIG. Infiltrate In addition, a cationic fixing agent is added to prevent separation of the adsorbed and impregnated material, which uses a chromium trivalent ion (Cr ³⁺ ) series or an amine series. And water, paints and coating aids can be added, coatings are used in the usual, coating aids are used in oils or waxes.

If more specifically described step by step manufacturing method of leather fabric according to the present invention.

The leather fabric used in the present invention is a dyed paper that has undergone a series of dyeing processes. Usually, the dyeing process of leather is performed in the order of neutralization, dyeing, and branching. In general, the dyeing paper is coated on the cotton or reticular layer without being used as it is to be used for various purposes. Next, the step of reprocessing the treated leather fabric with a cationic fixing agent. Such primary and secondary treatments may use a dyeing drum and a coating method. In the case of using a dyeing drum, the treatment time for penetrating the solution into the leather is preferably 20 to 120 minutes, and the treatment time for penetrating the cationic fixing agent is 20 to 120 minutes. When using the coating method, it can be selected from the spray, pad coating method and roller coating method. In addition, double surface treatment is also possible in which the leather treated by the dyeing drum is treated again by a coating method.

In the present invention, a leather fabric such as a natural leather cotton layer and a natural leather mesh layer (aka split or fine leather) may be used. When such a leather fabric is treated with the solution, the porous powder as shown in FIG. It has a structure in which itself and a photoactive material penetrate and coat the leather surface layer and the network layer.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by Examples.

The following Examples 1 to 6 and 10 to 11 are examples of surface treatment using a dyeing drum, and Examples 7 to 9 are examples of surface treatment using various coating methods, and Example 12 was then coated using a dyeing drum. It is an example of surface treatment using the method.

Example 1

1,000 kg of dyed natural leather fabrics were washed with water. 1.5 kg of mesoporous molecular sieve (MCM-41), 1 kg of [TiFe _0.3 O _x ] [Elvan rock], 1,500 kg of water at 40 ° C., 20 kg of acrylic resin are mixed and placed in a dyeing drum containing leather fabric for 60 minutes. Rotated. 5 kg of a cationic fixing agent (Byer, Chromitan B) was added thereto, followed by rotation for 30 minutes to prepare a fabric. Ultraviolet absorbance of the leather thus produced was measured and compared.

Example 2

1,000 kg of dyed natural leather fabrics were washed with water. 1.5 kg of mesoporous molecular sieve (MCM-41), 1 kg of [TiFe _0.3 O _x ] [silica gel], 1,500 kg of water at 40 ° C., 20 kg of acrylic resin were mixed and placed in a dyeing drum containing leather fabric for 60 minutes. Rotated. 5 kg of a cationic fixing agent (Byer, Chromitan B) was added thereto, followed by rotation for 30 minutes to prepare a fabric.

Example 3

1,000 kg of dyed natural leather fabrics were washed with water. 1.5 kg of mesoporous molecular sieves (MCM-41), 1 kg of [TiFe _0.3 O _x ] [Elvanite + silica gel], 1,500 kg of water at 40 ° C., and 20 kg of acrylic resin were mixed and placed in a dyeing drum containing leather fabric. Rotate for 60 minutes. 5 kg of a cationic fixing agent (Byer, Chromitan B) was added thereto, followed by rotation for 30 minutes to prepare a fabric.

Example 4

1,000 kg of dyed natural leather fabrics were washed with water. 1.5 kg of mesoporous molecular sieves (MCM-41), 1 kg of [TiFe _0.3 O _x ] [Elvanite + silica gel + jade], 1,500 kg of water at 40 ° C., 20 kg of acrylic resin were mixed, and then dyed drum containing leather fabric. And rotated for 60 minutes. 5 kg of a cationic fixing agent (Byer, Chromitan B) was added thereto, followed by rotation for 30 minutes to prepare a fabric.

Example 5

1,000 kg of dyed natural leather fabrics were washed with water. 1.5 kg of mesoporous molecular sieve (MCM-41), 1 kg of [TiAg _0.05 Zn _0.05 Fe _0.2 O _x ] [Elvanite], 1,500 kg of water at 40 ° C., 20 kg of acrylic resin were mixed and then dyed drum containing leather fabric. And rotated for 60 minutes. 5 kg of a cationic fixing agent (Byer, Chromitan B) was added thereto, followed by rotation for 30 minutes to prepare a fabric.

Example 6

1,000 kg of dyed natural leather fabrics were washed with water. 1.5 kg of mesoporous molecular sieve (MCM-41), 1 kg of powder mixed with [TiFe _0.3 O _x ] [Elvanite] and titanium dioxide (P-25, Degussa-Huel), 1,500 kg of water at 40 ° C , 20 kg of acrylic resin was mixed, and then placed in a dyeing drum containing leather fabric and spun for 60 minutes. 5 kg of a cationic fixing agent (Byer, Chromitan B) was added thereto, followed by rotation for 30 minutes to prepare a final fabric.

Comparative Example 1

1,000 kg of dyed natural leather fabrics were washed with water. 1,500 kg of water at 40 ° C. and 20 kg of acrylic resin were mixed, and then added to a dyeing drum containing leather fabric, and rotated for 60 minutes. 5 kg of a cationic fixing agent (Byer, Chromitan B) was added thereto, followed by rotation for 30 minutes to prepare a final fabric. Ultraviolet absorbance of the leather thus produced was measured and compared.

Example 7

50 g of mesoporous molecular sieves (MCM-41), 30 g of [TiFe _0.3 O _x ] [ban rock], urethane resin 300 g, acrylic resin 100 g, paint 150 g, coating aid (Bayer, LEPTON Wax A) 20 g, water The mixed solution of 350 g was coated on the leather by spraying. Ultraviolet absorbance of the leather thus produced was measured and compared.

Example 8

50 g of mesoporous molecular sieves (MCM-41), 30 g of [TiFe _0.3 O _x ] [ban rock], urethane resin 300 g, acrylic resin 100 g, paint 150 g, coating aid (Bayer, LEPTON Wax A) 20 g, The solution mixed with 350 g of water was coated on the leather by a pad coating method.

Example 9

50 g of mesoporous molecular sieves (MCM-41), 30 g of [TiFe _0.3 O _x ] [ban rock], urethane resin 300 g, acrylic resin 100 g, paint 150 g, coating aid (Bayer, LEPTON Wax A) 20 g, The solution mixed with 350 g of water was coated on the leather by a roller coating method.

Example 10

Wet coating on the natural leather mesh layer by the same method and components as in Example 7.

Example 11

The same method and components as in Example 7 were coated on the natural leather mesh layer, but a dry coating method was used.

Example 12

1,000 kg of dyed natural leather fabrics were washed with water. 150 g of mesoporous molecular sieve (MCM-41), 100 g of [TiFe _0.3 O _x ] [Elvanite], 1,500 kg of water at 40 ° C, and 20 kg of acrylic resin are mixed and placed in a dyeing drum containing leather fabric for 60 minutes. Rotated. 5 kg of a cationic fixing agent (Byer, Chromitan B) was added thereto, followed by rotation for 30 minutes to prepare a fabric.

Then, the solution used in Example 7 was sprayed to coat the leather. Ultraviolet absorbance of the leather thus produced was measured and compared.

As described above, the solution for processing the leather fabric according to the present invention can impart various functions to the leather using porous molecular sieves and photoactive materials, in particular, odor when used for a long time due to the problem that can not be washed due to the characteristics of the leather It is possible to eliminate the problem of the occurrence or surface contamination and to improve breathability while eliminating scratches of the leather itself at the same time as deodorization, decomposition of organic matter and emission of far infrared rays. Therefore, reticulated leather (also known as split or shed), a by-product of natural leather, can be used similarly to cotton leather, and the photoactive material is about 1/10 to 1/1 compared with conventional commercially available titanium dioxide photocatalyst. It can be manufactured at a price of 20, which creates economically high added value.

Claims (8)

a) 0.0001 to 5 parts by weight of porous molecular sieve, b) 0.001 to 3 parts by weight of photoactive material selected from oxide, titanium dioxide, zinc dioxide and zirconium oxide represented by the following formula (1), and c) binder resin is 0.5 Solution for treatment of leather fabrics, characterized in that containing 5 parts by weight. Formula 1 A _a Ti _b O _x In Formula 1 above: A is zinc, tungsten, iron, tin, vanadium, zirconium, chromium, silicon, copper, cobalt, nickel, niobium, silver, molybdenum, palladium, platinum, gold, aluminum, arsenic, bismuth, antimony, cadmium, boron, cesium, At least one element selected from cerium, magnesium, calcium, sodium, potassium, titanium, phosphorus and manganese; a and b represent the molar ratio of each component element, and a = 1-b, where b is in the range of 0.001 to 1; x is a value determined to fit the valence. The solution of claim 1, wherein the photoactive material is contained in an oxide state or impregnated with a porous molecular sieve. The solution of claim 1 or 2, wherein the porous molecular sieve is selected from zeolite, silica gel, elvan, jade, activated carbon and M41S, and has a pore size of 5 to 1,000 mm3. The solution for leather fabric treatment according to claim 1, wherein the binder resin is selected from an acrylic resin, a urethane resin, and a fluorine resin. 100 parts by weight of leather fabric a) 0.0001 to 5 parts by weight of porous molecular sieve, b) 0.001 to 3 parts by weight of photoactive material selected from oxide, titanium dioxide, zinc dioxide and zirconium oxide represented by the following formula (1), and c) binder Treating with a solution containing 0.5 to 5 parts by weight of a resin; And Reprocessing the treated leather fabric with 0.1 to 3 parts by weight of cationic binder; Leather fabrication method characterized in that it comprises a. Formula 1 A _a Ti _b O _x In Formula 1 above: A is zinc, tungsten, iron, tin, vanadium, zirconium, chromium, silicon, copper, cobalt, nickel, niobium, silver, molybdenum, palladium, platinum, gold, aluminum, arsenic, bismuth, antimony, cadmium, boron, cesium, At least one element selected from cerium, magnesium, calcium, sodium, potassium, titanium, phosphorus and manganese; a and b represent the molar ratio of each component element, and a = 1-b, where b is in the range of 0.001 to 1; x is a value determined to fit the valence. 6. The method of claim 5, wherein the leather fabric is a natural leather cotton layer or a natural leather mesh layer. The method of manufacturing a leather fabric as claimed in claim 5, wherein the treatment is performed by a dyeing drum or by a coating method selected from a spray, a pad coating method and a roller coating method. Multifunctional leather fabric, characterized in that produced by the method of claim 5.