KR20000036264A - The transcribing and printing method for hand washable leather - Google Patents

Abstract

PURPOSE: A transfer printing method of leather is provided that can enhances a photoresistance and a friction resistance, represents an elaborate pattern and particularly improves a cleaning resistance and dry cleaning property. CONSTITUTION: A transfer printing method of leather comprises the steps of using glutaraldehyde in a pretanning as a tanning assistant before chrome-tanning of raw leather; modifying a surface of tanned leather by coating the tanned leather with a composition comprising 45 to 55 parts of weight of water-dispersible polyester resin(10%), 10 to 20 parts of weight of acrylic resin, 3 to 8 parts of weight of polyurethane resin, 2 to 3 parts of weight of wax, 1 to 2 parts of weight of alcoholic permeating agent and 20 to 30 parts of weight of water; and printing a separately prepared transfer raw paper with a roller gravure printer.

Description

The transcribing and printing method for hand washable leather}

The present invention relates to a transfer printing method of leather, and more particularly, it is excellent in daylight fastness and friction fastness and can precisely express a pattern. It relates to a transcription printing method.

In the process of producing leather products (water-lime-lime-lime and hyohae-pickling-chrome-tanning-dehydration-retanning-neutralization-dyeing, eggplant-painting), when water consumption is high and heavy metals are not recovered, Pollution can be reduced.

In particular, when dyeing leather products, acid dyes and direct dyes are mainly used, and the dyeing property varies depending on the acidity of the leather. Therefore, the use of metal dyes causes little change in dyeing properties and thus good washing fastness and light resistance. Cause

In the case of reactive dyes, treatment with alkali baths covalently bonds with the fibers, which significantly improves the washing fastness, but it is difficult to obtain dark colors due to the many dyes that do not stick and dissolve from the leather. It is difficult. In addition, it is difficult to produce various patterns in case of soaking.

In order to solve the problem of soaking, there have been attempts to improve the added value of leather products by introducing a printing method to the leather to compensate for the surface damage of the leather during breeding and to produce various patterns.

As a method for printing textile products, various methods such as roller printing, silk screen printing, dry transfer printing, wet transfer printing or photosensitive printing are used.

However, in the case of leather, especially natural leather, it is difficult to use a general printing method due to the characteristics of the material, and only a roller printing method or a silk screen printing method has been used. However, when the roller printing method or silk screen printing method is applied to leather, it is difficult to express elaborate patterns due to the elasticity of the leather and the spread of the pigment, and the pigment is hardened by embossing the pigment on the surface of the leather, which deteriorates the touch. However, there is a problem in that the friction fastness of printing.

In addition, the general dry transfer printing method used in textile products can be applied to leather.

Transfer printing is a very simple printing technique that transfers and prints a dye printed on paper onto a cloth by heat. It is a technique proposed by British Celanese in 1929.

The transfer printing method is a simple method of applying color, and since it is a drying process itself, there is no need for post-treatment after application, so the process itself is clean and there is almost no water, so there is almost no problem of securing industrial water. It is one of the few clean processes in the dyeing process where there is very little cause of pollution pollution because it does not occur.

However, dyes and fiber types suitable for this transfer printing method are extremely limited in consideration of sublimation and stability at high transfer temperatures (around 200 ° C), and at present, some of the dyes are mainly applied in the printing process of polyester fibers. Doing.

Of course, in addition to research on dispersing, basic and reactive disperse dyes in natural and synthetic polyamide fibers and cotton, there are some practical applications. Examples of applying the transfer printing method to leather include Ciba-Geigy and Some Japanese companies have done research but have not yet commercialized.

The reason is that when applied to leather, the disperse dyes do not dye on the leather, so the light fastness is very bad. In the case of using the resin, the pigment mixed with the resin moves to the cloth as the resin melts, but the resin cracks or falls off due to friction, and the touch is also bad. The solution to this problem is to modify the surface of the leather so that the dye can be transferred without affecting the leather properties.

As a technique of modifying the surface of leather to improve dyeability, frictional fastness, and the like, Korean Patent Application No. 94-11450 (Patent No. 131342) by the inventors is given.

However, the present invention has a problem that the heat resistance of the leather, elasticity, dye fastness, and other various physical properties are insufficient.

As a technique for solving such a problem, there is a domestic patent application No. 95-43930 (Patent No. 156291) by the present inventor, this technique is unsaturated polyester, crosslinkable polymer, acid component on the surface of the leather paper , Alcohol components and the like were condensed by heat applied in the transfer process to modify the surface of the leather.

However, the product of this technology has improved the light fastness, friction fastness, and fineness of printed pattern.However, the surface of the leather is hardened by the reaction of unsaturated polyester component and acid component (fumaric acid). This soft feeling is lacking, and thus there is a problem that the friction fastness is lowered when used for a long time.

In addition, it can be pointed out that the product obtained by this technology is difficult to wash water due to the lack of water resistance as in general leather products.

The present invention is to solve the problems as described above, to maintain the soft feel of the leather surface, not only excellent friction fastness, but also excellent washing fastness to provide a printing method of leather paper that can be washed with water. The purpose.

According to the present invention, after tanning by adding a tartar (Glutaraldehyde) as a tanning aid in pretanning before chrome tanning raw hides, 45 to 55 parts by weight of a water-dispersible polyester resin (10%) in the tanning is completed, acrylic resin 10 Roller type gravure printing machine after modifying the surface with a composition composed of -20 parts by weight, 3-8 parts by weight of polyurethane resin, 2-3 parts by weight of wax, 1-2 parts by weight of alcohol-based penetrant, and 20-30 parts by weight of water. It is characterized by printing with.

Hereinafter, the present invention will be described in detail.

Raw hide goes through the process of Soaking, Fleshing, Unhairing, Liming, Splitting, Scudding, Deliming and Deliming & Bating Prepared raw materials, such as pickling, chrome tanning, dehydration, splitting, retanning, neutralization, dyeing, eggplant, dehydration, drying, humidity, stalking, and toggle It goes through a series of tanneries such as drying and painting.

The purpose of tanning is to change the protein of napel (pelt) to a stable material, not to decay, to improve heat resistance, elasticity, etc. to change to a stable material.

In general, tanning agents used in tanning are chromium sulfate (Chromium-Sulfate), aluminum sulfate (Aluminium-Sulfate), and the like. In the present invention, glutaraldehyde is used as a tanning aid. The use time is when pretanning before chrome tanning. Glutaraldehyde is much faster than formalin or glyoxal.

In chrome tanned leather, only 0.75% is bound in a 3% solution, but in the case of raw leather it is bound by 21%. Therefore, the use of glutaraldehyde as a tanning aid during pretanning before chrome tanning can effectively prevent the leather from shrinking.

At this time, excessive use of collagen and dialdehyde (Dialdehyde) is azomethine (Azomethine) is formed by the combination of yellowing phenomenon may occur, so be careful.

In addition, the reason for using eggplant is as follows. When animal blood survives, fat and various proteins lubricate between protein fibers in vivo, but most of the fat and protein components in the hides are in alkali or interface in the process of being tanned from raw skin to tanning. Proteins such as collagen, which have been dissolved and eluted due to the action of the activating enzyme, are also chemically denatured by chromium tanning, so when these leathers are dried, they become hard as wooden sticks.

Therefore, if the fat is added between the fibers or the fiber bundle before drying the leather, it acts as a lubricant between the fibers and reduces friction, so that the leather can maintain proper softness even after drying. It is put.

However, after washing, the eggplant, which is not combined with the leather, is pulled out and the leather is reduced, and the touch is bad. Therefore, in order to be able to wash water, it is necessary to use eggplant which does not fall out when washing with leather.

To be a transfer printing, the surface of the leather must be modified, and polyester-based resin should be applied to the leather to improve the dyeing property of the disperse dye.

The resin composition for surface modification used in the present invention is as follows.

(A) 45-55 parts by weight of water-dispersed polyester resin (10%), (B) 10-20 parts by weight of acrylic resin, (C) 3-8 parts by weight of polyurethane resin, (D) 2-3 parts by weight of wax. (E) 1 to 2 parts by weight of alcohol-based penetrant, 20 to 30 parts by weight of water

To increase the heat resistance, light resistance and dry cleaning resistance of the leather, before spraying the water-dispersible polyester and the crosslinkable polymer, the temperature of the temperature below 70 ° C after immersion in the alcohol-containing sorbent to homogenize the surface of the leather. It is preferable to dry at.

Selected dyes are preferably used to select the disperse dyes having excellent properties of the medium and low energy type. Mid-low energy dye means the dyeing temperature is within 220 ℃, examples are shown in Table 6 below. When using a high-energy dye, there is a problem that the dye is easily migrated after dyeing.

Viscosity enhancers used to print these dyes on transfer papers include ethyl cellulose, hydroxyoxycellulose, polyvinyl alcohol, and the like.

Selected dyes, viscosity enhancers, dye solvents, etc. are mixed and printed with a slice roller type gravure printing machine with a rollet 90 ~ 130mesh and a depth of 0.1 ~ 0.4㎜.

A gravure printing machine and a flatbed printing machine can be used for a transfer method, It is suitable to carry out transfer temperature in 4-8 second and pressure 4-5 kg / cm <2> conditions at 240 degreeC-260 degreeC. If it is out of this range, the dye transfer may be insufficient or the leather may be damaged.

Embodiments of the present invention are as follows.

<Production Example 1>

* Production Process of Washing Leather

(1) materials and equipment

Infestation: Napis divided after lime

Dyes: use the dyes listed in Table 5.

Other drugs: degreaser, ammonium chloride, formic acid, agonists, sulfuric acid,

Sodium bicarbonate reducing agent, white tanning agent, eggplant (5 types)

Sodium Acetate, Glutaraldehyde (25% aqueous solution), Fixing agent

Pretreatment Processing Agent: (PU resin, acrylic resin, Wax)

Post-Treatment Agent: (Laccar, Touch Product)

Experimental equipment

Gravure Printing Machine: (Product Name: Gravure Printer)

Flatbed compressors, weather-o-meter (Atlas)

Thermometer

(2) Deliming and Hindering Process

The drugs described in Table 1 below were used.

Operation flat% temp ℃ Chemical% Runningtime Control water 150 30 Degreaser ^{* 1} 1.5 20 minutes Ammonium chloride 1.2 30 minutes Formic acid 0.6 90 minutes ※ Deactivation ^{* 2} 1.2 180 minutes pH 7.5 Drainage and Cleaning

%: Based on divided weight

※: divided into 3 times every 30 minutes

* 1: Degneasend of ICI

* 2: Bactenicide2B of ICI

(3) tanning and neutralization process

The drugs described in Table 2 below were used.

operation flat% temp ℃ Chemical% Runningtime Control water 100 35 Salt 8.0 20 minutes Formic acid (85%) 0.1 30 minutes Glutaraldehyde 5.0 Proprietary Eggplant ^{* 3} 0.5 30 minutes Sulfuric acid 0.8 60 minutes Chrome powder 7.0 ※ Proprietary Eggplant 0.5 Bicarbonate soda 1.0 120 minutes pH 4.0 Fixing agent ^{* 4} 1.0 30 minutes Reductant ^{* 5} 1.0 30 minutes Drainage and Cleaning

※: divided into 4 times every 30 minutes

Split after 72 hours

* 3: ICI Conilen275

* 4: ICI EX52863

* 5: ICI Renekton QSSolution

(4) Retanning and Branch Process

The drugs described in Table 3 below were used.

operation flat% temp ℃ Chemical% Runningtime Control water 100 35 Glutaraldehyde 2 Proprietary Eggplant 2.0 30 minutes Chrome powder 2 40 minutes Soda Acetate 3.0 30 minutes Sodium bicarbonate 1.0 20 minutes Fixative 0.5 30 minutes reducing agent 1.0 30 minutes Drainage and Cleaning water 100 adjustment Retanning agent 3.0 30 minutes Oily eggplant ^{* 6} 10 40 minutes Formic acid (85%) 0.5 20 minutes pH 3.5 Drainage-drying-milling

* 6: Corilene F360 from ICI

<Production Example 2>

* Preparation process for transfer printing

100 kg of tanned cowhide was treated with 3 kg of polyethylene ethylene alkyl amine ester (PEAA), 3 kg of polyethylene glycol (Triton X-100), 74 kg of water, 20 kg of isobutyl alcohol, and soaked at 20 ° C. for 1 hour, followed by 60 ° C. to 70 ° C. Homogenize the surface of the leather by drying the leather in a dry chamber of gkduT.

The leather made by the above method was sprayed twice by using a sprayer having a diameter of about 0.1 mm, and the drug mixture of Table 4 was sprayed twice and dried at 50 ° C. or lower for 24 hours.

About product name usage Water Disperse Polyester Resin (10%) 50 parts by weight Acrylic resin 15 parts by weight Polyurethane resin 5 parts by weight Wax 2.5 parts by weight Penetrant 1.5 parts by weight water 26 parts by weight

<Production Example 3>

* Manufacture of transcription base

Using the medicament shown in Table 5 below, it was printed using a rollet gravure printing machine with a roller of Rollet 90 to 130 mesh and depth of 0.1 to 0.4 mm.

About product name usage Disperse dyes of Table 6 5 parts by weight Ethyl cellulose 20 parts by weight ethanol 20 parts by weight Isopropyl Alcohol 40 parts by weight water 15 parts by weight

: Disperse dye used division C.I. No Preparation Example 3-1 Disperse Yellow 3 Preparation Example 3-2 Disperse Yellow 54 Preparation Example 3-3 Disperse Yellow 71 Preparation Example 3-4 Disperse Orange 25 Preparation Example 3-5 Disperse Orange 29 Preparation Example 3-6 Disperse Red 127 Preparation Example 3-7 Disperse Blue 56 Preparation Example 3-8 Disperse Blue 87 Preparation Example 3-9 Disperse Violet 28 Preparation Example 3-10 Dianix Navy Blue BG-SE

<Example 1-10>

Preparation of leather modified by the method of Production Examples 1 and 2 Place the transfer paper printed with dispersion dye on the pretreated cowhide using the transfer paper produced in the method of Production Example 3, and use a flat plate compressor to heat the temperature 260 ° C. and the heating time. Transfer was carried out under conditions of a pressure of 300 gr / cm 2 for 6 seconds. Physical properties were tested after the following process and top lacquer process.

The results are shown in Table 7 below.

* Manufacturing process

1st step: 10% water-soluble resin spray (2 times) -drying-170 ℃ 1 minute fixing

2nd stage: 5% water dispersion resin spray (2 times) -Drying-170 ℃ 1 minute fixation

* Top lacquer process

30% lacquer emulsion spray-dry-plate 80 ℃, 25kg / ㎠

* Property test

Daylight Fastness Test: Related Standards: KS K 0218 (Direct Practice)

Equipment: Weatherometer (Atlas): Xenon arc

-Iron fastness test: Related standard: KS K 0460

Equipment: Thermometer (Daiei Kagakuseiki Seisakusho.Co.Ltd)

-Friction fastness test: Relevant standards: KS K 0650 (Clock Metric)

Equipment: Crock meter

-Dry cleaning fastness test: Related standard: KS K 0644 (Petroleum solvent method)

Device used: Launder-O-meter

-Laundry fastness test: Related standards: KS K

Equipment: Polymat (Ahiba)

division Type of used transfer paper Daylight fastness Friction fastness The sophistication of the pattern Example 1 Of Production Example 3-1 Grade 5 Grade 5 Great Example 2 Of Production Example 3-2 Grade 5 Grade 5 Great Example 3 Of Production Example 3-3 5-6 grade Grade 5 Great Example 4 Of Production Example 3-4 4-5 grade Grade 5 Great Example 5 Of Production Example 3-5 4-5 grade Grade 5 Great Example 6 Of Production Example 3-6 Grade 4 Grade 5 Great Example 7 Of Production Example 3-7 Grade 4 Grade 5 Great Example 8 Of Production Example 3-8 Grade 4 Grade 5 Great Example 9 Of Production Example 3-9 Grade 4 Grade 5 Great Example 10 Of Production Example 3-10 Grade 4 Grade 5 Great

division Type of used transfer paper Color fastness Ironing Fastness Dry cleaning Example 1 Of Production Example 3-1 Grade 5 Grade 5 Grade 5 Example 2 Of Production Example 3-2 Grade 5 Grade 5 Grade 4 Example 3 Of Production Example 3-3 Grade 5 Grade 5 Grade 5 Example 4 Of Production Example 3-4 Grade 5 Grade 5 Grade 5 Example 5 Of Production Example 3-5 Grade 5 Grade 5 Grade 5 Example 6 Of Production Example 3-6 Grade 5 Grade 4 Grade 4 Example 7 Of Production Example 3-7 Grade 5 Grade 5 Grade 4 Example 8 Of Production Example 3-8 Grade 5 Grade 5 Grade 4 Example 9 Of Production Example 3-9 Grade 5 Grade 5 Grade 5 Example 10 Of Production Example 3-10 Grade 5 Grade 5 Grade 4

As can be seen through the above embodiment, the printing method according to the present invention not only improves the light fastness and the fastness of friction and can accurately express the pattern, but also can improve the leather fastness and dry cleaning properties, thereby improving the leather products. Washing was possible.

Claims (4)

Glutaraldehyde is used as a tanning aid during pretanning before chrome tanning raw hides. 45-55 parts by weight of water-dispersible polyester resin (10%), 10-20 parts by weight of acrylic resin, After coating with a composition consisting of 3 to 8 parts by weight of polyurethane resin, 2 to 3 parts by weight of wax, 1 to 2 parts by weight of alcohol-based penetrant, and 20 to 30 parts by weight of water, and modifying the surface, the roller was separately produced. A transfer printing method of leather, characterized by printing with a gravure printing machine. The method of claim 1, wherein the transfer temperature is 240 ~ 260 ℃ leather transfer printing method. The method of claim 1, wherein the leather is immersed in a wetting agent containing an alcohol component before surface modification and dried at a temperature of 70 ° C or less. The method of claim 1, wherein the dye used to prepare the transfer paper is a medium-low energy type.