JPH02215900A - Method for imparting high water resistance and oil resistance to leather - Google Patents

Abstract

PURPOSE:To improve (the persistence of) water and oil resistance by reacting in a leather a cationic compound, which is capable of forming a complex, with a fluorine compound containing polyfluoroalkyl groups. CONSTITUTION:A leather containing cations (A) which preferably comprise chromium ions absorbed in the tanning step and are capable of forming a complex is dipped in a treating solution of a pH of 2.5 to 6.5 made of a fluorine compound (B) containing polyfluoroalkyl groups, having a number-average molecular weight of 300-10,000 in an amount of 0.05-20 pts.wt. based on 100 pts.wt. leather, a polyalkylene glycol nonionic surface active agent (C) in an amount of 0.05-20 pts.wt. based on 100 pts.wt. component B, and water (D), and then heated at 40-60 deg.C for 40-90min to react component A with component B in the leather so that a complex of component B is formed in the leather.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention provides durability to leather by forming a complex of a fluorine-based compound containing a polyfluoroalkyl group such as a fluoroalkyl phosphate compound in leather. The present invention relates to a method for imparting a high degree of water resistance and oil resistance to a material. [Prior Art and Problems to be Solved by the Invention] It has recently been known that treating chrome-tanned leather with an alkyl phosphate compound improves water resistance. However, treatment with an alkyl phosphoric acid compound could provide water resistance but not oil resistance. On the other hand, in order to obtain water resistance and oil resistance, the use of certain fluorochemicals such as perfluoropolyacrylate and chromium complexes of carboxylic acids containing perfluoroalkyl groups has been proposed. However, when these fluorochemicals are applied to tanned leather, such as chromium complexes,
Its uses are limited because it imparts a dark green color to leather, or when treated during the fatliquing process, such as with perfluoroacrylate, the desired water and oil resistance cannot be obtained, or it must be treated with a non-aqueous system. In addition, it is necessary to incorporate a water and oil resistant process separately from the series of leather manufacturing processes, which is unfavorable from the viewpoint of work efficiency, and therefore cannot be said to be commercially useful in leather processing. Several problems can be seen, such as the texture being rough and hard, and the quality being unfavorable. [Means for Solving the Problems] Thus, the present invention aims to solve the above-mentioned problems (it is a completed product that combines a cationic compound capable of forming a complex and a fluorine-based compound containing a polyfluoroalkyl group). The present invention relates to a method for imparting high water resistance and oil resistance to leather by reacting the fluorine-based compound in the leather to form a complex of the fluorine-based compound in the leather. As the compound, metal ions such as Cr, AI, Zr, and Na are preferred, and chromium ions absorbed into leather during the leather tanning process are particularly preferred. Polyfluoroalkyl groups (all or one of the H atoms of the alkyl group As fluorine-based compounds containing F atoms or those in which F atoms and F atoms are substituted with halogen atoms such as C1 atoms,
There are no limitations as long as it can react with the cationic compound in the leather, including acids such as carboxylic acids containing polyfluoroalkyl groups, urethane compounds, phosphoric acid compounds, and poly(meth)acrylate compounds. It is at least one kind or a mixture of two or more kinds selected from ester compounds such as. Phosphoric acid compounds are preferred because they form strong complexes with cationic compounds and have better water and oil resistance.
In order to
00, preferably 500 to 5000. A preferred fluorine-based compound from the viewpoint of water resistance and oil resistance is a single fluoroalkyl phosphoric acid compound represented by the following general formula (I) or a mixture of two or more compounds having different numbers of carbon atoms in Rf. ■ (RfRO)-P(OX)s-m-
(I) (wherein, Rf is a polyfluoroalkyl group having 3 to 21 carbon atoms, R is an alkylene group having 1 to 4 carbon atoms, and X is H
or -C) IzC:HJH, where m is an average value of 0.5 to 2.
The fluorine-based compound such as the fluoroalkyl phosphoric acid compound (representing the number 5) is usually solid and insoluble in water. Fluorine compounds that are insoluble in water include higher alcohol ethylene oxide adducts, alkylphenol ethylene oxide adducts, fatty acid ethylene oxide adducts, oil and fat ethylene oxide adducts, polyhydric alcohol fatty acid ester ethylene oxide adducts, and higher alkylamine ethylene oxide adducts. thing,
It is preferable to disperse it in water in a colorless and translucent form using a polyalkylene glycol nonionic surfactant such as a fatty acid amide ethylene oxide adduct or a polypropylene glycol ethylene oxide adduct, and then treat it to leather for absorption. The amount of fluorine compound used is O, per 100 parts by weight of leather.
OS~20 parts by weight, preferably 1 to 10 parts by weight, and the amount of the nonionic surfactant used to disperse the compound is 0 per 100 parts by weight of the fluoroalkyl phosphate compound.
．． 05 to 20 parts by weight, preferably 1 to IO parts by weight. The following treatment method is preferred as a method for reacting a cationic compound capable of forming a complex with a fluorine-based compound containing a polyfluoroalkyl group in leather. first,
Cationic compounds such as chromium ions are absorbed into the leather using the leather tanning process, and the leather containing this cationic compound is treated with fluorine, such as the colorless translucent aqueous dispersion mentioned above. In this method, a cationic compound and a fluorine-based compound are reacted by immersing the leather in a treatment solution containing a fluorine-based compound to form a complex of the fluorine-based compound in the leather. Appropriate treatment temperature is approximately 40 to 60°C and treatment time is approximately 40 to 90 minutes.The treatment liquid has a pH of 2.5 to 6.5, as alkalinity will have an adverse effect on the leather. The treatment liquid should be adjusted to be acidic (preferably; a number of fatliquors such as animal and vegetable oils, sulfated oils, sulfite oils, mineral oils, synthetic oils, etc.) may be used in combination with the processing liquid. [ Examples] Next, examples according to the present invention will be specifically described.
It goes without saying that the present invention is not limited in any way by the above description. In addition, in the following examples, water resistance and oil resistance were measured as follows. In other words, the water resistance is 1. U,
It was carried out according to the dynamic water resistance measurement method of P-10 and expressed as the average value. Oil resistance was measured according to the AATCC by applying a few drops of the test solution shown in Table 1 to several places on the sample (diameter 4 am
), and the state of penetration is judged after 30 seconds. Table 1 In addition, white charcoal was measured using a digital color difference meter manufactured by Nippon Isshoku Co., Ltd. at a wavelength of 450 μm, with magnesium oxide as 100, and expressed as an average value. The lower the number,
It shows that the coloration is large. Example 1 "Preparation of treatment bath" 1 part of Meiselin C350X [polyethylene glycol nonionic surfactant manufactured by Kaisei Kagaku Kogyo Co., Ltd.] was added and melted by heating at 80°C, and while stirring, 194 parts by weight was added at 80°C. Water is gradually added to emulsify the mixture to obtain a translucent aqueous dispersion, which is then cooled and adjusted to pH 3 to 3.5 with formic acid to form a predetermined treatment bath. ``Treatment'' Chrome tanned cowhide leather was used, soaked in the above treatment solution in a drum, treated at 50℃ for 60 minutes, washed with water, air dried, rubbed in the usual manner, and dried in a bottle. . Note that after 60 minutes at 50° C., the treatment bath became clear, indicating that the compound was essentially absorbed into the leather. For comparison, 5 parts by weight of dodecyl phosphate prepared in the same manner as above, 1 part by weight of Meiselin 0350X,
Mixed treatment solution of 200 parts by weight of water (pH 3-3.5 with formic acid)
The treatment was carried out under the same conditions as above. The performance after treatment is as shown below, and the method of the present invention provided excellent water resistance and oil resistance. Untreated product 5g lOg 20g comparative treated product
0.00g 0.03g 0.05gProduct treated according to the present invention 0.00g 0.02g 0.03g0.
08g 0.65g 0.7g0.04g 0.
08g 0.08g Initial stage of processing 22 hours later 0 Untreated product 0 Comparatively treated product 0 - Processed product according to the present invention 33°The sample was subjected to a dynamic water resistance tester, and after 22 hours, the sample was taken out and the sample was dried. Then measure. (The same applies hereinafter) Example-2 "Preparation of treatment bath" A translucent water dispersion was obtained, cooled, and adjusted to pH 3~ with formic acid.
3. Adjust the prescribed treatment bath to 5. ``Treatment'' Using chrome tanned cowhide leather, soaked in the above treatment solution,
The treatment was carried out under the same conditions as in Example 1. The performance after treatment is shown below. After 5 minutes After 30 minutes 0.00g 0.01g Initial 22 hours after 1 hour after 5 hours after 22 hours 0, 04g O, asg O, 1g 3-4 3-4 Example 3 "Preparation" fl Add 1 part of 10 mole adduct of stearic acid ethylene oxide, heat and melt at 80°C, and gradually add 194 parts by weight of water at 80°C while stirring to obtain 4 parts by weight of milk and 2 parts by weight of liquid paraffin. , Meiselin Old 70x [polyoxyethylene alkylphenol ionic surfactant manufactured by Kasei Kagaku Kogyo Co., Ltd.] 1 part by weight was added, heated and melted at 80°C, and while stirring, 193 parts by weight of water at 80°C was gradually added. In addition, emulsify to obtain a homogeneous dispersion, cool it, and add p) with formic acid.
Adjust the predetermined fatliquor mixture treatment bath to 13 to 3.5. "Treatment" Chrome tanned cowhide leather was soaked in the above mixed treatment solution and treated under the same conditions as in Example 1. For comparison, a sample without liquid paraffin was also subjected to the same treatment. The performance after treatment is as follows: even when liquid paraffin is added and treated at the same time, excellent water resistance and oil resistance can be obtained. After 9 hours After 9 hours After hours After hours Liquid paraffin-free treated product 0. OOg 0.02g 0.03g
0.04g 0.09g Liquid paraffin addition mixed treatment product 0.0010.02g o, o4g
o, osg 0.095g After the initial 22 hours of rainbow processing, no liquid paraffin added, mixed with liquid paraffin, one color white road chrome tanned cowhide 75 No liquid paraffin added 75 Mixed with liquid paraffin 75 This Separately, the following comparative example was conducted. Chromium complex compound of perfluoroalkyl polyacrylate 4 parts by weight Liquid paraffin 2 parts by weight Meiselin H170X
1 part by weight water
193 parts by weight Total 200 parts by weight (adjusted to 3 to 3.5 with formic acid) Chrome tanned cowhide leather was soaked in the above mixed treatment solution and treated under the same conditions as above. The performance after treatment is as follows, and very good water resistance and oil resistance were not obtained. In addition, the white road was 54. After 5 minutes After 30 minutes After 1 hour 1 g 2 g log After processing 9 2 After 1 hour 0 The above results were the same for those to which liquid paraffin was not added, and good water resistance and oil resistance were not obtained. [Effects of the Invention] Thus, the leather products obtained by the method of the present invention are free from coloring due to complexes, have good feel, texture, and appearance, and exhibit high water resistance and oil resistance.

Claims (1)

[Claims] 1. Reacting a cationic compound capable of forming a complex with a fluorine-based compound containing a polyfluoroalkyl group in leather to form a complex of the fluorine-based compound in the leather. A method of imparting high water and oil resistance to leather. 2. Leather containing a cationic compound capable of forming a complex is immersed in a treatment solution containing a fluorine-based compound containing a polyfluoroalkyl group, thereby removing the cationic compound and the fluorine-based compound from the leather. A method for imparting a high degree of water and oil resistance to leather according to claim 1, wherein the reaction is carried out in a leather.