TW200848517A - Soil-repellent composition for leather - Google Patents

Abstract

The present invention relates to the use of amino-functional organopolysiloxanes for improving the soiling behaviour of leather, the active substance preferably being used in the topcoat or as an overspray solution. By chemical modification with reactive groups, the properties of the amino-functional organopolysiloxane can be adjusted in a targeted manner.

Description

200848517 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to the use of an organopolyoxyalkylene having an amine functional group for improving the staining properties of leather. The dirt of leather and leather products is highly dependent on color. There is no problem when dirt occurs on black leather, because the leather has been finished with workmanship' but it is a great problem for light tones. As is well known to those skilled in the art, this aspect can be improved by the use of polymeric binders and matting components specifically selected for final finishing. Further, the formulation can be improved by adding an additive. In the final application of the outer skin (tank), the last layer applied is usually composed of a number of layers and contains a coating of adhesives and additives to protect the surface of the damaged leather. However, in some cases, the outer skin is only treated with oil or wax. If a system consisting of multiple layers of laminate and containing a binder is used, the uppermost layer is called a surface coating, which has a strong influence on physical properties, so the influence on the staining property is stronger than that of the lower layer. The additive used to reduce soiling may be applied to all layers of the final finish, but is preferably applied to the surface coating. [Prior Art] It is known to use an aqueous polyoxo-oxygenated composition having an amine functional group. These compositions are used, for example, for the water repellent treatment of cloth or building materials or as a component of a cosmetic or skin care composition. Those skilled in the art are aware of organic polyoxo-oxygenates having an amine functional group in the form of an oil-in-water or oil-in-water emulsion. These emulsions may be in the form of so-called microemulsions or macroemulsions which are typically stabilized with a nonionic, cationic or amphoteric emulsifier or a ketone 126258.doc 200848517 keto-polyether copolymer emulsifier. -: This, for example: DE 43 28 917 ^, describes a method for preparing a microemulsion based on an organopolyoxane having an amino group B, which is sequentially combined as a constituent in any order. Polysecond oxygen burning, emulsifier, X can be selected as a common surfactant and the acid to be used. Therefore, the use of the amine group g-based organic polyoxin emulsion on the leather is also illustrated by, for example, DE 1〇 2()() 4 () 4() 266 Al. However, at this time, only the organopolyphosphorus having an amino functional group is used for the hydrophobic action of the surface of the leather for the time required for the water droplets applied to the surface thereof to penetrate into the interior of the leather. This hydrophobic effect is the water repellency of the surface, so the surface or substrate is not: wetted. In contrast, the non-staining property is related to the surface's ability to prevent soil adhesion or to avoid wood color or other damage due to dirt. Dirt may include different compositions based on, for example, carbon black, oil scum, succulent beverage dyes or chemical chains, depending on the substrate being processed and the field. In the field of leather, carbon black, oil smash and/or dye are most often applied for the test (iv). Organic polyoxoxizes containing perfluoroalkyl side chains or perfluoro side groups and their use on different substrates such as leather are known. This point is illustrated, for example, by adding (9) 49 953 A1. The hydrophobicity and oleophobicity of the disclosed compounds are emphasized in DE 196 49 953 A1. However, the oil-repellent effect due to the hydrophobicity or the oleophobic property of the hydrophobicity cannot be regarded as having the antifouling ability, which means that such treatment does not impart antifouling properties. The relevant tests for soil release showed that 'when using their fluorides and polymers for final finishing of leather, there was no or substantially no improvement in antifouling properties. In addition, in other technical fields, hydrophobic or oleophobic treatment is also 126258.doc 200848517. Hydrophobic-treated exterior components are more susceptible to contamination, and it has been identified that water-resistant additives cause this problem due to higher drillability (_ ^ E.Bagda? A. IJlgen; Farbe and Lack, 112 (2006) S. 36-42). The fabric also showed no correlation between oil resistance and stain resistance (see D. F. Cooke, Textile Chemist and Colorist, 19 (1987), S' 31-41). The correlation between the hydrophobicity and/or the oleophobicity and the antifouling property is also shown in the present application (see the example examples T〇P6 and Dingop7). Fluorine chemicals are also often used in antifouling processing, but they have the disadvantage of being unsuitable and do not meet all the necessary conditions for leather customers in terms of efficiency. In addition, fluorochemicals may be unsafe because they accumulate in animal tissues and have an adverse health effect. Therefore, there is still a need to provide a leather which has antifouling processing and which does not adversely affect its performance characteristics. /, [Summary of the Invention] It has now been found that the use of organopolyoxyalkylenes having an amino functional group (hereinafter referred to as amino alanes) can dramatically reduce the amount of fouling, especially when used in surface coatings or When on an additional layer. The invention is therefore directed to the use of an amine oxirane for the antifouling treatment of leather surfaces. However, the compound as the amino siloxane in accordance with the present invention is preferably not limited to the linear or branched organopolyoxane of the formula (1). R2wR13.wSi-〇-[SiRl2-〇]x[SiRlRN〇]y.[SiRlQ〇]rSiRl3wR2^ (1) At this time, R1' independently represents the monovalent saturation with 丨-20 carbons and / 126258.doc 200848517 $No A saturated linear or cyclic hydrocarbon group. The hydrocarbon-oxyl group is particularly equivalent to the formula 1 or a combination thereof, and when it is a polyethylene glycol or a polypropylene group, the set value of j may be between 1 and 50. Aliphatic unsaturation - Examples of oximes are vinyl, propenyl, butenyl or hexenyl groups, and • Examples of groups are phenyl, alkaryl groups such as tolyl or aralkyl V groups. Examples of the n-alkyl group are a methyl group, an ethyl group, a butyl group and a hexyl group. Examples of the cycloaliphatic hydrocarbon are a cyclopentyl group or a cyclohexyl group, an example of an isoalkyl group is a "propyl group or a pentyl group, and an example of an alkyl group having a tertiary carbon atom is a third group (.' group and a third group Preferably, it is preferably a short-chain alkyl group having 1 to 5 carbon atoms, particularly preferably a methyl group or an ethyl group. / represents a gas, a methyl group, an ethyl group or a hydrazine group, and may represent, for example: Methyl ethyl, propyl, butyl, pentyl and methoxyethyl groups, methyl and ethyl are preferred. r2 may also have a nitrogen-containing group as defined for rN, and R may represent a value between 丨. R represents a group of formula (II) ('-(CR^)m - [NR3k . (CR32)n]p . NR3 , R4 (9) NR3k group or nr3 fluorenyl group The group may also be a 饱和t , 1 力 force to have a saturated or partially saturated heterocyclic ring containing 5-10 ring atoms, and Q represents a group of the formula (in) _ · _ - _2) η ]ρ - NR3 · (CR32W*Si (m) or a group of formula (IV) -(CRJ2)m · N[ · (CR32)n - NR3]p -*Si (iV)

Si represents an inter- or intra-molecular chain linking a molecule of the formula (I). An example of Q is 126258.doc 200848517 -(CH2)3-NH-(CH2)2-NH-(CH2)3- and CH2CH(CH3)CH2-NH-(CH2)2-NH-CH2CH(CH3)CH2- . The values of x, y and z are chosen such that the amine content is 〇·〇1 meq/g-20 meq/g (milli equivalents per gram of amine oxirane), ie in the acid/hydrazine titration, 1 g of amine The oxane consumes 0.01 ml to 20 ml of 1 molar concentration of hydrochloric acid, and its viscosity is in the range of 20 mPa.s to 1,000,000 mPa.s at 25 °C. The value of z is 0 or as large as the average value per mole of oxime oxime. The values of k and 1 can be independently 〇, 1 or 2. The values of m, η and η are each independently 1-10; and p can be set to 〇, 1 or 2. R3, independently, is a saturated and/or unsaturated linear and/or cyclic hydrocarbon group or hydrogen having 1 to 30 carbon atoms, preferably hydrogen or methyl. k R4 may represent hydrogen or a hydrocarbon group, for example, an -n-alkyl group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, a butyl group or a hexyl group; a cycloalkyl group; an isoalkyl group having 3 to 20 carbon atoms, For example: isopropyl and pentyl, and alkyl groups having a total of 4 to 20 carbon atoms having a tertiary carbon atom, such as a tert-butyl group and a third pentyl group. Hydrogen or a burnt group having 1 to 4 carbon atoms is preferred, and hydrogen is particularly preferred. RN^J ^ ^ -(CH2)3-NH2,KCH2)3NH.C2H4-NH2,-(CH2)2-NH2,-(CH2)2-NH-CH3, -(CH2)4-NH2, -(CH2 2-NH-(CH2)2-NH-C4H9, -(CH2)2-CH-(CH3)-NH-(CH2)2-nh2, (CH2)4-NH-(CH2)3-NH-C2H5 , -(ch2)3-n(ch3)-(ch2)2-n(ch3)2, ί -(<:Η2)2〇:Η((:Η3)-ΝΗ·((:Η2)4· ΝΗ2, -(CH2)2CH(CH3)-NH-(CH2)2-NH-C4H9, -CH2-CH-(CH3)-NH-(CH2)2-NH2. However, examples of nitrogen-containing groups may also be They are the following chemical formulas:

'hc-- ' 126258.doc -10- 200848517 The preferred group is <CH2)3NfrC2H4^NH2^CH2~CHKCH3

R5 represents a divalent hydrocarbon group having no aliphatic multiple bond and each group having 1 to 4 carbon atoms. The amine groups of some amino alkoxynes may be present in the form of amidino or imine groups, for example by reaction of a primary or secondary amine with an anhydride or a mercaptoamine gas. Furthermore, the amino aristochene may be partially quaternized in a suitable manner. For use in accordance with the present invention, the amine functional group in the amine oxane can be reacted with a protonated organic or inorganic acid to produce the corresponding ammonium salt. Examples of the organic acid may be mentioned, for example, acetic acid, oxalic acid, benzoic acid, citric acid, acrylic acid, caproic acid, dodecanoic acid, cyclohexanecarboxylic acid, bromobenzoic acid, nitrobenzoic acid, orthophthalic acid. Maleic acid, oleic acid and phenylacetic acid. Examples of inorganic acids which can be used are hydrochloric acid, hydrofluoric acid, sulfuric acid, phosphoric acid, diethyl phosphate and the like. The organic acid is preferred, and formic acid and acetic acid are particularly preferred. The amine oxyhydrogenation used in accordance with the present invention may also be a mixture of compounds of the formula (1) which may also be a reactive component which forms a chemical bond with other components. [Embodiment] There is no uniform standard for the staining of leather. Especially in the automotive sector, more than 126258.doc 200848517 standards can be obtained from the specifications of many different car manufacturers. In most cases, the test cloth with a standardized amount of mud was applied to a special test machine of the so-called Martindale tester on the surface of the leather (4). Compared with the unstained leather surface, the degree of grayscale and dirt is from! (Strongly contaminated) _5 (no contamination) grading evaluation. Sometimes, the stained leather sheet is also treated with a cleaning solution, and the gray level is used again to assess the cleaning effectiveness. The action mode of the amine-based oxy- oxygenation has not yet been formed. 4 The sulphur-burning sulphur can be formed between the final coating and the test fabric. The layer first changes the friction coefficient and then prevents the leather surface from directly contacting the dirt. It is impossible for the dirt to enter the final finishing surface. The possible interaction between the amino-functionalized Oxygen-based functional group and the soil or the finished leather surface is shown to improve on non-staining compared to the unfunctionalized Oxygen. At the office. In the final finish layer, it is preferred to add a certain amount of long-lasting property when the amine-based oxy-oxygen is added to the surface coating, so that the linalone can provide long-term protection for the finished leather product. Part of the amino-based stone hospital is also chemically bonded by a cross-linking agent commonly used for surface coating. Therefore, I5 has used the leather for a period of time or after the cleaning step, and there is still a significant amount of amine-based oxane. Present on leather. The use of a cut emulsion, particularly an amine-based calcined or emulsion thereof, according to the present invention, is the addition of an amine-based oxyhydrogenate formulation to a formulation corresponding to the prior art, particularly a surface coating formulation. Alkyl oxyhydrogenation is used in the form of a water-soluble or cosolvent-soluble compound (for example, an alkoxylated amine oxane), in a water-dispersible form with or without a co-solvent, or A microemulsion or a coarse emulsion is formed. The amount used depends on the rolling in the chosen form, the necessary conditions and application methods for the finished leather. 126258.doc -12 - 200848517 Often, based on the weight ratio of 1000 parts of the formulation, the amount of amine oxazane added in the weight ratio of i-500 parts, specifically 5 _ 3 parts by weight, very specific 20-200 parts by weight to weight ratio. It is well understood by those skilled in the art that the addition of an amine oxirane to the surface coating can result in a change in the properties of the surface coating, thereby altering the properties of the final finish, which may be limited by corresponding changes in the formulation. In addition to the use on the surface coating, the amine oxane can also be used in the above-mentioned application form as a so-called surface spray. In addition to the surface coating, the re-applied functional properties are in particular one of the high levels of amine oxane to the final finish. The amine oxirane at this time can be used alone in various application forms, diluted with water or mixed with a binder, a matting agent, a crosslinking agent or other additives commonly used for final finishing. If the surface coating uses a relatively large amount of the amine-based oxirane formulation or especially as a surface spray, the leather feel is somewhat affected by the equivalent processing of the leather. Because the evaluation of the hand is a very subjective question, this change may be included in the positive or negative evaluation of the analysis. In addition to hydrazine and other additives that affect the feel (so-called feel agents), chemical modification can also be used to modify the k-amino oxane. In addition to the hand, the degree of emulsifying and antifouling properties are also changed by chemical modification. Reactive groups such as, for example, compounds having an epoxy group, an isocyanate group, an acid anhydride group and a mercapto chloride group can be considered as suitable groups for carrying out this chemical modification. Depending on the amine group between the ruthenium and osmium The conversion 'can change the nature of the amine oxirane as the target requires. The following examples are intended to explain the invention in more detail. Unless otherwise stated, the meaning of "parts, amounts, and parts by weight" means Example 126258.doc -13- 200848517 The method of testing the amine-based oxane and the control compound on the leather is carried out by adding the test substance to the surface coating or as a surface spray, or in two ways, after being placed in a shallow manner. Color leather bottom. For surface coating, mix 200 parts by weight of Aqualen® Top D-20I8.A, 90 parts by weight of Aqualen8 Top 2007.A, 30 parts by weight of Melio® LV-03, 340 parts by weight Specific water and 60 parts by weight of Aqualen® IW-80.A. This surface coating formulation (Top 1) has no further additives, as a reference for soil testing. Through the addition of anthrone emulsion, amine hydrazine Oxyalkane or carbon fluoride (Table 1), a surface coating with less soil is available (Table 2). Table 1

Topi Top2 Top3 Top4 Top5 Top6 Top7 Topi 720 720 720 720 720 720 720 Suparex® DE05 0 150 0 0 0 0 0 Melio® 09-F-20 0 0 150 0 0 0 0 Melio® 09-F-41 0 0 0 150 0 0 0 Bavon® Oil WR-600 0 0 0 0 50 0 0 Nuva® 2110 0 0 0 0 0 150 0 Nuva® HPC 0 0 0 0 0 0 150

Suparex® DE05 is a water-based oil emulsion, Melio® 09-F-20 is an aqueous mixture of polyurethane and decane, and Melio® 09-F-41 is an aqueous amine-based oxime emulsion. Bavon® Oil WR-600 is an organic mixture based on amino alkane. Nllva® 2110 and Nllva8HPC are aqueous solutions of resins and perfluoroalkylates. The staining characteristics of the leather after processing were tested on a Martindale tester using Eidgen Sssische Materialpriifanstalt's standardized test cloth 1 〇 4 (EMPA, Swiss Federal Materials Testing and Research 126258.doc -14-200848517 laboratory). On the Martindale tester, the finished leather and test cloth to be tested were respectively clamped on the jig, and then the jig was moved along with the test cloth on the leather test piece in the specified manner (1000 cycles). By comparing with the gray scale, the degree of fouling was evaluated according to 1 (strongly stained (no dirt) classification method (Table 2) compared to the unstained leather surface. Table 2

Topi Top2 Τορ3 Τορ4 Τορ5 Τορ6 Τορ7 Staining 1 2 2-3 4-5 4-5 2 1-2 As seen in Table 2, the degree of contamination is substantially reduced by the use of amine oxiranes in Top 4 and Top 5 'However, an anthranone-free emulsion (such as τ ° ρ2) achieved a slight improvement. The addition of a perfluoroalkyl group can only improve a small degree of antifouling ability. 126258.doc -15-

Claims (1)

200848517 X. Patent application scope: The use of amine-based oxirane for the antifouling treatment of leather surface. 2. The use of the item i, characterized in that the amine oxime is a linear or branched organopolyoxane of the formula (1) wherein: Ri independently represents the monovalent saturation of the carbon atom and/or Or an unsaturated linear or cyclic hydrocarbon group, or an aryl group having 6 to 20 carbon atoms, or a hydrocarbon-oxy group; R independently represents RN, hydrogen or -OX group, and X is hydrogen, methyl, ethyl, Propyl, butyl, pentyl or methoxyethyl; RN is independently a group of the formula (π). -(CR^2)m - [NR^ - (CR^)n]p - NR^ jR^ (II) The NR k group or the NR 3 ! group may also be a saturated or partially saturated heterocyclic ring of 5 -1 ring atoms; R is independently saturated and/or unsaturated with 1 to 30 carbon atoms. Linear and / or cyclic hydrocarbon or hydrogen; R4 is hydrogen 'alkyl containing 1-20 carbon atoms, isoalkyl containing 3-20 carbon atoms or having tertiary carbon atoms and containing a total of 4-20 carbons Alkyl group; Q is a group of formula (in) • (CR32)m _ [NR3 - (CR32)n]p - NR3 · (CR32V*Si (III) 126258.doc . 1 _ 200848517 or (IV) Group -(CR32)m - N[ - (CR32)n - NR3]p -*Si (IV) * Si stands for Link (I) Intermolecular or intramolecular links of molecules; k, 1 and p are each independently 0, 1 or 2; m and η are each independently a number 1 -1 0 ; w has a value of 1 -3 ; The X, y and hydrazine should have an amine content of from 0.01 to 20 meq/g of an amine oxetane. 3. The use of claim 2, characterized in that: R1 is an alkyl group having 1 to 5 carbon atoms; Is methyl or ethyl; Rn is -(CH2)3NH-C2H4-NH2, -ch2-ch, (ch3)-nh-(ch2)2-nh2 or R3 is hydrogen or methyl; and R4 is hydrogen or an alkyl group having from 1 to 4 carbon atoms. 4. The use of claim 3, characterized in that: R1 is methyl or ethyl; R2 is fluorenyl or ethyl; RN is -(CH2)3NH-C2H4-NH2, -CH2-CH-(CH3)- NH-(CH2)2-NH2 or 126258.doc 200848517 R3 is hydrogen; and R4 is hydrogen. The use according to any one of claims 4 to 4, characterized in that the amine oxirane is chemically modified by a reactive group selected from the group consisting of epoxy groups, isocyanates, acid anhydrides and sulfhydryl groups. The use according to any one of claims 1 to 4, characterized in that the amine siloxane is used in a surface coating or as a surface spray. The use according to any one of claims 1 to 4, characterized in that the amino azane is used in the form of a compound which is soluble in water or soluble in a cosolvent or in an aqueous dispersion or emulsion. 8. The use according to any one of claims 1 to 4, characterized in that, when used in the form of a surface coating formulation, the concentration of the amine oxirane is from 2% to 20% by weight of the total formulation; When the surface spray method is used, the concentration of the amine-based oxygen burning is up to 1 〇〇 and the weight is 0/〇. The use of any one of items 1 to 4, characterized in that, in addition to the amine siloxane, an additive selected from the group consisting of a sensitizer, a matting agent and other additives is used. 126258.doc 200848517 VII. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: 8. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: R2wR13.wSi-0-[SiR12-0]x[SiR1RN0]y-[SiRlQ0]z-SiR13.wR2w (I) 126258.doc