JPH02133500A - Leather finish composition - Google Patents

Abstract

PURPOSE: To form a leather finishing composition particularly suitable for softening treatment of leather by mixing a specified ester or its sulfonated product, a synthetic aromatic tanning agent and, optionally, an existing tanning agent salt and a conditioning agent.

CONSTITUTION: This composition is obtained by mixing the following four components (a)-(d). (a) A reaction product of a saturated or unsaturated 6-24C fatty acid, a 2-18C polyol, and an aliphatic or aromatic dicarboxylic acid or its anhydride, or the sulfonation reaction product thereof; or a reaction product of a 12-24C aliphatic alcohol or alkoxylated 12-24C aliphatic alcohol with dicarboxylic acid or its anhydride, or the sulfonation reaction product thereof, (b) a synthetic aromatic tanning agent, its uncondensed precursor, or its alkali metal salt or ammonium slat and, as optional additive component, (c) a water-soluble chromium salt, aluminum salt, iron salt, zirconium salt or a mixture thereof and (d) a conditioning agent.

COPYRIGHT: (C)1990,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a leather finish composition, a process for its preparation and its use for the softening treatment of leather.

The leather finishing composition of the present invention contains the following components.

(a) A reaction product of a saturated or unsaturated C6-C24-fatty acid, a polyol having 2 to 18 carbon atoms, and an aliphatic or aromatic dicarboxylic acid or its anhydride, or a sulfonation reaction product thereof , or C, -C
24-fatty alcohol or alkoxylated C+2-C
24-reaction products of fatty alcohols with dicarboxylic acids or their anhydrides or sulfonated reaction products thereof, (b) synthetic aromatic tanning agents or their uncondensed precursors or their alkali metal or ammonium salts, and (c) a water-soluble chromium salt, aluminum salt, iron salt, zirconium salt, or a mixture thereof as an optional additive component.

and (d) Conditioning agent.

The subject matter of the present invention also includes a method for producing the leather finishing composition as well as a method for using it for the softening treatment of leather.

Component (a) is known per se. Thus, for example, West German Publication No. 1,669,347 describes the esterification of fat- or oil-containing compounds containing alcoholic hydroxyl groups as well as lipophilic groups with maleic anhydride.

The fatty acids of component (a) contain 6 to 24, preferably 12 to 24 carbon atoms and can be saturated or unsaturated. Examples of such fatty acids include capric acid, lauric acid, myristic acid, valmitic acid or stearic acid, as well as decenoic acid, dodecenoic acid, tetradecenoic acid, hexadecenoic acid, oleic acid, linoleic acid, liluic acid,
Such as ricinoleic acid.

Suitable polyols of component (a) are dihydric to hexahydric aliphatic alcohols of 2 to 18, preferably 2 to 12 carbon atoms.

Preferred are glycerin, trimethylolpropane, erythritol, mannitol, pentaerythritol,
Such as sorbitol. The dicarboxylic acid of component (a) can be a saturated or ethylenically unsaturated aliphatic dicarboxylic acid or an aromatic dicarboxylic acid. Examples of suitable saturated aliphatic dicarboxylic acids include malonic acid, succinic acid, or higher homologs thereof such as glutaric acid, adipic acid,
pimelic acid or anhydride thereof. The ethylenically unsaturated dicarboxylic acid is preferably fumaric maleic acid,
Itaconic acid, as well as methaconic acid, citraconic acid, glutaconic acid, and methylene malonic acid. The preferred anhydride of these acids is maleic anhydride. Examples of suitable aromatic dicarboxylic acids are phthalic acid, isophthalic acid, terephthalic acid and their anhydrides.

12 to 24 suitable fatty alcohols for component (a);
Preferably it contains 12 to 22 carbon atoms. These alcohols can be saturated or unsaturated, linear or branched. It can be used alone or as a compound. Natural alcohols such as myristyl alcohol, cetyl alcohol, stearyl alcohol, and oleyl alcohol can also be used.
Furthermore, oxo alcohols, especially synthetic alcohols such as 2-ethyl-n-hexanol, trimethylhexanol, trimethylnonyl alcohol, hexadecyl alcohol, and alfol, can also be used.

Preferred component (a) is the reaction product of glycerin, oleic acid and maleic anhydride, or the reaction product of stearyl alcohol and maleic anhydride.

Component (a) can be produced by a method known per se. i.e. by esterification of the reaction product of a polyol as defined above with a fatty acid, or by esterification of a fatty alcohol or an alkoxylated fatty alcohol as defined above with a dicarboxylic acid or anhydride thereof as defined above. Can be done. Polyol:
The molar ratio of fatty acid dicarbonate (or its anhydride) is 1:1:2, preferably 1:2:1. Most preferably 1
:1:2. The molar ratio of fatty alcohol dicarboxylic acid (or its anhydride) is 1:1. These reaction products are alkali metal sulfites or ammonium sulfites, such as Na25O:r, Na25zOs,
(NH4) 250:l or Na HS Oy
can be sulfonated with

Component (b), the synthetic aromatic tanning agent itself, is described, for example, in Ullman's Encyclopedia of Applied Chemistry.
anns enzyklopaedie dertec
Hnischen Chemie), Volume 16, (4
), pp. 138-140 (1979), or
Ju. Partridge, J., ``Chemical treatment of bites and leather'' (chelIIic)
al Treatment of llides and
Leather) Noye Data Corporation, Park Ridge, New York
s Data (:organization), 19
Published in 1972].

A particularly useful component (b) is a synthetic anionic aromatic tanning agent (simply anionic aromatic tanning agent).
s)] and their uncondensed precursors, or alkali metal salts or ammonium salts of these compounds.

Examples of suitable precursors are naphthalene, diphenyl, tylphenyl, phenol, cresol, 4.4°-dihydroxydiphenylsulfone, β-naphthol, dihydroxybenzene, resorcinol, 2,2'-bis(hydroxyphenyl)propane, and diaryl ethers. Examples include diphenyl ethers, diaryl ethers, etc., which can be sulfonated with anionic foreign condensation precursors in a manner known per se.

Suitable anionic aromatic syntances include condensations obtained by condensing the sulfonated precursors exemplified above, alone or together with other normally unsulfonated precursors, with formaldehyde and/or urea. It is a product. An example is shown below.

(I) Condensate of sulfonated phenol or cresol and formaldehyde; (II) Condensate of naphthalene sulfonic acid and formaldehyde; (III) 4,4'-dihydroxydiphenyl sulfone condensed with (hydroxy)arylsulfonic acid and formaldehyde. Condensate; (IV) Condensate of a sulfonated aromatic hydroxy compound together with an aralkyl halide and formaldehyde; (V) Phenol or phenolsulfonic acid and urea/
Condensate with formaldehyde; (■) The molar ratio of (phenol)=(Sh) is (1):(1,1 to 2.
2) reaction product of phenol and sulfonating agent; (VII) condensate of sulfonated diaryl ether and formaldehyde; (■) condensate of sulfonated diphenyl or tylphenyl and formaldehyde; (IX) 4,4 Condensate of °-dihydroxydiphenylsulfone and sulfonated 4,4°-dihydroxydiphenylsulfone condensed with formaldehyde: (X) Condensate of diarylethersulfonic acid and 4゜4゛-dihydroxydiphenylsulfone condensed with formaldehyde.

Among the above, (I)-(III), (V), (■)-(X
) type condensates, for example, Ullmann's Encyclopedia of Applied Chemistry, Volume 16 (4), ±, (1θ79)
and can be prepared by the methods known from and described in the literature cited herein.

(IT) type condensates and methods for their production are disclosed in GB 986,621.

Condensates of type (V) and methods for their production are disclosed in British Patent Nos. 890,150 and 935,678.

Reaction products of the (Vl) type and methods for their preparation are described in European Patent Application No. 0245205 Nogawa M. This reaction product is obtained in a manner known per se by the type (V
) can be condensed to a condensate of (British Patent No. 683)
(See specification No. 084).

Ready-made tanning salts suitable for use as optional component (c) are described in the relevant technical literature. These salts are usually chromium, aluminum, iron or zirconium salts. Typical examples of such salts include basic chromium (III) chloride or basic chromium sulfate (■);
Chrome alum, basic or non-basic aluminum chloride or M, bulk aluminum, alum, iron chloride (
III) or iron sulfate (■), zirconium oxychloride, and zirconyl sulfate 11. Mixtures of the aforementioned chromium salts and aluminum salts are also very suitable as component (c). Preferred are the salts listed below.

[CrC12(OHt)blcl・2H2O, [Cr
(Olh)clcl>, Cr(01()Sob, C
rt(OH)bsO+,.

KCr(SOJ2・12 H2O,,,F+4(Sob
)1.9 H2O.

If component (d) is also used in the leather finish composition of the invention, it is suitably a non-tannic substance. For example, inorganic salts of acids, inorganic salts combined with organic acids, non-swelling aromatic sulfonic acids, fluorosilicates or dextrins. Specific examples include anhydrous sodium sulfate, sodium bisulfite, chromium alum, and alkali total fluorosilicate. Preferred non-tannin materials are sodium fluorosilicate or dextrin.

The leather finishing composition according to the present invention comprises component (a) and component (
b) and optional components (c) and (d) in the presence of water at 2° to 100°C, preferably 2° to 90°C.
It can be produced by simply mixing at a temperature of 0. The homogeneous mixture thus obtained is firstly dried or spray-exploded to form a powder.

The leather finish composition according to the invention preferably has the following M
It has a single structure. Note that the amounts are based on the total amount of the composition.

Component (a): 10 to 40% by weight, preferably 25 to 35% by weight, Component (b): 20 to 80% by weight, preferably 60 to 70% by weight, Component (c): O to 50% by weight, preferably is 0 to 35
% by weight, component (d): o to 20% by weight, preferably O to 15% by weight
% by weight, and water: up to 100% by weight in total.

The finishes novel according to the invention are particularly suitable for the softening treatment of leather.

The invention therefore also relates to a method for treating leather. The method of the invention is characterized in that, before dyeing or particularly preferably after dyeing, these leathers are treated with a leather finishing composition according to the invention. do.

The treatment can be carried out by conventionally known and commonly used methods. That is, hide or pretanned leather is treated with an aqueous solution containing the composition according to the invention, and the tanned material is then washed in the usual manner, for example by neutralization and washing.

It is carried out by finishing treatment by fatliquing and drying. Staining can also be carried out if desired.

Usually 50 to 300 parts by weight, preferably 140 to 180 parts by weight of water per 100 parts of hide or leather.
Then, 5 to 40 parts by weight of the finishing composition according to the invention are used.

In a particularly preferred embodiment, 100 parts of preferably demineralized hide is tanned using 140 to 160 parts of water and 10 to 20 parts by weight of the finishing composition according to the invention. Alternatively, 100 parts of leather, conventionally chrome-tanned and neutralized with, for example, charcoal salt or heavy carbon salt, are mixed with 140 to 160 parts by weight of water and 5 to 151 parts of a finishing composition according to the invention. Used and then tanned. The leather thus tanned is washed and, if desired, fatliquored with customary fatliquors, such as those based on sulfonated fish oil, whale oil or oxfoot oil. After dry explosion.

Beautiful, glossy leather with excellent light fastness can be obtained. This leather was tight. It has a dense and smooth silver surface, and has a soft texture.

Hereinafter, the present invention will be further explained by examples. Parts and percentages in the examples are on a one-dip basis.

Example 1 83 parts (0,215 moles) of industrial grade glycerin monooleate are charged to a 750 ml capacity sulfonation flask equipped with a nitrogen inlet, stirrer and thermometer, and to this is added maleic anhydride. 21 parts (0.215 mol) are added at 85°C. After the anhydride has dissolved, the temperature is maintained at 100° C. for 1 hour. The half ester of maleic acid thus obtained was treated at about 60°C with polyhydroxypolyphenylsulfonesulfonic acid (European Patent Application No. 02452).
2005), 100 parts of water, and 118 parts of a 48% aqueous solution of sodium hydroxide. This mixture is spray-dried to obtain 442.3 parts of a dry powder containing 324 parts of phenolic tanning agent, 108.3 parts of fatliquor and 10 parts of water.

Example 2 55 parts of the industrial grade glycerin monooleate/half ester of maleic acid obtained in Example 1 were mixed with 77.3 parts of sodium salt of polyhydroxypolyphenylsulfonesulfonic acid and Or(OH)SO481, 45 parts of chromium salt (corresponding to 25.62 parts of chromium) and 130 parts of water. This mixture is spray dried. Therefore, 77.3 parts of phenolic tanning agent,
288.3 parts of dry powder are obtained containing 146 parts of chromium salt, 55 parts of fatliquor and 10 parts of water.

Example 3 50 parts (0.18 moles) of stearyl alcohol are charged to a 1-liter sulfonation flask equipped with a nitrogen inlet, a stirrer, and a thermometer, and to this is added 1 part of maleic anhydride.
8.3 parts (0.18 mol) are added at 70°C. After the anhydride has dissolved, the temperature is maintained at 90° C. for 1.5 hours. The half ester of maleic acid thus obtained was heated to about 70°C.
A solution of 17.6 parts of sodium sulphite (0.09 mol) in 163.5 parts of water and 20 parts of a 50% aqueous solution of potassium hydroxide is added and the mixture is stirred for 2 hours. The resulting viscous emulsion is added to a solution of 170 parts of polyhydroxypolyphenylsulfonesulfonic acid, 40 parts of water and 110 parts of a 48% aqueous solution of sodium hydroxide.

This mixture was spray-dried and the phenolic tanning agent 19
A dry powder is obtained containing 6 parts of fatliquor, 90 parts of fatliquor and 5 parts of water.

Example 4 Sodium 1 of industrial grade glycerin monooleate/half ester of maleic acid obtained in Example 1
108.3 parts of formaldehyde and polyhydroxypolyphenylsulfonesulfonic acid (West German Patent No. 96135)
348 parts of the sodium salt of the condensate (see Specification No. 1), 70 parts of sodium fluorosilicate and 300 parts of water. This mixture is spray-dried to obtain a dry powder containing 348 parts of phenolic tanning agent, 108.3 parts of fatliquoring agent, 70 parts of sodium fluorosilicate and 20 parts of water.

11 industrial grade sorbitol monooleate esters
4 parts (0.30 mol) in a 750I! equipped with nitrogen inlet, stirrer and thermometer. A 1 volume sulfonation flask is charged and to it is added 30 parts (0.30 mol) of succinic anhydride at 95°C. After the anhydride has dissolved, reduce the temperature to 1
Hold at 00°C for 1 hour. The half ester of succinic acid thus obtained was treated at 60°C with polyhydroxypolyphenylsulfonesulfonic acid (European Patent Application No. 0245205).
(see specification), 150 parts of water, and about 162 parts of a 48% aqueous solution of sodium hydroxide. This mixture was spray dried to produce 535 parts of a dry powder containing 367 parts of phenolic tanning agent, 156 parts of fatliquoring agent and 12 parts of water.
get the part.

APPLICATION EXAMPLE

The treated noids were stored for about 10 hours, racked and hung to dry. Beautiful and flexible leather with a soft and full texture was obtained.

Example 7 100 parts of pricked and neutralized full-grain chrome-tanned calf leather were washed and dyed for 20 minutes at a temperature of 50'C using 1 part of leather dye, C,1, Acid Brown 189. , followed by post-treatment at 50"C for 1 hour using 10 parts of the composition prepared in Example 1. 85% Gi #0.
After acidification with 5 parts, this dyed and post-treated leather was
It was stored for an hour, placed on a rack, vacuum dried at 75°C for 1 minute, and then hung to dry on a string. As a result, a beautiful brown, soft leather with a full texture was obtained without further softening treatment.

Claims (1)

[Claims] 1. A leather finishing composition containing the following components: (a) a saturated or unsaturated C_6-C_2_4-fatty acid, a polyol having 2 to 18 carbon atoms, and an aliphatic or aromatic Reaction products of dicarboxylic acids or their anhydrides or sulfonated reaction products thereof, or reaction products of C_1_2-C_2_4-fatty alcohols or alkoxylated C_1_2-C_2_4-fatty alcohols with dicarboxylic acids or their anhydrides, or (b) a synthetic aromatic tanning agent or its uncondensed precursor or an alkali metal or ammonium salt thereof, and as optional additives (c) a water-soluble chromium salt, aluminum salt, iron salt. , a zirconium salt or a mixture thereof, and (d) a conditioning agent. 2. The fatty acid in component (a) contains 12 to 14 carbon atoms, the polyol contains 2 to 12 carbon atoms, and the fatty alcohol contains 12 to 24 carbon atoms. A leather finishing composition according to claim 1. 3. The leather finishing composition according to claim 1, wherein component (a) is a reaction product of glycerin, oleic acid, and maleic anhydride. 4. The leather finishing composition according to claim 1, wherein component (a) is a reaction product of stearyl alcohol and maleic anhydride. 5. The leather finishing composition according to claim 1, wherein component (b) is a synthetic anionic aromatic tanning agent or an uncondensed precursor thereof. 6. The leather finishing composition according to claim 5, wherein component (b) is a condensation product of sulfonated phenol or cresol with formaldehyde, or an alkali metal salt or ammonium salt thereof. 7. The leather finishing composition according to claim 5, wherein component (b) is a condensation product of naphthalene sulfonic acid and formaldehyde, or an alkali metal salt or ammonium salt thereof. 8. The leather finishing composition according to claim 5, wherein component (b) is a condensation product of 4,4'-dihydroxydiphenylsulfone, (hydroxy)arylsulfonic acid, and formaldehyde, or an alkali metal salt or ammonium salt thereof. . 9. The leather finishing composition according to claim 5, wherein component (b) is a condensation product of a sulfonated aromatic hydroxy compound, an aralkyl halide, and formaldehyde, or an alkali metal salt or ammonium salt thereof. 10. The leather finishing composition according to claim 5, wherein component (b) is a urea/formaldehyde condensation product of phenol or phenolsulfonic acid, or an alkali metal salt or ammonium salt thereof. 11. The leather finishing composition according to claim 5, wherein component (b) is a condensation product of a sulfonated diaryl ether and formaldehyde, or an alkali metal salt or ammonium salt thereof. 12. The leather finishing composition according to claim 5, wherein component (b) is a condensation product of sulfonated diphenyl or tylphenyl with formaldehyde, or an alkali metal salt or ammonium salt thereof. 13. The leather according to claim 5, wherein component (b) is 4,4'-dihydroxydiphenylsulfone, a condensation product of sulfonated 4,4'-dihydroxydiphenylsulfone, and formaldehyde, or an alkali metal salt or ammonium salt thereof. Finish composition. 14. The leather finishing composition according to claim 5, wherein component (b) is a condensation product of diarylethersulfonic acid, 4,4'-dihydroxydiphenylsulfone, and formaldehyde, or an alkali metal salt or ammonium salt thereof. 15. Component (b) is a reaction product of phenol and a sulfonating agent or an alkali metal salt or ammonium salt thereof, and the molar ratio of (phenol):(SO_3) is (1):(1)
．． 1 to 2.2). The leather finishing composition according to claim 5. 16. The leather finishing composition according to claim 1, which contains a chromium salt as an optional additive component (c). 17. 10 to 40% by weight of component (a), 20 to 80% by weight of component (b), 0 to 50% by weight of component (c), 0 to 20% by weight of component (d), and the total amount of water. The leather finishing composition according to claim 1, which contains up to 100%. 18. A method for softening leather using the finishing composition according to claim 1. 19. A method for softening leather, characterized in that the leather material is treated with a composition containing the following components during or after dyeing: (a) saturated or unsaturated C_6-C_2_4-fatty acid; and the reaction product of a polyol having 2 to 18 carbon atoms with an aliphatic or aromatic dicarboxylic acid or its anhydride or a sulfonated reaction product thereof, or C_1_2-C_2_4-fatty alcohol or alkoxylated C_1_2- C_2_4-reaction products of fatty alcohols and dicarboxylic acids or their anhydrides or sulfonated reaction products thereof, (b) synthetic aromatic tanning agents or their uncondensed precursors or their alkali metal or ammonium salts, and Optional additional ingredients include (c) a water-soluble chromium salt, aluminum salt, iron salt, zirconium salt, or a mixture thereof, and (d) a conditioning agent. 20. Claim 19, wherein the treatment with the composition is performed after dyeing.
Method described. 21. Leather treated by the method according to claim 19.