EP0784707B1 - Verfahren zur herstellung von lederfettungsmitteln - Google Patents
Verfahren zur herstellung von lederfettungsmitteln Download PDFInfo
- Publication number
- EP0784707B1 EP0784707B1 EP95934112A EP95934112A EP0784707B1 EP 0784707 B1 EP0784707 B1 EP 0784707B1 EP 95934112 A EP95934112 A EP 95934112A EP 95934112 A EP95934112 A EP 95934112A EP 0784707 B1 EP0784707 B1 EP 0784707B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- carbon atoms
- component
- fatty acid
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
- C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring
Definitions
- the invention relates to processes for the production of leather greasing agents with high emulsion stability, containing cationic surfactants of the esterquat type, sulfated oils and nonionic surfactants.
- the mutual friction is reduced and consequently the suppleness and stretchability of the fabric is improved. That has positive things Impact on the tear resistance of the leather, because In a stretchy material, many fibers are attached Tensile stress in the direction of tension and then expose it Tearing up a greater resistance than the same Fibers within a brittle material. Through the hydrophobization tanning effects are also achieved because it is associated with a displacement of water from the skin is.
- Fat mixtures used for greasing leather tend to have a particular tendency then to form a rash when they have a lot of free Contain fatty acids.
- Free fatty acids generally have a higher melting point than their glycerides.
- the hydrolytic Splitting of fatty substances during storage of the Leather accordingly increases the risk of occurrence of Fat rashes.
- Soaps and licker greases are split in chrome leather, especially in insufficiently deacidified chrome leather, with the release of fatty acids. Sulphated oils and fats show a different tendency to form fat rashes, the tendency to rash generally decreases with a longer lifespan [cf. J.Int.Soc.Leath.Trad.Chem. 47 , 379 (1952) ].
- Greasy rashes occur the easier the leather contains fatty substances that tend to develop rashes.
- the scope and composition of the rash are quantity, Composition and location of the fat mixture present in the leather decisive from natural fat and lickerfat.
- Loosely structured leather is less prone to rash than leather with dense fiber structure. Fat rashes are low Temperatures observed more often than at warmer outside temperatures.
- the crystalline fat rashes develop in the hair holes and gland canals, whereby small crystals are initially formed in the depth, which gradually fill the entire hair hole as larger fat crystals, swell out over the leather surface and matted into a dense crystal film. All fats that contain stearin or palmitin derivatives can cause crystalline fat rashes, with increasing concentration the risk of rashes increases [Ledertechn.Rundsch. 1 (1949) ].
- the so-called neutral fats i.e. such substances suitable for leather greasing which are not ionic Contain groups in the molecule, e.g. Fats, waxes and hydrocarbons, for the formation of fat rashes.
- the neutral fats, the stearin and / or palmitin derivatives, such as corresponding ones Triglycerides or the free fatty acids are especially preferred.
- Greasing agents are halogenated compounds such as chlorinated hydrocarbons.
- cationic compounds of the quaternary ammonium compound (QAV) type such as, for example, dimethyldistearylammonium chloride, are also important as fatliquoring agents.
- QAV quaternary ammonium compound
- An overview of this topic by S.Gupta can be found in J.Am.Leath.Chem.Ass. 83: 239 (1988) .
- QAV are under discussion for ecological reasons and therefore also in leather auxiliaries.
- An alternative are cationic surfactants of the esterquat type which, however, cannot readily be processed into stable emulsions together with anionic surfactants, in particular those of the sulfated oil type.
- the object of the invention was therefore a method for the production of stable emulsions for the lubrication of To provide leathers that act as cationic surfactants Ester quats and sulfated oils as anionic components contain.
- esterquats and allow sulfated oils to be processed into a stable emulsion, if you use nonionic surfactants as emulsifiers and these either the esterquats or the sulfated oils adds to form a premix.
- ester quats is generally understood to mean quaternized fatty acid triethanolamine ester salts. These are known substances that can be obtained using the relevant methods of preparative organic chemistry.
- WO 91/01295 Hexide
- EP-A2 0239910 EP-A2 0293955, EP-A2 0295739 and EP-A2 0309052 .
- the quaternized fatty acid triethanolamine ester salts follow the formula (I) in which R 1 CO stands for an acyl radical with 6 to 22 carbon atoms, R 2 and R 3 independently of one another for hydrogen or R 1 CO, R 4 for an alkyl radical with 1 to 4 carbon atoms or a (CH 2 CH 2 O) q H- Group, m, n and p in total stands for 0 or numbers from 1 to 12, q for numbers from 1 to 12 and X for halide, alkyl sulfate or alkyl phosphate.
- R 1 CO stands for an acyl radical with 6 to 22 carbon atoms
- R 2 and R 3 independently of one another for hydrogen or R 1 CO
- R 4 for an alkyl radical with 1 to 4 carbon atoms or a (CH 2 CH 2 O) q H- Group
- m, n and p in total stands for 0 or numbers from 1 to 12
- X for halide, alky
- ester quats which can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid and their technical mixtures, such as they occur, for example, in the pressure splitting of natural fats and oils.
- Technical C 12/18 coconut fatty acids and in particular partially hardened C 16/18 tallow or palm fatty acids as well as C 16/18 fatty acid cuts rich in elaidic acid are preferably used.
- the fatty acids and the triethanolamine can be used in a molar ratio of 1.1: 1 to 3: 1 to produce the quaternized esters.
- an application ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1 has proven to be particularly advantageous.
- the preferred esterquats are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C 16/18 tallow or palm fatty acid (iodine number 0 to 40).
- quaternized fatty acid triethanolamine ester salts of the formula (I) have proven to be particularly advantageous in which R 1 CO for an acyl radical having 16 to 18 carbon atoms, R 2 for R 1 CO, R 3 for hydrogen, R 4 for a methyl group, m , n and p is 0 and X is methyl sulfate.
- quaternized ester salts of fatty acids with diethanolalkylamines of the formula (II) are also suitable as esterquats, in which R 1 CO for an acyl radical with 6 to 22 carbon atoms, R 2 for hydrogen or R 1 CO, R 4 and R 5 independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate.
- ester quats in which R 1 CO for an acyl radical with 6 to 22 carbon atoms, R 2 for hydrogen or R 1 CO, R 4 , R 6 and R 7 independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents halide, alkyl sulfate or alkyl phosphate.
- ester quats of the formulas (II) and (III).
- the ester quats are usually in the form of 50 to 90% by weight alcoholic solutions in the trade, if necessary can be easily diluted with water.
- Sulfated oils are reaction products of predominantly unsaturated fats and oils of natural or synthetic origin with sulfuric acid or oleum. This reaction leads to the addition of sulfuric acid to the double bonds and - if available - hydroxyl groups of the triglycerides with the formation of sulfate groups. A saponification of the ester bond can also occur as a side reaction. However, the resulting partial glycerides in turn have free OH groups and are sulfated particularly quickly. Typical examples are sulfation products from olive oil, cottonseed oil, peanut oil, linseed oil, rapeseed oil from old and new breeds, sunflower oil from old and new breeds, castor oil, beef tallow and fish oil.
- nonionic surfactants which are suitable as emulsifying component (c) in the context of the process according to the invention are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polygylcol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, mixed ethers or mixed formals, fatty acid (alk) enol glycole alkyl glucamides, protein hydrolyzates (especially vegetable products based on soy), polyol fatty acid esters, sugar esters, sorbitan esters and polysorbates.
- the nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
- fatty alcohol polyglycol ethers of the formula (IV) are used as nonionic surfactants, in which R 8 represents an alkyl and / or alkenyl radical having 6 to 22 carbon atoms, x for numbers from 1 to 25 and y for 0 or numbers from 1 to 5.
- the nonionic surfactants of component (c) used are alkyl and alkenyl oligoglycosides which follow the formula (V) R 9 O- [G] p (V) in which R 9 represents an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G represents a sugar radical having 5 or 6 carbon atoms and p represents numbers from 1 to 10.
- Alkyl and / or alkenyl oligoglycosides can be obtained by the relevant methods of preparative organic chemistry. As representative of the extensive literature, reference is made here to the documents EP-A1 0301298 and WO 90/03977 .
- the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose.
- the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligo glucosides .
- the alkyl or alkenyl radical R 9 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capronic alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.
- the alkyl or alkenyl radical R 9 can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, and their technical mixtures, which can be obtained as described above. Alkyl oligoglucosides based on hardened C 12/14 coconut alcohol with a DP of 1 to 3 are preferred.
- preferred nonionic surfactants which make up component (c) are also fatty acid N-alkylpolyhydroxyalkylamides of the formula (VI) , in which R 10 CO for an aliphatic acyl radical with 6 to 22 carbon atoms, R 11 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 12 carbon atoms and 3 to 10 hydroxyl groups stands.
- the fatty acid N-alkyl polyhydroxyalkylamides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
- a reducing sugar with ammonia
- an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
- US Pat. Nos. US 1985424, US 2016962 and US 2703798 and international patent application WO 92/06984 An overview of this topic by H. Kelkenberg can be found in Tens. Surf.Det. 25 , 8 (1988) .
- the fatty acid N-alkylpolyhydroxyalkylamides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.
- the preferred fatty acid N-alkyl polyhydroxyalkylamides are therefore fatty acid N-alkylglucamides , as represented by the formula (VII):
- the fatty acid N-alkylpolyhydroxyalkylamides used are preferably glucamides of the formula (VII) in which R 11 represents hydrogen or an amine group and R 10 CO represents the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, Isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachic acid, gadoleic acid, behenic acid or erucic acid or their technical mixtures.
- R 11 represents hydrogen or an amine group
- R 10 CO represents the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, Isostearic acid, oleic acid, elaidic acid, petrose
- Fatty acid N-alkylglucamides of the formula (VII) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or C 12/14 coconut fatty acid or a corresponding derivative are particularly preferred.
- the polyhydroxyalkylamides can also be derived from maltose and palatinose.
- a preferably aqueous premix is first prepared from the sulfated oil and the nonionic surfactant. This premix is then processed with a preferably aqueous solution of the ester quat with stirring, optionally at an elevated temperature of 30 to 40 ° C., to form a smooth emulsion which is distinguished by a high degree of stability. This is a purely mechanical process, there is no chemical reaction.
- the emulsions according to the invention are notable for good hydrophobic properties and are also increased Temperature stable without phase separation.
- Procedure IV (for comparison) .
- Procedure I was repeated, but the nonionic surfactant was added to the solution of sulfated fish oil and ester quat.
- the details of the experiments are summarized in Table 1.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4435398A DE4435398A1 (de) | 1994-10-04 | 1994-10-04 | Verfahren zur Herstellung von Lederfettungsmitteln |
DE4435398 | 1994-10-04 | ||
PCT/EP1995/003798 WO1996010652A1 (de) | 1994-10-04 | 1995-09-25 | Verfahren zur herstellung von lederfettungsmitteln |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0784707A1 EP0784707A1 (de) | 1997-07-23 |
EP0784707B1 true EP0784707B1 (de) | 1999-03-31 |
Family
ID=6529893
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95934112A Expired - Lifetime EP0784707B1 (de) | 1994-10-04 | 1995-09-25 | Verfahren zur herstellung von lederfettungsmitteln |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0784707B1 (ja) |
JP (1) | JPH10506424A (ja) |
DE (2) | DE4435398A1 (ja) |
ES (1) | ES2129856T3 (ja) |
TR (1) | TR199501210A2 (ja) |
WO (1) | WO1996010652A1 (ja) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10202041A1 (de) * | 2002-01-18 | 2003-10-23 | Basf Ag | Kationisch-emulgierte Fettungsmittel |
CN105771790B (zh) * | 2016-05-18 | 2017-12-08 | 烟台大学 | 一种蛋白基表面活性剂的制备方法 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3668124A (en) * | 1970-05-13 | 1972-06-06 | Pennwalt Corp | Composition and method for treating dry-cleanable soil-resistant leathers |
DE3317422A1 (de) * | 1983-05-13 | 1986-11-06 | Dr. Th.Böhme KG Chem. Fabrik GmbH & Co, 8192 Geretsried | Fettungsmittel fuer leder |
DE3444864A1 (de) * | 1984-12-08 | 1986-06-12 | Henkel KGaA, 4000 Düsseldorf | Verfahren zur fettung von leder und pelzen |
-
1994
- 1994-10-04 DE DE4435398A patent/DE4435398A1/de not_active Withdrawn
-
1995
- 1995-09-25 WO PCT/EP1995/003798 patent/WO1996010652A1/de active IP Right Grant
- 1995-09-25 JP JP8511369A patent/JPH10506424A/ja active Pending
- 1995-09-25 ES ES95934112T patent/ES2129856T3/es not_active Expired - Lifetime
- 1995-09-25 DE DE59505527T patent/DE59505527D1/de not_active Expired - Fee Related
- 1995-09-25 EP EP95934112A patent/EP0784707B1/de not_active Expired - Lifetime
- 1995-10-03 TR TR95/01210A patent/TR199501210A2/xx unknown
Also Published As
Publication number | Publication date |
---|---|
DE59505527D1 (de) | 1999-05-06 |
DE4435398A1 (de) | 1996-04-11 |
WO1996010652A1 (de) | 1996-04-11 |
TR199501210A2 (tr) | 1996-06-21 |
JPH10506424A (ja) | 1998-06-23 |
ES2129856T3 (es) | 1999-06-16 |
EP0784707A1 (de) | 1997-07-23 |
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