EP0651828A1 - Use of guerbet alcohols to prevent the formation of fatty spew on leather. - Google Patents
Use of guerbet alcohols to prevent the formation of fatty spew on leather.Info
- Publication number
- EP0651828A1 EP0651828A1 EP93915869A EP93915869A EP0651828A1 EP 0651828 A1 EP0651828 A1 EP 0651828A1 EP 93915869 A EP93915869 A EP 93915869A EP 93915869 A EP93915869 A EP 93915869A EP 0651828 A1 EP0651828 A1 EP 0651828A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- leather
- fat
- guerbet alcohols
- carbon atoms
- rash
- 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.)
- Granted
Links
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 the use of special nonionic organic dialkyl compounds for preventing fat rash on leather.
- greasing agents are the most important tools to shape the character of leather.
- the effect of the fatliquoring agents comes about through fiber-insulating lubrication and through hydrophobization.
- the mutual friction is reduced and, consequently, the suppleness and stretchability of the fabric are improved.
- This has positive effects on the tensile strength of the leather, because in a stretchable material, many fibers align in the direction of tension when subjected to tensile stress and then resist tearing more than the same fibers within a brittle material.
- Vegetable and animal oils, fats and waxes are generally used as leather greasing agents, furthermore the hydrolysis, sulfation, oxidation and hardening products obtained from these substances by chemical conversion and finally mineral greasing agents; in detail:
- the saponifiable fats and oils as well as the natural waxes and resins belong to the esters.
- oils and fats are the leather specialist Designated esters of glycerin and fatty acids that are solid or liquid at room temperature.
- the leather specialist Designated esters of glycerin and fatty acids that are solid or liquid at room temperature.
- the fatty acids are esterified with higher molecular weight alcohols instead of glycerin.
- waxes are bees wax, Chinese wax, carnauba wax, montan wax and wool fat;
- the most important resins include rosin, yeast oil and shellac.
- the chemical conversion of vegetable and animal fats gives products which are water-soluble and which, moreover, have a different effect on water-insoluble fatty substances.
- the sulfated water-soluble oils of various types are known, the tears modified by oxidation, which are referred to as degras or moellon, the soaps which are formed during the hydrolytic splitting of natural fats, hardened fats and finally free fatty acids such as stearic acid as stoving fats.
- Most animal and vegetable fats have a certain affinity for the leather substance, which is considerably increased by the introduction or exposure of hydrophilic groups.
- Mineral greasing agents are also important for leather production. These hydrocarbons are similar to natural fats and oils in some properties, but cannot be saponified. These are fractions from petroleum distillation, which are called mineral oil in liquid form, petroleum jelly in pasty form and paraffin in solid form.
- Fat mixtures used to grease leather tend to develop a rash if they contain a lot of free fatty acids.
- Free fatty acids generally have a higher melting point than their glycerides.
- the hydrolytic cleavage of fatty substances during the storage of the leather increases the risk of fat rashes accordingly (cf. B. Kohnstein, Collegium 1913. 68; W. Fahrion, Chem. Umschau 1917. 29), but such fat rashes by no means only need to be free To consist of fatty acids.
- Oxy fatty acids can also give rise to fat rashes (C. Riess, Collegium 1926, 419).
- 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 declines generally with longer lifespan (A. Pankhurst, RGMitton, RFInnes, N. Johnson, Journal of International Society of Leather Trades Che ists 1952. 379).
- Greasy rashes occur more easily the more the fatty substances in the leather tend to form rashes.
- the quantity, composition and location of the fat mixture of natural fat and lickerfat present in the leather are decisive for the extent and the composition of the rash (cf. 0.Grimm, ⁇ sterr. Lederzeitung 1954, 253).
- Loosely structured leather is less prone to rash than leather with a dense fiber structure.
- Grease rashes are observed more often at low temperatures than at warmer outside temperatures.
- the crystalline fat rashes develop in the hair holes and gland canals, initially forming small crystals in the depth, which gradually fill the entire hair hole as larger fat crystals, swell out over the leather surface and form a dense crystal film. All fats containing stearin or palmitin derivatives can cause crystalline fat rashes with increasing Concentration increases the risk of a rash (see O. Hagen, Switzerland. Ledertechn. Rundsch. 1949. 1).
- neutral fats i.e. substances suitable for leather greasing that do not contain any ionic groups in the molecule, e.g. Fats, waxes and hydrocarbons to form fat rashes.
- Those neutral fats which represent stearin and / or palmitin derivatives, e.g. corresponding triglycerides.
- Neutral greases are of particular importance in the so-called licker process of chrome-tanned leather.
- a licker usually contains about 20 to 40% by weight of an emulsifier and 60 to 80% by weight of a neutral fat. It is a widespread practice in the leather processing industry to use neutral greases for greasing the tanned leather which can be sulfated in a simple manner.
- reaction mixture obtained can be used directly as a licker since it contains an emulsifier in the form of the sulfated triglyceride and the neutral fat in the form of the unreacted triglyceride contains.
- a triglyceride is reacted with a minor amount of concentrated sulfuric acid or oleum
- the reaction mixture obtained can be used directly as a licker since it contains an emulsifier in the form of the sulfated triglyceride and the neutral fat in the form of the unreacted triglyceride contains.
- Skin fat consists of a mixture of differently structured lipids, the type and proportions of which are summarized in Table 1 for some important animal species (cf. Martin Hollstein, "Leather library; Volume 4: degreasing, greasing and waterproofing in leather production”; p. 116- 136).
- Scheme 1 shows that the triglycerides represent the most significant group of skin lipids in terms of quantity. From the point of view of the leather technician, it is otherwise critical in connection with the formation of fat rash that these triglycerides are predominantly based on saturated fatty acids: lauric, myristic, palmitic and stearic acid are typical components of this group.
- the wax esters also contain as Components include these fatty acids, which are particularly critical with regard to their tendency to fat rash.
- Fat swings which can be clearly distinguished from mineral rashes by their disappearance when heated with a burning match, can e.g. be removed by rubbing the leather with a cloth soaked in petrol; In order to prevent a rash from developing again, it has been recommended to oil the scars with a neutral mineral oil (see F. Stather, "Tannery Chemistry and Tanning Technology", Berlin 1967, p. 740).
- A.Gluszcak and KJBienkiewicz report on the use of a mixture of wood dust, water, hexane and carbon tetrachloride to remove fat rash (cf. Przegl. Skorzany 1985. 40 (11-12), 232; cited from Chem. Abstracts 105 ( 6): 45160e).
- a class of fatliquoring agents commonly used in this regard is halogenated compounds such as chlorinated hydrocarbons.
- chlorinated paraffins as additives to lipid emulsions to the J.Golonka (Przegl. Skorzany 42 (2), 35; cited from Chem. Abstracts 107 (18): 156865z) describes how to prevent rash formation on chrome-tanned pig fields.
- the present invention therefore relates to the use of Guerbet alcohols to prevent fat rash on leather, one or more Guerbet alcohols of the general formula (I) being used in the oiling of leather
- radicals R 1 and R2 independently of one another represent an alkyl group with 6 to 12 carbon atoms, with the proviso that the total number of carbon atoms per alcohol molecule is in the range from 16 to 24, with a pour point below 6 ° C. .
- those Guerbet alcohols are used whose pour point is below -10 ° C.
- Very particularly suitable Guerbet alcohols (I) with a pour point below -10 ° C. are 2-hexyldecan-l-ol and 2-0ctyldodecan-1-ol for the purposes of the invention.
- the invention further relates to compositions which prevent a fat rash and which contain a fatliquor and an additive preventing a fat rash, the additive comprising one or more Guerbet alcohols of the general formula (I)
- radicals R and R2 independently of one another represent an alkyl group having 6 to 12 carbon atoms, with the proviso that the total number of carbon atoms per alcohol molecule is in the range from 16 to 24, with a pour point below 6 ° C. .
- compositions are those in which the fatliquor is a neutral fat.
- Neutral fat is understood in the sense of the nomenclature common in leather technology to mean any greasy and slightly water-soluble substance.
- Examples of neutral oils are triglycerides, alkanes and fatty acids.
- the invention furthermore relates to a process for greasing leather, in which tanned leather is treated with an additive which prevents fat and a fat rash, one or more Guerbet alcohols of the general formula (I) being used as the additive.
- radicals R1 and R2 independently of one another represent an alkyl group with 6 to 12 carbon atoms, with the proviso that the total number of carbon atoms per alcohol molecule is in the range from 16 to 24, with a pour point below 6 ° C.
- a neutral fat is used as the fatliquor.
- the method according to the invention is particularly suitable for greasing chrome-tanned leather.
- Guerbet alcohols of the formula (I) which have a pour point below -10 ° C. are used as additives.
- the greasing process is carried out in a conventional manner.
- the grease must be transported into the capillary spaces between the leather fibers and the fibrils, and fibers and fibrils must be coated with a grease film as uniformly as possible.
- the greasing process is always carried out on moist leather, because the leather fibers are separated from one another by water in the moist state. The fat then penetrates slowly, but very evenly into the damp leather.
- the amount of fatty substances deposited in the leather is not subject to any particular restrictions and depends essentially on the particular type of leather.
- vegetable-tanned floor leather and insole leather contain only a little fat (approx. 0.5-2%), vegetable-tanned pale leather 15-23%, drive belt leather 5-20%, harness leather and some technical special leather 25% and more.
- Chrome-garment upper leather usually contain only 2-6% fat, chrome-garment leather a little more (4-10%), waterproof leather about 15-21%.
- the practical implementation of leather greasing can be done by simply oiling the wet leather before drying, also by lubricating the wet leather on the board (“cold greasing”), by greasing the wet leather in the drum (“War greasing”), by baking the dry leather and by treating the wet leather with an aqueous fat emulsion, the so-called fat licker.
- the latter process plays a major role in particular in the case of chrome-tanned leathers. It is therefore the preferred form of leather greasing in the context of the present invention.
- the Guerbet alcohols (I) are prepared by conventional synthetic methods of organic chemistry. In addition, many of them are commercially available.
- the extent to which fat rash is suppressed by the Guerbet alcohols (I) is original and novel compared to the prior art mentioned.
- the effectiveness of the compounds according to the invention is not based on individual parameters such as, for example, pour point, but rather results only from the combination of all ⁇ kmale.
- the amount in fatliquoring agents ranges from 5 to 70 percent by weight, preferably from 5 to 30 percent by weight, based on the mixture as a whole.
- the fatliquor was first mixed with the respective additive (see Table 3) and this mixture was emulsified in water. 3. Assessment of fat rashes
- the leather pretreated according to No. 2 was tested for its tendency to form fat rashes.
- the method used here is a modification of the method by H.A. Ollert (see "Das Leder" 1989, p. 256).
- the good correlation of the test results with the results of long-term storage indicated by Ollert could be confirmed in our own investigations.
- agents known from the prior art such as chlorinated paraffins, was recorded and confirmed in the test.
- the leather to be tested (pretreated according to No. 2) was punched out in a circle - without conditioning - (diameter: 155 mm).
- the leather washers were then used to cover the opening of a 1 to 1 flat ground cup filled with 300 ml of tap water (outside diameter: 155 mm), the grain side being on the top (outside).
- the leather was fixed with a tension ring and then the water was heated to boiling and kept at the boiling temperature for 2 minutes. In this way, the treated leather was exposed to a defined thermal load, water vapor escaping from the scars.
- the clamping ring was then removed, the leather disc covering the flat ground cup was removed and the water poured out.
- test B1 and B2 were free of fat rashes.
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4223706A DE4223706A1 (en) | 1992-07-18 | 1992-07-18 | Use of Guerbet alcohols to prevent fat rash on leather |
DE4223706 | 1992-07-18 | ||
PCT/EP1993/001806 WO1994002651A1 (en) | 1992-07-18 | 1993-07-10 | Use of guerbet alcohols to prevent the formation of fatty spew on leather |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0651828A1 true EP0651828A1 (en) | 1995-05-10 |
EP0651828B1 EP0651828B1 (en) | 1996-05-29 |
Family
ID=6463543
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93915869A Expired - Lifetime EP0651828B1 (en) | 1992-07-18 | 1993-07-10 | Use of guerbet alcohols to prevent the formation of fatty spew on leather |
Country Status (7)
Country | Link |
---|---|
US (1) | US5476517A (en) |
EP (1) | EP0651828B1 (en) |
JP (1) | JPH07509509A (en) |
AT (1) | ATE138693T1 (en) |
DE (2) | DE4223706A1 (en) |
ES (1) | ES2087752T3 (en) |
WO (1) | WO1994002651A1 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4405415A1 (en) * | 1994-02-21 | 1995-08-24 | Henkel Kgaa | Use of sulfated substances to grease leather |
US6630001B2 (en) | 1998-06-24 | 2003-10-07 | International Heart Institute Of Montana Foundation | Compliant dehyrated tissue for implantation and process of making the same |
US6352708B1 (en) | 1999-10-14 | 2002-03-05 | The International Heart Institute Of Montana Foundation | Solution and method for treating autologous tissue for implant operation |
KR101883189B1 (en) * | 2016-07-19 | 2018-07-31 | 주식회사 대호레더 | Manufacturing method of natural leather with prevented whitening phenomenon |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2136961A1 (en) * | 1971-05-10 | 1972-12-29 | Vichemont Marcel | Leather conditioning compsn - for improved permeability water vapour |
AR202669A1 (en) * | 1973-11-03 | 1975-06-30 | Henkel & Cie Gmbh | COMPOSITION FOR THE PREPARATION OF LEATHERS RESISTANT TO THE ACTION OF WATER AND THE CORRESPONDING PROCEDURE |
US4299994A (en) * | 1980-02-06 | 1981-11-10 | Sandoz, Inc. | Polyoxyalkylene condensation products |
WO1990015127A1 (en) * | 1989-06-09 | 1990-12-13 | Ag-Seed Pty Limited | Artificial jojoba oil |
-
1992
- 1992-07-18 DE DE4223706A patent/DE4223706A1/en not_active Withdrawn
-
1993
- 1993-07-10 WO PCT/EP1993/001806 patent/WO1994002651A1/en active IP Right Grant
- 1993-07-10 AT AT93915869T patent/ATE138693T1/en not_active IP Right Cessation
- 1993-07-10 JP JP6504108A patent/JPH07509509A/en active Pending
- 1993-07-10 EP EP93915869A patent/EP0651828B1/en not_active Expired - Lifetime
- 1993-07-10 ES ES93915869T patent/ES2087752T3/en not_active Expired - Lifetime
- 1993-07-10 DE DE59302762T patent/DE59302762D1/en not_active Expired - Fee Related
- 1993-07-10 US US08/373,330 patent/US5476517A/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
See references of WO9402651A1 * |
Also Published As
Publication number | Publication date |
---|---|
ATE138693T1 (en) | 1996-06-15 |
ES2087752T3 (en) | 1996-07-16 |
US5476517A (en) | 1995-12-19 |
DE59302762D1 (en) | 1996-07-04 |
EP0651828B1 (en) | 1996-05-29 |
DE4223706A1 (en) | 1994-01-20 |
WO1994002651A1 (en) | 1994-02-03 |
JPH07509509A (en) | 1995-10-19 |
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