EP3286342B1 - Skins tanning process - Google Patents
Skins tanning process Download PDFInfo
- Publication number
- EP3286342B1 EP3286342B1 EP16723529.0A EP16723529A EP3286342B1 EP 3286342 B1 EP3286342 B1 EP 3286342B1 EP 16723529 A EP16723529 A EP 16723529A EP 3286342 B1 EP3286342 B1 EP 3286342B1
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- EP
- European Patent Office
- Prior art keywords
- tanning
- skins
- drum
- process according
- retanning
- 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.)
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- 238000000034 method Methods 0.000 title claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 12
- 239000010985 leather Substances 0.000 claims description 8
- 235000018553 tannin Nutrition 0.000 claims description 8
- 229920001864 tannin Polymers 0.000 claims description 8
- 239000001648 tannin Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000005554 pickling Methods 0.000 claims description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 235000019253 formic acid Nutrition 0.000 claims description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 4
- 238000004040 coloring Methods 0.000 claims description 4
- 239000004571 lime Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 125000001174 sulfone group Chemical group 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 239000004280 Sodium formate Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 235000013824 polyphenols Nutrition 0.000 claims description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 2
- 235000019254 sodium formate Nutrition 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 239000000047 product Substances 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 235000013311 vegetables Nutrition 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- 102000016942 Elastin Human genes 0.000 description 1
- 108010014258 Elastin Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- -1 basically Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000002500 effect on skin Effects 0.000 description 1
- 229920002549 elastin Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 230000037368 penetrate the skin Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
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
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
- C14C3/18—Chemical tanning by organic agents using polycondensation products or precursors thereof
-
- 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
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
- C14C3/16—Chemical tanning by organic agents using aliphatic aldehydes
-
- 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
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
- C14C3/18—Chemical tanning by organic agents using polycondensation products or precursors thereof
- C14C3/20—Chemical tanning by organic agents using polycondensation products or precursors thereof sulfonated
-
- 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
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
- C14C3/22—Chemical tanning by organic agents using polymerisation products
-
- 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
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/28—Multi-step processes
-
- 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 present invention relates to a skins tanning process.
- a tanning process includes preliminary operations producing the so-called pelt; the actual tanning; the retanning; and dressing treatments.
- Preliminary operations are basically aimed at removing, from the skins, various impurities and the preservatives used to maintain the skins intact until the tanning process as well as at restoring the features of the skins, thus making them suitable for the following actual tanning treatments.
- tanning transforms the pelt into leather by means of proper tanning substances, which penetrate the skin and are steadily fixed to the dermal fibres.
- tanning vegetable tanning, mineral tanning, etc.
- manufacturers select the tanning process that is deemed to be the most appropriate to obtain specific features of the end product.
- the skins are then subjected to dressing operations, even based on the uses for which the skins are intended.
- US4245996A discloses sulphonated condensation products based on naphtalene and phenol and which are used as tanning agents for the production of leather and as re-tanning agents for re-tanning mineral-tanned leather.
- Tanning processes known at the moment have proven to be not good enough, in particular from the point of view of their environmental impact.
- known processes because of the products used in the different processing steps and of the techniques involved, cause the production of waste waters and of processing waste that are highly polluting and, anyway, are very difficult to be handled from an environmental point of view; moreover, they do not lead to an end product or to a processing waste that are completely (or at least largely) biodegradable or compostable.
- the object of the present invention is to provide a tanning process that is not affected by the above-mentioned drawbacks shown by prior art processes; in particular, it is an object of the present invention to provide a tanning process that allows manufacturers to obtain a fully biodegradable product, besides being versatile and effective, which leads to the production of high-quality products.
- the present invention relates to a tanning process as defined, in its essential aspects, in appended claim 1 and, in its additional features, in the dependent claims.
- the process according to the present invention thanks to the specific products used and to the processing techniques applied, allows manufacturers to obtain a fully biodegradable product.
- the process according to the present invention allows the skins to gain (after having been dried) features that are comparable with the ones obtained with traditional techniques, in particular softness, a peasant feel, colouring and technical performances that are suitable for the use in different fields, such as shoes, leather products, furniture, car upholstery, etc.
- the process according to the invention is advantageously carried out in drums, for example in the ways (processing recipes) shown, by way of example, in the appended tables.
- a rotary drum which is manually or semi-manually operated or is controlled by a control unit, which automatically manages, based on operating schedules corresponding to pre-set recipes, the operation of the drum and, therefore, the different steps of the process.
- the drum can be set so as to rotate for predetermined time intervals at the desired speed, if necessary alternating rest times (still drum).
- an indication such as "automatic cycle x-y-x" indicates that the drum rotates for periods of x minutes alternated with rest periods of y minutes.
- the drum is drained, when the processing recipe requires to do so, through suitable openings.
- the process according to the present invention is used to treat raw skins, for example skins that are freshly salted immediately after having flayed the animal.
- Raw skins are firstly introduced into the drum for a preliminary soaking-liming step, during which, in substantially known ways, the first processing in preparation of the tanning is carried out, thus obtaining the so-called pelt (state of the skin at the end of the preliminary soaking-liming step).
- the preliminary step is carried out in the ways shown in appended Table I of figure 1 where the compositions of the products used are indicated as percentage of the weight of the raw skin treated in the preliminary step.
- tanning macro-step carried out, for example, in the ways shown in Table II of figure 2 , which comprises four main steps: deliming, bating, pickling, tanning.
- compositions of the products used in the tanning macro-step are indicated as percentage of the weight of the pelt of the skin i.e. of the weight of the material obtained from the preliminary step and destined to the tanning macro-step.
- the deliming step has the function of completely removing the lime absorbed by the skin during the preliminary soaking-liming step.
- a first bath which contains:
- the drum is caused to rotate for 15-45 minutes, then it is drained.
- a deliming agent is added, in particular 30-100%; then, in successive stages, a deliming agent is added, in particular a sulfamic acid-based deliming agent (e.g.: DECALCINANTE A-OS SPECIAL), in increasing quantities:
- the drum is drained and a delimed skin is obtained, which is completely free from lime.
- the skin undergoes a bating treatment, which basically consists in the removal of the so-called surface shield (residues of proteins, albumins, etc.) and of elastin.
- the bating step can be carried out in basically known ways, through suitable degreasing substances and enzymes as indicated, for example, in Table II.
- the skin is subjected to a pickling step, consisting in conditioning the skin at a highly acid pH below 4 and approximately ranging from 2.7 to 3.5, preferably around 3-3.2.
- the pickling step is carried out with known products, basically, sodium chloride, formic acid and sulfuric acid, but, according to the invention, it requires specific operating techniques, which ensure a particular balance among the content of water, salts and acids in the treatment bath contained in the drum, this condition being necessary to make sure that the subsequent addition of the tanning substance and the penetration into the section of the skin produce good results.
- known products basically, sodium chloride, formic acid and sulfuric acid
- the pickling step is carried out as follows: After having emptied the drum from the water left by the previous bating step, the drum is filled with a bath containing:
- the drum is caused to rotate for 10-20 minutes and then density of the bath is controlled to make sure that it ranges from 8 to 10 degrees Baumé.
- the result is a bath with a pH below 4 and approximately ranging from 2.7 to 3.5, preferably ranging from approximately 3 to 3.2.
- the total content of water at the end of the pickling step (hence, before the tanning step), starting from 25% of initial water and after the addition of the diluted acids, is approximately 40% +/- 5%.
- the content of water at the beginning of the tanning step should range from 25% to 55%.
- experiments have shown that a total water content below 25% or exceeding 55% slows down - or even completely blocks - the penetration of the tanning product and, therefore, the stability of the tanning itself.
- a tanning product (2-10%) is added to the drum, which contains an acid naphthalene tannin, an acid phenolic tannin and sodium sulphate; and a synthetic ester (0.1-1.0%).
- the drum is rotated for 5 hours.
- the skins are discharged from the drum without being washed (contrary to what normally happens in traditional tanning processes).
- This type of tanning allows manufacturers to obtain a partial stabilization of the skins, which can be stored after having been subjected to pressing or, if necessary, complete drying, split, shaved and, at the end, sent to the retanning and drying steps.
- the skins Once the skins have been split and/or shaved to obtain the desired thickness, they are reintroduced into drums, in which a retanning step is carried out so as to give to the skins, after the drying thereof, high softness, a peasant feel, colouring and technical performances that are useful in the production of articles such as shoes, leather products, furniture, car upholstery, etc.
- the retanning step is carried out, for example, in the ways shown in Table III of figure 3 , where, like in the description below, the compositions of the products used are indicated as percentage of the weight of the shaved skin (material ready for the retanning step).
- the retanning step is carried out using a retanning compound containing a C4-C6 linear di-aldehyde in an aqueous solution, wherein the di-aldehyde is available in quantity ranging from 1 to 15% of the weight of the treated skin.
- the retanning compound is prepared by mixing, for example, through rotation in the drum for approximately 20 minutes:
- the skins are introduced into the drum, which is rotated for 60 minutes.
- a fatliquor (8-12%) is added, for example a synthetic oil mixed with deodorized sulphited fish oil (e.g.: COSMOFAT G), rotating for 30 minutes; then a liquid tanning product (8-12%) is added, which contains sulphone-based synthetic tannins, in particular phenolsulphone-based and/or di-idroxy-diphenilsulphonebased (e.g.: COSMOWHITE SR), rotating for 120 minutes.
- sulphone-based synthetic tannins in particular phenolsulphone-based and/or di-idroxy-diphenilsulphonebased (e.g.: COSMOWHITE SR), rotating for 120 minutes.
- the drum is drained and two washing steps are carried out with 300% of hot water (40°C).
- the drum is drained and two further washing steps are carried out.
- the skin is pressed, vacuum-dried at a temperature not exceeding 40°C and then hung in a catenary for complete drying.
- the skin Once the skin has dried, it can be processed to manufacture any kind of article.
- the products used for the dressing of the skins must be selected so as not to jeopardize the biodegradability of the leather obtained with the process according to the invention.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Description
- The present invention relates to a skins tanning process.
- Skins tanning, i.e. the processing undergone by animal skins to turn them into leather, in an ancient process, but nowadays it is carried out with advanced techniques.
- Generally speaking, a tanning process includes preliminary operations producing the so-called pelt; the actual tanning; the retanning; and dressing treatments.
- Preliminary operations are basically aimed at removing, from the skins, various impurities and the preservatives used to maintain the skins intact until the tanning process as well as at restoring the features of the skins, thus making them suitable for the following actual tanning treatments.
- Then, tanning transforms the pelt into leather by means of proper tanning substances, which penetrate the skin and are steadily fixed to the dermal fibres. There are different types of tanning (vegetable tanning, mineral tanning, etc.), which differ from one another because of the tanning substances used and of the ways in which these substances are applied; some types of tanning are better than others for the treatment of certain skins and, generally speaking, manufacturers select the tanning process that is deemed to be the most appropriate to obtain specific features of the end product.
- After the actual tanning there is a retanning step, which is used to define the specific features of the skins depending on the article to be manufactured; the skins are then subjected to dressing operations, even based on the uses for which the skins are intended.
-
US4245996A discloses sulphonated condensation products based on naphtalene and phenol and which are used as tanning agents for the production of leather and as re-tanning agents for re-tanning mineral-tanned leather. - Tanning processes known at the moment have proven to be not good enough, in particular from the point of view of their environmental impact. As a matter of fact, known processes, because of the products used in the different processing steps and of the techniques involved, cause the production of waste waters and of processing waste that are highly polluting and, anyway, are very difficult to be handled from an environmental point of view; moreover, they do not lead to an end product or to a processing waste that are completely (or at least largely) biodegradable or compostable.
- The object of the present invention is to provide a tanning process that is not affected by the above-mentioned drawbacks shown by prior art processes; in particular, it is an object of the present invention to provide a tanning process that allows manufacturers to obtain a fully biodegradable product, besides being versatile and effective, which leads to the production of high-quality products.
- Therefore, the present invention relates to a tanning process as defined, in its essential aspects, in appended claim 1 and, in its additional features, in the dependent claims.
- The process according to the present invention, thanks to the specific products used and to the processing techniques applied, allows manufacturers to obtain a fully biodegradable product.
- Furthermore, the process according to the present invention allows the skins to gain (after having been dried) features that are comparable with the ones obtained with traditional techniques, in particular softness, a peasant feel, colouring and technical performances that are suitable for the use in different fields, such as shoes, leather products, furniture, car upholstery, etc.
- Further features and advantages of the invention will be best understood upon perusal of the description of the following non-limiting embodiments, with reference to the accompanying figures, wherein:
-
figure 1 contains a table (Table I) showing examples of the ways in which a preliminary step, in particular a soaking-liming step, of the process according to the invention can be carried out; -
figure 2 contains a table (Table II) showing examples of the ways in which further steps, defining - as a whole - a tanning macro-step, of the process according to the invention can be carried out; -
figure 3 contains a table (Table III) showing examples of the ways in which a retanning step of the process according to the invention can be carried out. - The process according to the invention is advantageously carried out in drums, for example in the ways (processing recipes) shown, by way of example, in the appended tables.
- Advantageously, all operations are carried out in a rotary drum, which is manually or semi-manually operated or is controlled by a control unit, which automatically manages, based on operating schedules corresponding to pre-set recipes, the operation of the drum and, therefore, the different steps of the process.
- For example, the drum can be set so as to rotate for predetermined time intervals at the desired speed, if necessary alternating rest times (still drum).
- In the appended tables, an indication such as "automatic cycle x-y-x" indicates that the drum rotates for periods of x minutes alternated with rest periods of y minutes.
- Obviously, the indications provided below and contained in the appended tables must be interpreted as merely explanatory and the operating modes of the process, in particular the products used, their quantity and the duration of the single operations and steps, can be different from the ones shown.
- The drum is drained, when the processing recipe requires to do so, through suitable openings.
- The process according to the present invention is used to treat raw skins, for example skins that are freshly salted immediately after having flayed the animal.
- Raw skins are firstly introduced into the drum for a preliminary soaking-liming step, during which, in substantially known ways, the first processing in preparation of the tanning is carried out, thus obtaining the so-called pelt (state of the skin at the end of the preliminary soaking-liming step).
- By mere way of example, the preliminary step is carried out in the ways shown in appended Table I of
figure 1 where the compositions of the products used are indicated as percentage of the weight of the raw skin treated in the preliminary step. - Here and below and in all tables, the commercial names of the products used are provided by mere way of example; each product indicated herein can be replaced with equivalent products.
- Then, there is a tanning macro-step carried out, for example, in the ways shown in Table II of
figure 2 , which comprises four main steps: deliming, bating, pickling, tanning. - In Table II and in the description below, the compositions of the products used in the tanning macro-step are indicated as percentage of the weight of the pelt of the skin i.e. of the weight of the material obtained from the preliminary step and destined to the tanning macro-step.
- The deliming step has the function of completely removing the lime absorbed by the skin during the preliminary soaking-liming step.
- According to the invention, it is important that the lime is completely removed.
- In the deliming step, at first, a first bath is used, which contains:
- 50-100% cold water;
- 0.1-0.5% ammonium sulfate;
- 0.1-1.0% thioglycolic acid (e.g.: COSMOCAL E).
- The drum is caused to rotate for 15-45 minutes, then it is drained.
- Subsequently, after having drained the drum, (cold) water is added, in particular 30-100%; then, in successive stages, a deliming agent is added, in particular a sulfamic acid-based deliming agent (e.g.: DECALCINANTE A-OS SPECIAL), in increasing quantities:
- 0.5-2.0%, preferably approximately 1.0%, rotating for 15-45 minutes (for example, 30 minutes);
- 0.5-3.0%, preferably approximately 1.5%, rotating for 15-45 minutes (for example, 30 minutes);
- 1.0-5.0%, preferably approximately 3.0%, rotating for 120-240 minutes (for example, 180 minutes);
- The drum is drained and a delimed skin is obtained, which is completely free from lime.
- After having been delimed, the skin undergoes a bating treatment, which basically consists in the removal of the so-called surface shield (residues of proteins, albumins, etc.) and of elastin. The bating step can be carried out in basically known ways, through suitable degreasing substances and enzymes as indicated, for example, in Table II.
- Subsequently, the skin is subjected to a pickling step, consisting in conditioning the skin at a highly acid pH below 4 and approximately ranging from 2.7 to 3.5, preferably around 3-3.2.
- The pickling step is carried out with known products, basically, sodium chloride, formic acid and sulfuric acid, but, according to the invention, it requires specific operating techniques, which ensure a particular balance among the content of water, salts and acids in the treatment bath contained in the drum, this condition being necessary to make sure that the subsequent addition of the tanning substance and the penetration into the section of the skin produce good results.
- The pickling step is carried out as follows:
After having emptied the drum from the water left by the previous bating step, the drum is filled with a bath containing: - 20-30% cold water;
- 4-10% sodium chloride;
- 0.3-0.7% sodium formate.
- The drum is caused to rotate for 10-20 minutes and then density of the bath is controlled to make sure that it ranges from 8 to 10 degrees Baumé.
- Then there is the addition of:
- 1% formic acid at 85%, rotating for 30-60 minutes;
- 1% sulfuric acid at 98%, rotating for 3-4 hours.
- This is followed by a rest step lasting 12-24 hours, during which the drum rotates, for example, with cycles of 5-10 minutes alternated with pauses of 60-90 minutes.
- The result is a bath with a pH below 4 and approximately ranging from 2.7 to 3.5, preferably ranging from approximately 3 to 3.2.
- The total content of water at the end of the pickling step (hence, before the tanning step), starting from 25% of initial water and after the addition of the diluted acids, is approximately 40% +/- 5%.
- In any case, it is important to remember that the content of water at the beginning of the tanning step should range from 25% to 55%. As a matter of fact, experiments have shown that a total water content below 25% or exceeding 55% slows down - or even completely blocks - the penetration of the tanning product and, therefore, the stability of the tanning itself.
- Then there is the actual tanning step, during which a tanning product (2-10%) is added to the drum, which contains an acid naphthalene tannin, an acid phenolic tannin and sodium sulphate; and a synthetic ester (0.1-1.0%). The drum is rotated for 5 hours.
- At the end of the tanning step, the skins are discharged from the drum without being washed (contrary to what normally happens in traditional tanning processes).
- This type of tanning allows manufacturers to obtain a partial stabilization of the skins, which can be stored after having been subjected to pressing or, if necessary, complete drying, split, shaved and, at the end, sent to the retanning and drying steps.
- Once the skins have been split and/or shaved to obtain the desired thickness, they are reintroduced into drums, in which a retanning step is carried out so as to give to the skins, after the drying thereof, high softness, a peasant feel, colouring and technical performances that are useful in the production of articles such as shoes, leather products, furniture, car upholstery, etc.
- The retanning step is carried out, for example, in the ways shown in Table III of
figure 3 , where, like in the description below, the compositions of the products used are indicated as percentage of the weight of the shaved skin (material ready for the retanning step). - In particular, the retanning step is carried out using a retanning compound containing a C4-C6 linear di-aldehyde in an aqueous solution, wherein the di-aldehyde is available in quantity ranging from 1 to 15% of the weight of the treated skin.
- For example, the retanning compound is prepared by mixing, for example, through rotation in the drum for approximately 20 minutes:
- 150-250% hot water (at 40°);
- 1-15% of a C4-C6 linear di-aldehyde in an aqueous solution (e.g.: COSMOWHITE 58).
- Then the skins are introduced into the drum, which is rotated for 60 minutes.
- Subsequently, a fatliquor (8-12%) is added, for example a synthetic oil mixed with deodorized sulphited fish oil (e.g.: COSMOFAT G), rotating for 30 minutes; then a liquid tanning product (8-12%) is added, which contains sulphone-based synthetic tannins, in particular phenolsulphone-based and/or di-idroxy-diphenilsulphonebased (e.g.: COSMOWHITE SR), rotating for 120 minutes.
- Then the drum is rotated for periods of 3 minutes with rest intervals of 30 minutes for a whole night (8 hours).
- The drum is drained and two washing steps are carried out with 300% of hot water (40°C).
- Then a bath of 100% hot water (40°C) is added, as well as a metal-free colouring agent, rotating for 30 minutes.
- Subsequently, there is the addition of:
- 15-25% of a vegetable fatliquor, for example a vegetable lecithin-based one (e.g.: COSMOFAT C), rotating for 30 minutes;
- 5-15% of an acrylic resin at 25% (e.g.: COSMOWHITE H), rotating for 30 minutes;
- 5-15% of a vegetable extract-base filler (e.g.: COSMOWHITE F), rotating for 120 minutes;
- 2-3% of formic acid, rotating for 30 minutes;
- 2-3% of formic acid, rotating for 30 minutes;
- 5-15% of the tanning product containing sulphone-based synthetic tannins (e.g.: COSMOWHITE SR), rotating for 120 minutes.
- The drum is drained and two further washing steps are carried out.
- Subsequently, the skin is pressed, vacuum-dried at a temperature not exceeding 40°C and then hung in a catenary for complete drying.
- Once the skin has dried, it can be processed to manufacture any kind of article.
- The products used for the dressing of the skins must be selected so as not to jeopardize the biodegradability of the leather obtained with the process according to the invention.
- The process described and explained herein can be subjected to further changes and variants, which do not go beyond the scope of protection of the appended claims.
Claims (7)
- Tanning process, comprising a tanning step and a retanning step; the process being characterized in that the tanning step comprises the steps of: treating skins in a drum with a bath containing a tanning product comprising an acid naphthalene tannin, an acid phenolic tannin and sodium sulphate; and optionally a synthetic ester; and the retanning step comprises the steps of: treating the skins in a drum with a retanning bath containing an aqueous solution of a di-aldehyde, in particular a C4-C6 linear di-aldehyde; adding a fatliquor; adding a liquid tanning product containing sulphone-based synthetic tannins, in particular phenolsulphone-based and/or di-idroxy-diphenilsulphonebased; adding a vegetal-base filler.
- A process according to claim 1, wherein the retanning step comprises then the further steps of: draining the drum; effecting at least one and preferably two washes with water; optionally adding a coloring bath; adding a vegetal-base fatliquor; adding an acrylic resin; adding a vegetal-base filler; adding formic acid, in one or more times; adding a tanning product containing sulphone-base synthetic tannins; draining the drum; effecting at least one and preferably two more washes with water.
- A process according to claim 1 or 2, wherein at the end of the tanning step the skins are discharged from the drum without being washed for being then subjected to the retanning step.
- A process according to one of the preceding claims, comprising, before the tanning step, a step of deliming, performed so as to remove completely the lime that the skins have absorbed previously, in particular in a preliminary step of soaking-liming.
- A process according to one of the preceding claims, comprising, before the tanning step, a pickling step, comprising the steps of: treating the skins in a drum with a bath containing sodium chloride and sodium formate, the bath having a density ranging between 8 and 10 degrees Baumé; adding formic acid; adding sulfuric acid, for obtaining a bath having a pH lower than 4 and ranging between 2,7 and 3,5 and preferably ranging between 3,0 and 3,2.
- A process according to one of the preceding claims, wherein the total water content at the end of the pickling step and before the tanning step is comprised between 25% and 55% of the pelt weight of the skins treated.
- Tanned skin, i.e. leather, characterized by being obtained by the tanning process according to one of the preceding claims.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ITTV2015A000055A ITTV20150055A1 (en) | 2015-04-21 | 2015-04-21 | SKIN TANNING PROCESS |
PCT/IB2016/052282 WO2016170503A1 (en) | 2015-04-21 | 2016-04-21 | Skins tanning process |
Publications (2)
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EP3286342A1 EP3286342A1 (en) | 2018-02-28 |
EP3286342B1 true EP3286342B1 (en) | 2021-07-28 |
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EP16723529.0A Active EP3286342B1 (en) | 2015-04-21 | 2016-04-21 | Skins tanning process |
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EP (1) | EP3286342B1 (en) |
CN (1) | CN107743525B (en) |
ES (1) | ES2887790T3 (en) |
IT (1) | ITTV20150055A1 (en) |
WO (1) | WO2016170503A1 (en) |
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CN106834563B (en) * | 2017-01-20 | 2018-08-17 | 辽宁富新新材料有限公司 | A method of few salt pickling, tanning leather |
WO2020044250A1 (en) * | 2018-08-30 | 2020-03-05 | Santori Pellami S.P.A. | Metal-free tanning method |
CN116397059B (en) * | 2023-05-10 | 2024-06-14 | 顾家家居股份有限公司 | Anti-odor composition for retanning of cowhide |
Family Cites Families (6)
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DE2834121C2 (en) * | 1978-08-03 | 1980-08-21 | Bayer Ag, 5090 Leverkusen | Condensation products from terphenyl sulfonic acids, naphthalene sulfonic acids, bis (4-hydroxyphenyl) sulfone and formaldehyde |
CN1208470C (en) * | 2001-12-20 | 2005-06-29 | 单凯波 | Processing method of making leather using frog skin |
TW200641140A (en) * | 2004-12-17 | 2006-12-01 | Tfl Ledertechnik Gmbh | Composition for the treatment of leather |
DE102006029408A1 (en) * | 2006-06-23 | 2007-12-27 | Lanxess Deutschland Gmbh | Condensation products containing sulfonic or carboxylic acid groups and based on di-aldehyde and amino compounds, e.g. glutaraldehyde and melamine and-or urea, used for tanning leather and furs |
CN102586505B (en) * | 2012-01-13 | 2014-04-23 | 浙江中辉皮草有限公司 | Circularly-tanning technology for chrome tanning liquor of sheep garment leather |
CN103215391B (en) * | 2013-04-23 | 2015-02-04 | 何裕华 | Non-chromium leather tanning method |
-
2015
- 2015-04-21 IT ITTV2015A000055A patent/ITTV20150055A1/en unknown
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2016
- 2016-04-21 WO PCT/IB2016/052282 patent/WO2016170503A1/en active Application Filing
- 2016-04-21 CN CN201680023111.1A patent/CN107743525B/en active Active
- 2016-04-21 EP EP16723529.0A patent/EP3286342B1/en active Active
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WO2016170503A1 (en) | 2016-10-27 |
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CN107743525A (en) | 2018-02-27 |
ES2887790T3 (en) | 2021-12-27 |
ITTV20150055A1 (en) | 2016-10-21 |
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