WO2013072063A1 - Method for tanning or retanning rawhide, rawhide scraps, or an untanned article containing collagen - Google Patents
Method for tanning or retanning rawhide, rawhide scraps, or an untanned article containing collagen Download PDFInfo
- Publication number
- WO2013072063A1 WO2013072063A1 PCT/EP2012/004773 EP2012004773W WO2013072063A1 WO 2013072063 A1 WO2013072063 A1 WO 2013072063A1 EP 2012004773 W EP2012004773 W EP 2012004773W WO 2013072063 A1 WO2013072063 A1 WO 2013072063A1
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- WO
- WIPO (PCT)
- Prior art keywords
- tanning
- carbon atoms
- polyorganosiloxane
- group
- composition
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 45
- 102000008186 Collagen Human genes 0.000 title claims abstract description 12
- 108010035532 Collagen Proteins 0.000 title claims abstract description 12
- 229920001436 collagen Polymers 0.000 title claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 60
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 32
- 125000004432 carbon atom Chemical group C* 0.000 claims description 46
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 38
- 230000008569 process Effects 0.000 claims description 35
- 239000010985 leather Substances 0.000 claims description 34
- 239000000839 emulsion Substances 0.000 claims description 32
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 229920005989 resin Polymers 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- 239000004094 surface-active agent Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
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- 238000006243 chemical reaction Methods 0.000 claims description 7
- FWVCSXWHVOOTFJ-UHFFFAOYSA-N 1-(2-chloroethylsulfanyl)-2-[2-(2-chloroethylsulfanyl)ethoxy]ethane Chemical compound ClCCSCCOCCSCCCl FWVCSXWHVOOTFJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
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- 229910021555 Chromium Chloride Inorganic materials 0.000 description 2
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
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- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 125000002951 idosyl group Chemical class C1([C@@H](O)[C@H](O)[C@@H](O)[C@H](O1)CO)* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- GVIIRWAJDFKJMJ-UHFFFAOYSA-N propan-2-yl 3-oxobutanoate Chemical compound CC(C)OC(=O)CC(C)=O GVIIRWAJDFKJMJ-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000003307 slaughter Methods 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229950004959 sorbitan oleate Drugs 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 238000009283 thermal hydrolysis Methods 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
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
- C14C3/04—Mineral tanning
- C14C3/06—Mineral tanning using chromium compounds
-
- 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
-
- 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
- C14C9/04—Fixing tanning agents in the leather
Definitions
- a process for tanning or retanning raw hides, raw hides waste or a non-tanned article containing collagen is provided.
- the invention relates to a process for tanning or retanning raw hides, raw hides waste or a non-tanned article containing collagen.
- the present invention is in the field of processing raw leather skins.
- the "picklage" which by an acid treatment aims to reduce the pH of the skins so as to improve the conservation of the skins
- the "tanning” in which the collagen fibers are stabilized by the tanning agents so that the skin becomes rot-proof
- the "wrought” which comprises the following operations: a neutralization and a washing, followed by a retannage, of drying and bathing food, which are mostly carried out in a single treatment tank.
- the leather is called “leather in crust", and the “finishing” which includes several mechanical treatments, as well as the application of a surface layer to improve the appearance and feel of the leather.
- the tanning step is considered to be the most important in the processing chain of raw hides, which after storage are stiff and putrescible and are thus transformed into a soft and rotproof material that is leather.
- the most widely used tanning systems are: mineral tanning, which uses trivalent chromium salts, vegetable tanning based on the tanning power of plant extracts of wood or bark from certain trees and tanning achieved via synthetic products .
- the existing mineral tanning processes are carried out in an aqueous medium. Tanning with chromium chloride or chromium sulphate is the most common.
- Chromium tanning is most often preceded by acid treatment in a stage known as "picklage". The picklage makes it possible to preserve the skin in guts and to reduce the reactivity of the reaction sites, with respect to the chromium, so as not to hinder its diffusion in the collagen.
- the trivalent chromium is inserted between the collagen fibers and the reticles by forming complexes with the anionic sites of the polypeptide chains.
- Tanning with chromium salts leads to leather having excellent physicochemical characteristics, including flexibility, tear resistance and high thermal resistance.
- it is harmful to the environment because of the use of metals that are difficult to recycle or eliminate, such as chromium.
- the tanning baths are never completely depleted of chromium, which leads to rejects of bath containing significant amounts of chromium (of the order of 25 to 30% compared to the amounts introduced).
- chromium is a toxic pollutant and releases are legally required to undergo chromium removal treatments which are very expensive and do not allow recovery direct chromium.
- chromium is a toxic pollutant and releases are legally required to undergo chromium removal treatments which are very expensive and do not allow recovery direct chromium.
- releases of chromium pollute the baths and require disposal treatments as for the tanning baths.
- the use of metals such as chromium sometimes causes, because of the allergenic action of the latter, cutaneous reactions in the user.
- chromium salts so that more chromium can be fixed by the skin thus treated. This retannage step is intended to provide better dye penetration, improved overall feel, thickness, toughness, chemical resistance and heat resistance.
- US Pat. No. 4,039,281 describes a tanning process consisting of preparing a tanning bath using a water-immiscible organic solvent in which are successively introduced a mineral tanning agent and a synthetic tanning agent. . The skins are wiped by centrifugation to reduce their hydration rate to a very low value, then the organic solvent is removed to proceed to the following steps that are the food of the leather to soften, the dye ...
- one of the main objects of the present invention is to provide a process for tanning or retanning raw hides, raw hides waste or a non-tanned article containing collagen which improves the exhaustion of the agents. tanning or retanning and improve the fixing of tanning materials in the leather which reduces the amount of tanning agent used and the amount of pollutants released into the effluents from tanneries.
- Another object of the present invention is to propose a process for tanning or retanning raw skins, raw hide waste or a non-tanned article containing collagen which makes it possible to produce tanned leathers, in particular tanned leathers.
- chromium whose quality in terms of their physicochemical characteristics (soft touch, chemical resistance and heat resistance) is at least equal to or greater than that of leather tanned by traditional methods.
- Another object of the present invention is to provide a process for preparing leather comprising the tanning or retannage step according to the invention.
- a final object of the present invention is to provide novel tanned leathers, in particular chromium, prepared according to the method of the invention and having better physicochemical properties, namely a clean staining tone, satisfactory dye penetration, grain lubrication, softness, flexibility, extensibility, flexibility and robustness.
- At least one tanning agent T which is a mineral agent
- at least one silicone composition E which is capable of forming a silicone elastomer either at ambient temperature or by raising the temperature, and preferably the silicone composition E is under the form of a silicone emulsion in water or in the form of an aqueous silicone dispersion, and
- the components of the composition E are chosen so that said composition can form a silicone elastomer by condensation, hydrosilylation or dehydrogenation condensation reactions at either ambient temperature or by temperature rise.
- the inventors have had the merit of surprisingly and unexpectedly updating the association in a step of tanning or retanning a tanning agent and a composition capable of forming a silicone elastomer either at ambient temperature or by raising the temperature, makes it possible to improve the exhaustion of the tanning or retanning agents and to improve the fixing of the tanning materials in the leather, which makes it possible to reduce the quantity of tanning agent used and the quantity of pollutants released into the effluents from tanneries.
- the silicone composition changes from a liquid (or viscous) state before crosslinking (i.e. the components have not yet reacted between they) to a solid state (or elastomer) which results in a physical hardening of the silicone composition (the reactive components reacted with each other).
- a catalyst is mixed with other reactive silicone species just before use thus inducing the start of the reaction of crosslinking, ie the water is removed (by drying) thus allowing the reactive silicone species that are present in the "goutellets" of the emulsion or dispersion to come into contact with each other so as to be able to initiate the reaction crosslinking.
- a silicone network is formed by condensation, hydrosilylation or dehydrogenation reactions according to the reactive silicone components used in the silicone composition E.
- the silicone composition E has the advantage of being in the form of a silicone oil in water emulsion or of an aqueous silicone dispersion thus avoiding the problems inherent in the use of organic solvent phase tanning.
- Such an increase in the fixing of the tanning agent, in particular chromium, or a reduction in its exhaustion is an important advantage in that the properties relating to the touch, to the thickness, to the strength, to the resistance to chemicals and the heat, richness and absorption of dyes are also improved.
- the components of the silicone composition E are defined with reference to their initial chemical structure, that is to say the one which characterizes them before the formation of the silicone oil in water emulsion or the aqueous silicone dispersion. Since they are in an aqueous medium, their structure is likely to be modified following the hydrolysis and condensation reactions.
- the silicone oil emulsions in water can be prepared as follows:
- one or more component (s) of the silicone composition E may be in the form of an oil-in-water emulsion before their addition.
- the emulsions will then be simply mixed, optionally in an aqueous medium, so as to control the final dilution of the silicone composition E.
- the silicone composition E further comprises at least one polyorganosiloxane (A) having identical or different siloxyl units of general formula (I):
- R 1 or R 2 is a hydroxyl radical -OH or alkoxy -OR 2 with R 2 being a front alkyl of 1 to 6 carbon atoms.
- the polyorganosiloxane (A) comprises the following loxyl units:
- R 2 , R 3 and R 4 are radicals, identical or different, selected from the group consisting of: linear or branched C1-C6 alkyl radicals (such as for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl); t-butyl, n-pentyl, n-hexyl), C 3 -C 8 cycloalkyl radicals (such as, for example, cyclopentyl, cyclohexyl), aryl radicals,
- C6-C10 such as eg phenyl, naphthyl
- alkylarylene radicals such as for example tolyl, xylyl
- the polyorganosiloxane (A) may be a linear polydiorganosiloxane oil having at least two SiOH silanol groups per molecule and having a dynamic viscosity at 25 ° C generally between 50mPa.s and 50x10 6 mPa.s. All the viscosities referred to herein correspond to a dynamic viscosity quantity which is measured, in a manner known per se, at 25.degree.
- R 3 and R 4 which may be identical or different, represent: an alkyl having from 1 to 6 carbon atoms; cycloalkyl having 3 to 8 carbon atoms; aryl, alkylarylene or arylalkylene; and
- polyorganosiloxane (A) most useful according to the invention, because of their industrial availabilities, are those for which R 3 and R 4 are independently chosen from the group of radicals consisting of: a methyl, an ethyl, a propyl , isopropyl, cyclohexyl, phenyl, and 3,3,3-trifluoropropyl. Preferably, at least about 80% by number of these radicals are methyl radicals.
- the polyorganosiloxane (A) may have a viscosity that can reach
- a component is chosen whose viscosity is generally of the order of 100,000 to 200,000 mPa.s.
- ⁇ , ⁇ -bis (hydroxy) polydimethylsiloxanes are more particularly preferred.
- the polyorganosiloxane (A) may also be chosen from organosilicon resins bearing at least two condensable hydroxyl or alkoxyl groups and comprising at least two different types of siloxyl units chosen from those of formula M, D, T and Q with:
- said resin having a weight content in hydroxyl or alkoxy substituents of between 0.1 and 10% by weight relative to the weight of the resin, and preferably a weight content of hydroxyl or alkoxy substituents of between 0.2 and 5% by weight relative to the weight of the resin.
- Organosilicon resins generally have from about 0.001 to about 1.5 OH and / or alkoxyl per silicon atom. These organosilicon resins are generally prepared by co-hydrolysis and co-condensation of chlorosilanes such as those of formulas (R 9 ) 3 SiCl, (R 9 ) 2 Si (Cl) 2 , R 9 Si (Cl) 3 or Si (Cl ) 4 .
- the radicals R 9 are identical or different and are generally chosen from: linear or branched C 1 -C 6 alkyl, phenyl and 3,3,3-trifluoropropyl radicals.
- alkyl radicals R 9 are methyl, ethyl, isopropyl, tert-butyl and n-hexyl. These resins are branched organopolysiloxane oligomers or polymers well known and commercially available. They exhibit, in their structure, at least two different siloxyl units chosen from those of formula (R 9) 3 SiO / 2 (M unit), (R 9) 2 Si0 2/2 (D unit), R 9 Si0 3 / 2 (T unit) and S1O4 / 2 (Q unit), at least one of these units being a T or Q unit.
- the weight content of OH and / or alkoxyl groups is generally between 0.2 and 10% by weight. weight.
- silicic resins commonly known as T (OH) , DT (OH) , DQ (OH) , DT (OH) , MQ (OH) , MDT (OH) , MDQ (OH) or these, with the m and D having the m me meaning as above and:
- the polyorganosiloxane (A) may be used in a proportion of 1 to 50% by weight, and preferably 3 to 40% by weight and more preferably in a proportion of 5 to 30% by weight relative to the total weight of the composition E .
- the composition E further comprises at least one polyorganosiloxane (B) having per molecule at least two hydrogenosiiane SiH groups and preferably at least three hydrogenosiiane SiH groups.
- polyorganosiloxanes (B) useful according to the invention mention may be made of those comprising:
- the groups L which are identical or different, each represent a monovalent hydrocarbon group and preferably an alkyl group having from 1 to 8 carbon atoms inclusive, optionally substituted by at least one halogen atom, an aryl group and, advantageously, a xylyl, tolyl or phenyl radical,
- d is 1 or 2
- e is 0, 1 or 2
- the sum (d + e) is 1, 2 or 3
- the polyorganosiloxane (B) comprises at least two siloxyl units (11-1) and preferably at least three siloxyl units (11-1).
- the L groups which are identical or different, are preferably chosen from the group consisting of: a methyl, an ethyl and a phenyl.
- the dynamic viscosity of this polyorganosiloxane (B) is most often at least 10 mPa.s and preferably between 20 and 1000 mPa.s. For economic reasons, its viscosity is preferably less than 100 mPa.s, that is to say between 10 mPa.s and 100 mPa.s.
- the polyorganosiloxane (B) may be formed solely of units of formula (II-1) or may further comprise units of formula (II-2).
- Useful examples of siloxyl units of formula (11-1) are: H (CH 3) 2 SiO / 2, H (CH 3) Si0 2/2 and H (C 6 H 5) Si0 2/2.
- Useful examples of siloxyl units of formula (II-2) are the siloxy units: Si0 4/2, (CH 3) 2Si0 2/2, (CH 3) 3 SiO / 2, (CH 3) Si0 3/2, (CH 3) (C e H 5) Si02 / 2.
- polyorganosiloxane (B) are linear or cyclic compounds such as:
- the polyorganosiloxane (B) may optionally be a mixture of a dimethylpolysiloxane with hydrogenodimethylsilyl ends and a polyorganosiloxane carrying at least 3 SiH (hydrogenosiloxyl) functional groups.
- the composition E further comprises at least one polyorganosiloxane (C) and / or at least one silane (D) each comprising at least one group comprising at least one nitrogen atom and preferably an amine function primary, secondary, tertiary or quaternary.
- C polyorganosiloxane
- D silane
- silane (D) As an example of silane (D) according to the invention, mention may be made of 3-aminopropyltrihydroxysilane or the compound Silquest® VS142 sold by the company Momentive Performance Materials, in aqueous solution, which consists of a silane oligomer described below. partially condensed via its SiOH functions:
- This constituent when it is present in the emulsion, is used at a rate of 0.5 to
- this particular silane can also act as a crosslinker via the presence of the three reactive functions that are hydroxyl groups and this while being water soluble.
- the construction of the silicone network after crosslinking the composition (E) is only facilitated.
- polyorganosiloxane (C) mention may be made of those which comprise identical or different siloxyl units of general formula:
- R 3 are identical or different and each represents a monovalent hydrocarbon radical chosen from alkyl radicals having from 1 to
- R 4 are identical or different radicals and represent radicals of general formula (IV):
- R 6 being a divalent hydrocarbon group having from 1 to 40 carbon atoms
- R 7 being a hydrogen atom or a monovalent hydrocarbon group having from 1 to 40 carbon atoms
- R 8 being a hydrogen atom or a radical of formula (V) below:
- R 9 being a divalent radical of formula (VI) below:
- At least one siloxyl unit carrying an R 4 group is present per molecule.
- radicals R 4 useful according to the invention may include the following radicals:
- the indices i, j and k are identical or different integers having a value greater than or equal to 0 and less than or equal to 20 and the sum i + j + k is preferably between 0 and 30.
- the radical R 4 is chosen from the group consisting of the following radicals: - (CH 2 ) 3 -NH 2 and - (CH 2 ) 3 -NH- (CH 2 ) 2 -NH 2 .
- the polyorganosiloxane (C) is characterized in that it comprises, per molecule, at least one siloxyl unit substituted with at least one functional group V directly bonded to a silicon atom, said functional group V being a sterically hindered piperidinyl group (s) group (s) selected from the group consisting of:
- R 4 is a divalent hydrocarbon radical chosen from the group consisting of:
- alkylene-carbonyl radicals whose linear or branched alkylene part contains 2 to 20 carbon atoms;
- alkylene-cyclohexylene radicals whose linear or branched alkylene part contains 2 to 12 carbon atoms and the cyclohexylene part comprises an OH group and optionally 1 or 2 alkyl radicals having 1 to 4 carbon atoms; the radicals of formula R 7 -O-R 7 in which the radicals R 7, which are identical or different, represent alkylene radicals having 1 to 12 carbon atoms;
- radicals of formula R 8 -OR 9 -O-CO-R 8 in which the radicals R 8 and R 9, which are identical or different, represent alkylene radicals having 2 to 12 carbon atoms and the radical R 9 is optionally substituted by a hydroxyl radical;
- U represents -O- or -N (R 10 ) -, with R 10 being a radical chosen from the group consisting of a hydrogen atom, a linear or branched alkyl radical containing 1 to 6 carbon atoms and a divalent radical; of formula (II) below:
- R 12 has the same meaning as for R 4 indicated above, R 13 and R 14 have the meanings indicated below and R 11 represents a divalent alkylene radical, linear or branched, having from 1 to 12 carbon atoms, l one of the valid bonds (that of R 11 ) being connected to the atom of -NR 10 -, the other (that of R 12 ) being connected to a silicon atom;
- the radicals R 13 are identical or different, chosen from linear or branched alkyl radicals having 1 to 3 carbon atoms and the phenyl radical; and the radical R 14 represents a hydrogen radical, the radical R 13 or the atom O * ;
- R ' 4 is selected from the group consisting of:
- n represents a number from 2 to 20
- p represents a number from 2 to 20;
- R 12 represents -O- or -N (R 12 ) -, with R 12 being a radical selected from a hydrogen atom, a linear or branched alkyl radical having 1 to 6 carbon atoms;
- R 5 and R 6 have the same meanings as those given about the formula (I);
- the polyorganosiloxane (C) according to the invention are compounds of the following general formula (IX):
- p represents a number greater than or equal to 0 and preferably between 1 and 2000;
- r represents a number greater than or equal to 0 and preferably between 1 and 2000;
- q represents a number greater than or equal to 1, preferably between 1 and 50;
- R 10 represents a linear or branched alkyl radical having 1 to 18 carbon atoms
- the sum p + r is between 1 and 800.
- the functional group V is a propyloxytetramethylpiperidine radical of formula (X) below:
- composition E comprises:
- At least one polyorganosiloxane (A) according to the invention and as defined above
- surfactant (G) will be readily determined by those skilled in the art, the objective being to prepare a stable emulsion.
- the anionic, cationic, nonionic and zwitterionic surfactants can be used alone or as a mixture.
- composition E according to the invention may also comprise protective colloids such as polyvinyl alcohol.
- protective colloids such as polyvinyl alcohol.
- anionic surfactant mention may be made of the following surfactants:
- R a represents a C 8 -C 2 o alkyl radical, preferably C 1 -C 16 radical, R b a C 1 -C alkyl radical; -C6, preferably C 1 -C 3 and M an alkaline cation (sodium, potassium, lithium), substituted or unsubstituted ammonium (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium) or derived from an alkanolamine (monoethanolamine , diethanolamine, triethanolamine),
- R c represents a C 1 -C 24, preferably C 12 -C 20 , alkyl or hydroxyalkyl radical
- M representing a hydrogen atom or a cation of the same definition as above, as well as their ethoxylenated (EO) and / or propoxylenated (PO) derivatives, preferably having from 1 to 20 EO units
- the alkylamide sulphates of formula R d CONHR e OSO 3 M where R d represents a C2-C22 alkyl radical, preferably a C6-C20 alkyl radical, R e represents a C2-C3 alkyl radical, M represents a hydrogen atom or a cation having the same definition as above, as well as their ethoxylenated (EO) and / or propoxylenated (PO) derivatives, preferably having 1 to 20 EO units,
- alkylbenzenesulfonates C9-C20 having preferably 1 to 20 EO units, C 9 -C 20 alkylbenzenesulfonates, C 8 -C 2 primary or secondary alkylsulfonates, alkylglycerol sulfonates, sulfonated polycarboxylic acids described in GB-A-1 082 179, paraffin sulfonates , N-acyl N-alkyltaurates, mono- and dialkylphosphates, alkylisethionates, alkylsuccinamates, alkylsulfosuccinates, sulfosuccinates monoesters or diesters, N-acyl sarcosinates, alkylglycoside
- nonionic surfactants mention may be made of alkyl or aryl ethers of polyalkylene oxide, polyoxyethylene sorbitan hexastearate, polyoxyethylenated sorbitan oleate and cetylstearyl ethers and polyethylene oxide ethers. ).
- polyalkylene ether aryl ether mention may be made of polyoxyethylenated alkylphenols.
- alkyl ether of polyalkylene oxide mention may be made of polyethylene glycol isodecyl ether and polyethylene glycol trimethylnonyl ether containing from 3 to 15 ethylene oxide units per molecule.
- a surfactant of ionic, nonionic or amphoteric fluorinated surfactants and mixtures thereof, for example:
- fluorinated surfactant is meant, as is well known per se, a compound formed of an aliphatic perfluorocarbon moiety, comprising at least three carbon atoms, and a hydrophilic, ionic, nonionic or amphoteric moiety.
- the perfluorocarbon portion of at least three carbon atoms may represent either all or only a fraction of the fluorocarbon portion of the molecule.
- surfactants include, in particular, anionic perfluoroalkyl compounds, cationic, nonionic and amphoteric surfactants, and among them, particularly, the surfactants of the class of ZONYL ® marketed by Du Pont, marketed by Du under the respective bridge ZONYL ® FSA, ZONYL ® FSO, ZONYL ® FSC and ZONYL ® FSK.
- ZONYL ® FSN CAS 65545-80-4, 99-100%, the remainder being sodium acetate and 1,4-dioxane
- ZONYL ® FS-300 CAS 65545-80-4, 40%, the remainder being 1,4-dioxane ( ⁇ 0.1%) and water
- ZONYL ® FSD CAS 70983-60-7 30%, (cationic), the remainder being hexylene glycol (10%), sodium chloride (3%) and water (57%).
- perfluoroalkyl betaines such as that marketed by DU PONT under the name Forafac ® 1157
- ethoxylated polyfluoroamides nonionic
- DU PONT ethoxylated polyfluorocarbon
- FORAFAC 1179 polyfluoroalkyl salts ammonium (cationic), such as that marketed by DU PONT under the name FORAFAC 1179;
- hydrophilic part contains one or more saccharide unit (s) containing from 5 to 6 carbon atoms (units derived from sugars such as fructose, glucose, mannose, galactose, talose, gulose, allose, altose, idose, arabinose, xylose, lyxose and / or ribose) and whose hydrophobic part contains a unit of formula R F (CH 2 ) n , where n can from 2 to 20, preferably from 2 to 10, and R F represents a perfluoroalkyl unit of formula C m F2m + i with m possibly ranging from 1 to 10, preferably from 4 to 8, chosen from those having the characteristics defined herein.
- saccharide unit containing from 5 to 6 carbon atoms (units derived from sugars such as fructose, glucose, mannose, galactose, talose, gulose, allose, altose, idose, arabinose,
- perfluoroalkylated fatty acid monoesters and sugars such as sucrose
- the monoester function being represented by the formula R F (CH 2) n C (O), where n can range from 2 to 10 and R F represents a perfluoroalkyl unit of formula CmF2m + i with m being able to range from 4 to 8, described in JAOCS, Vol. 69, no. 1 (January 1992) and selected from those having the characteristics defined above;
- Polyelectrolytes having perfluoroalkyl fatty side groups such as polyacrylates having R F (CH 2 ) n groups where n can range from 2 to 20, preferably from 2 to 10 and R F represents a perfluoroalkyl unit of formula C m F 2 m + i with m being able to range from 1 to 10, preferably from 4 to 8, chosen from those presenting the characteristics defined above; polyacrylates having CH 2 C 7 F 5 groups described in J. Chim. Phys. (1996) 93, 887-898 and selected from those having the characteristics defined above. reference, the composition E comprises:
- At least one polyorganosiloxane (A) which is an organosilicon resin carrying at least two condensable hydroxyl or alkoxyl groups and comprising at least two different types of siloxyl units chosen from those of formula M, D, T and Q with:
- said resin having a weight content in hydroxyl or alkoxy substituents of between 0.1 and 10% by weight relative to the weight of the resin, and preferably a weight content of hydroxyl or alkoxy substituents of between 0.2 and 5% by weight relative to the weight of the resin
- At least one catalyst (E) of the condensation or dehydrogenation condensation reaction such as a tin salt, a guanidine derivative, an iron derivative, or a metal salt or complex of zinc; water (F),
- catalyst (E) As catalyst (E) according to the invention, mention may be made of catalysts derived from tin, iron, zinc, titanium or an optionally silylated guanidine.
- tin-derived condensation catalyst tin monocarboxylates and dicarboxylates such as tin ethyl-2-hexanoate, dibutyltin dilaurate, dibutyltin diacetate can be used (see NOLL's book “Chemistry”). and technology of silicone ", page 337, Academy Press, 1968-2th edition or EP-147323 or EP235049).
- radicals R 1 which may be identical or different, represent, independently of each other, a linear or branched monovalent alkyl group, a cycloalkyl group or a (cycloalkyl) alkyl group, the ring being substituted or unsubstituted and which may comprise at least one minus one heteroatom or one fluoroalkyl group,
- the radical R 2 represents a hydrogen atom, a linear or branched monovalent alkyl group, a cycloalkyl group, a substituted or unsubstituted ring-substituted alkyl group and may comprise at least one heteroatom, an aromatic group or an arylalkyl group, a fluoroalkyl group, an alkylamine or alkylguanidine group, and
- the radical R 3 represents a linear or branched monovalent alkyl group, a cycloalkyl group, a substituted or unsubstituted ring-substituted alkyl group and may comprise at least one heteroatom, an arylalkyl, fluoroalkyl, alkylamine or alkylguanidine group, when the radical R 2 is not a hydrogen atom, the radicals R 2 and R 3 may be bonded to form a 3-, 4-, 5-, 6- or 7-membered aliphatic ring optionally substituted by one or more substituents.
- catalyst (E) useful according to the invention, mention may be made of the family of guanidines of formula:
- the ring being substituted or unsubstituted and may comprise at least one heteroatom or a fluoroalkyl group, an aromatic group an arylalkyl group, a fluoroalkyl group, an alkylamine or alkylguanidine group, and
- radicals R 1 , R 2 , R 3 or R 4 may be linked in pairs so as to form a 3-, 4-, 5-, 6- or 7-membered aliphatic ring optionally substituted with one or more substituents.
- They are pentasubstituted guanidines and have the advantage of being liquid, colorless, odorless and soluble in silicone matrices.
- the catalyst (E) is a metal complex or salt of zinc of formula:
- L 1 represents a ligand which is a ⁇ -dicarbonylato anion or the enolate anion of a ⁇ -dicarbonyl compound or an acetylacetato anion derived from a ⁇ -ketoester, and
- L 2 represents an anionic ligand different from L 1 .
- the catalyst (E) may be selected from the following compounds:
- This catalyst has the advantage of being liquid at ambient temperature (25 ° C.) and soluble in organic solvents, even in alkanes, and in silicone oils.
- the tanning agent T is a mineral agent, preferably a chromium salt.
- chromium chloride or sulphate can be used which, under acidic conditions, penetrates into the structure of the leather.
- the chromium salts form a complex with carboxylic groups of the proteins of the skin to be treated during the subsequent basification step.
- chromium treatment is preferred over vegetable extracts because it gives better chemical and physical properties and, in addition, it improves the resistance to thermal hydrolysis and microorganisms. organizations.
- the composition (E) When the composition (E) is in the form of an emulsion, it may be prepared conventionally using standard methods of the state of the art. Emulsification can be direct or by inversion.
- direct emulsification the process consists of emulsifying in an aqueous phase containing a surfactant and the constituents of the composition (E). An oil-in-water emulsion is obtained directly. Then the missing constituents can be added, either directly to the emulsion (case of water-soluble constituents), or later in the form of emulsion (case of constituents insoluble in the aqueous phase).
- the particle size of the emulsion obtained above can be adjusted by conventional methods known to those skilled in the art, in particular by continuing the stirring in the reactor for a suitable period.
- the preparation of the composition (E) is carried out at room temperature.
- the temperature rise that can result from the grinding or stirring steps is limited.
- Another object of the invention is a method of preparing a leather comprising a step of tanning, retanning or tanning and retannage, according to the invention and as described above.
- the skin to be treated is subjected to a neutralization step.
- the purpose of the neutralization is to give the skins an appropriate pH before they are subjected to retanning, drying and bathing (lubrication) operations, during which chromium is cross-linked with carboxylic groups present in the skin. Collagen of the skin to treat. This tanned skin is known in the art under
- the leather is subjected to the standard retannage step or according to the invention.
- This retannage step allows:
- the dyeing step which aims to produce uniform colors over the entire surface of each skin (the typical dyes are aqueous acid dyes),
- oils used are in general oils of animal or vegetable origin, or synthetic oils based on mineral oil, and
- the drying step which aims to dry the leather while optimizing the quality and the surface yield.
- the process according to the invention makes it possible to confer on the leather better properties, namely a clean staining tone, satisfactory dye penetration, grain lubrication, softness, flexibility, extensibility, flexibility and robustness.
- Another advantage of the invention is to prevent a significant depletion of the tanning agent from the treated leather, that is to say that the amount of the tanning agent (in particular chromium) passing into the effluent is greatly reduced, thereby mitigating the problem of process effluent pollution.
- Another subject of the invention consists of skins characterized in that they have been tanned or retanned by a process according to the invention and as described above.
- one of the last subject of the invention consists of a leather characterized in that it has been prepared according to the method of the invention as described above.
- the following examples which illustrate the invention demonstrate the excellent lubricating properties of the compositions of the invention.
- the emulsions are prepared as follows: In an IKA ® reactor, a portion of the water, a nonionic surfactant are mixed. Then, the mixture (s) to be emulsified with stirring is added to this mixture so as to obtain an oil-in-water emulsion; and
- the components are added in the form of emulsions which are prepared according to the procedure described above.
- Emulsion 1 (amino silicone): consisting of 51% by weight of a Bluesil ® 21648 amino silicone oil (sold by Bluestar Silicones).
- Emulsion 2 consisting of 50% by weight of a copolymer with (dimethyl) (hydrogenomethyl) polysiloxane units with hydrogenodimethyl ends,
- Emulsion 4 consisting of 57% by weight of a mixture comprising a silicone resin MDT 0H , silane Silquest ® VS142 (marketed by Momentive Performance Materials) and an emulsion of a catalyst (dioctyltin dilaurate).
- Composition (E1) mixture of 25 parts by weight of Emulsion 1 + 15 parts by weight of Emulsion 2 + 5 parts by weight of Emulsion 3.
- Composition (E2) mixture of 35 parts by weight of Emulsion 4 + 15 parts by weight of Emulsion 2 + 5 parts by weight of Emulsion 3
- Composition (E3) mixture of 20 parts by weight of Emulsion 3 + 10 parts by weight of Emulsion 4.
- composition according to the invention [(E1), (E2) or (E3)] and a comparative test carried out without addition of the composition according to the invention.
- the composition according to the invention (in various amounts by weight) is added just before, simultaneously or just after the addition of the tanning agent.
- the operating conditions are those of a conventional tanning step. Then the skins follow the classic steps of a leather treatment. 4) Retannaqe process according to the invention:
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Abstract
The invention relates to a method for tanning or retanning rawhide, rawhide scraps, or an untanned article containing collagen using a crosslinkable silicone composition.
Description
Procédé de tannage ou de retannage de peaux brutes, de déchets de peaux brutes ou d'un article non tanné contenant du collagène. A process for tanning or retanning raw hides, raw hides waste or a non-tanned article containing collagen.
L'invention concerne un procédé de tannage ou de retannage de peaux brutes, de déchets de peaux brutes ou d'un article non tanné contenant du collagène. The invention relates to a process for tanning or retanning raw hides, raw hides waste or a non-tanned article containing collagen.
La présente invention se situe dans le domaine de la transformation des peaux brutes en cuir. The present invention is in the field of processing raw leather skins.
Ainsi, à l'abatage, la peau d'un animal présente une grande souplesse. Cependant, au stockage la peau perd rapidemment cette propriété, et surtout ses qualités mécaniques. C'est pour cette raison que lors de la préparation de cuirs à partir de peaux brutes, il est d'usage courant de soumettre les peaux brutes à plusieurs traitements physiques et chimiques afin de conférer les propriétés physiques et chimiques requises au cuir et le rendre ainsi approprié pour diverses applications telles que la maroquinerie, la sellerie,... Thus, at the slaughter, the skin of an animal has a great flexibility. However, in storage the skin quickly loses this property, and especially its mechanical qualities. It is for this reason that when preparing raw hides skins, it is common practice to subject raw hides to several physical and chemical treatments in order to impart the necessary physical and chemical properties to the leather and to make it thus suitable for various applications such as leather goods, upholstery, ...
Les procédés mis en oeuvre dans les tanneries comprennent les étapes suivantes: The processes implemented in tanneries comprise the following steps:
le « travail en rivière » qui est une phase de nettoyage de la peau en milieu aqueux et/ou via des moyens mécaniques de manière à éliminer les sels de conservation, les poils, la chair, les graisses, la kératine, les protéines solubles et les souillures superficielles. Les peaux sont lavées, pelannées, écharnées et épilées si nécessaire et sont dénommées "river work" which is a phase of cleaning the skin in an aqueous medium and / or by mechanical means so as to eliminate the preserving salts, the hair, the flesh, the fats, the keratin, the soluble proteins and superficial stains. The skins are washed, pelannée, écharnées and épilées if necessary and are denominated
« peaux en tripe », "Skins in tripe",
le « picklage » qui par un traitement acide a pour objectif de réduire le pH des peaux de manière à améliorer la conservation des peaux, the "picklage" which by an acid treatment aims to reduce the pH of the skins so as to improve the conservation of the skins,
le « tannage » dans lequel les fibres de collagène sont stabilisées grâce aux agents de tannage de telle sorte que la peau devient imputrescible, le « corroyage » qui comporte les opérations suivantes: une neutralisation et un lavage, suivis d'un retannage, d'un séchage et d'une nourriture en bain, qui sont la plupart du temps menés dans une seule cuve de traitement. A ce stade, le cuir est appelé « cuir en croûte », et
le « finissage » qui comprend plusieurs traitements mécaniques, ainsi que l'application d'une couche de surface pour améliorer l'apparence et le toucher du cuir. L'étape de tannage est considérée comme étant la plus importante dans la chaîne de transformation des peaux brutes qui après stockage sont raides et putrescibles et sont ainsi transformées en une matière souple et imputrescible qu'est le cuir. Les systèmes de tannage les plus utilisés sont: le tannage minéral, qui utilise des sels de chrome trivalent, le tannage végétal basé sur le pouvoir tannant des extraits végétaux du bois ou de l'écorce de certains arbres et le tannage réalisé via des produits synthétiques. Les procédés de tannage minéral existant sont mis en œuvre en milieu aqueux. Le tannage au chlorure de chrome ou au sulfate de chrome est le plus répandu. Les tannages par le chrome sont le plus souvent précédés par un traitement acide dans une étape connue sous le nom de « picklage ». Le picklage permet de conserver la peau en tripes et de diminuer la réactivité des sites réactionnels, vis-à-vis du chrome, afin de ne pas gêner sa diffusion dans le collagène. En effet, dans l'étape de tannage, le chrome trivalent s'insère entre les fibres de collagène et les réticule en formant des complexes avec les sites anioniques des chaînes polypeptidiques. Le tannage par les sels de chrome conduit à un cuir possédant d'excellentes caractéristiques physicochimiques, notamment souplesse, résistance à la déchirure et grande résistance thermique. Cependant, il se révèle nocifs à l'environnement en raison de l'utilisation de métaux difficilement recyclables ou éliminables comme le chrome. Ainsi, les bains de tannage ne sont jamais totalement épuisés en chrome, ce qui conduit à des rejets de bains contenant des quantités notables de chrome (de l'ordre de 25 à 30 % par rapport aux quantités introduites). Or, le chrome est un agent polluant toxique et les rejets doivent réglementairement subir des traitements d'élimination du chrome qui sont très onéreux et n'autorisent pas une récupération
directe du chrome. De plus, on observe au cours des opérations de finition qui suivent le tannage des peaux (en particulier au cours des opérations de teinture) des relargages de chrome qui polluent les bains et nécessitent des traitements d'élimination comme pour les bains de tannage. En outre, l'utilisation de métaux tels que le chrome engendre parfois, en raison de l'action allergisante de ces derniers, des réactions cutanées chez l'utilisateur. Il est à noter qu'étant donné qu'une quantité limitée de chrome est fixée sur la peau à traiter lors d'un simple tannage, celle-ci peut subir une nouvelle étape de tannage avec des sels de chrome de telle sorte qu'une plus grande quantité de chrome puisse être fixée par la peau ainsi traitée. Cette étape de retannage a pour but d'assurer une meilleure pénétration des colorants, d'améliorer le toucher général, l'épaisseur, la robustesse, la résistance aux produits chimiques et la résistance à la chaleur. the "tanning" in which the collagen fibers are stabilized by the tanning agents so that the skin becomes rot-proof, the "wrought" which comprises the following operations: a neutralization and a washing, followed by a retannage, of drying and bathing food, which are mostly carried out in a single treatment tank. At this stage, the leather is called "leather in crust", and the "finishing" which includes several mechanical treatments, as well as the application of a surface layer to improve the appearance and feel of the leather. The tanning step is considered to be the most important in the processing chain of raw hides, which after storage are stiff and putrescible and are thus transformed into a soft and rotproof material that is leather. The most widely used tanning systems are: mineral tanning, which uses trivalent chromium salts, vegetable tanning based on the tanning power of plant extracts of wood or bark from certain trees and tanning achieved via synthetic products . The existing mineral tanning processes are carried out in an aqueous medium. Tanning with chromium chloride or chromium sulphate is the most common. Chromium tanning is most often preceded by acid treatment in a stage known as "picklage". The picklage makes it possible to preserve the skin in guts and to reduce the reactivity of the reaction sites, with respect to the chromium, so as not to hinder its diffusion in the collagen. Indeed, in the tanning step, the trivalent chromium is inserted between the collagen fibers and the reticles by forming complexes with the anionic sites of the polypeptide chains. Tanning with chromium salts leads to leather having excellent physicochemical characteristics, including flexibility, tear resistance and high thermal resistance. However, it is harmful to the environment because of the use of metals that are difficult to recycle or eliminate, such as chromium. Thus, the tanning baths are never completely depleted of chromium, which leads to rejects of bath containing significant amounts of chromium (of the order of 25 to 30% compared to the amounts introduced). However, chromium is a toxic pollutant and releases are legally required to undergo chromium removal treatments which are very expensive and do not allow recovery direct chromium. In addition, during the finishing operations that follow the tanning of the skins (especially during the dyeing operations), it is observed that releases of chromium pollute the baths and require disposal treatments as for the tanning baths. In addition, the use of metals such as chromium sometimes causes, because of the allergenic action of the latter, cutaneous reactions in the user. It should be noted that since a limited amount of chromium is fixed on the skin to be treated during a simple tanning, it can undergo a new step of tanning with chromium salts so that more chromium can be fixed by the skin thus treated. This retannage step is intended to provide better dye penetration, improved overall feel, thickness, toughness, chemical resistance and heat resistance.
Une approche alternative a consisté à utiliser des procédés en milieu organique pour réduire les rejets de chrome des bains. Par exemple, le brevet US 4.039.281 décrit un procédé de tannage consistant à préparer un bain de tannage au moyen d'un solvant organique non miscible à l'eau dans lequel sont introduits successivement un agent de tannage minéral et un agent de tannage synthétique. Les peaux sont essorées par centrifugation pour ramener leur taux d'hydratation à une valeur très faible, puis le solvant organique est éliminé pour procéder aux étapes suivantes que sont la nourriture du cuir afin de l'assouplir, la teinture... An alternative approach has been to use organic processes to reduce chromium emissions from baths. For example, US Pat. No. 4,039,281 describes a tanning process consisting of preparing a tanning bath using a water-immiscible organic solvent in which are successively introduced a mineral tanning agent and a synthetic tanning agent. . The skins are wiped by centrifugation to reduce their hydration rate to a very low value, then the organic solvent is removed to proceed to the following steps that are the food of the leather to soften, the dye ...
Toutefois, ces procédés ont beaucoup de mal à se développer car, d'une part, ils exigent des modifications importantes des installations existantes et d'autre part, ils sont soumis aux contraintes qui pèsent sur l'utilisation des solvants organiques. Ces procédés qui effectivement réduisent les rejets de chrome, ne constituent donc pas à l'heure actuelle des solutions satisfaisantes au problème des rejets de chrome des industries du tannage. Ainsi, les procédés connus de tannage au chrome sont caractérisés par un degré d'épuisement assez faible, car 25 à 30 % du chrome introduit est perdu avec l'eau rejetée.
Il est donc souhaitable que le rendement et l'efficacité de l'agent de tannage, en particulier l'agent de tannage minéral tel que le chrome, soient maintenus à des valeurs aussi élevées que possible, que ce soit pour obtenir un (re) tannage à haut rendement ou pour diminuer autant que possible la teneur résiduelle en agent de tannage de l'eau de sous-bac. Dans le retraitement du cuir avec des agents graissants, il est aussi souhaitable d'améliorer le rendement et l'efficacité du traitement. However, these processes are very difficult to develop because, firstly, they require significant modifications of existing facilities and secondly, they are subject to constraints on the use of organic solvents. These processes, which effectively reduce chromium discharges, are therefore not at the present time satisfactory solutions to the chromium release problem of the tanning industries. Thus, the known chrome tanning processes are characterized by a fairly low degree of exhaustion, since 25 to 30% of the chromium introduced is lost with the rejected water. It is therefore desirable that the efficiency and effectiveness of the tanning agent, in particular the mineral tanning agent such as chromium, be kept as high as possible, whether to obtain a (re) high efficiency tanning or to reduce as much as possible the residual content of tanning agent in the sub-tank water. In the treatment of leather with greasers, it is also desirable to improve the efficiency and effectiveness of the treatment.
On a maintenant découvert que si l'on utilise dans les étapes de tannage et/ou de retannage des émulsions ou des dispersions réactives de silicone, on peut atteindre ces buts à un degré étonnamment élevé. It has now been found that if one uses in the tanning and / or retanning steps of reactive emulsions or silicone dispersions, these goals can be achieved to a surprisingly high degree.
Par conséquent, un des objets principaux de la présente invention est de proposer un procédé de tannage ou de retannage de peaux brutes, de déchets de peaux brutes ou d'un article non tanné contenant du collagène qui permet d'améliorer l'épuisement des agents de tannage ou de retannage et d'améliorer la fixation des matières tannantes dans le cuir ce qui permet de diminuer la quantité d'agent tannant utilisée et la quantité de polluants rejetés dans les effluents issus de tanneries. Therefore, one of the main objects of the present invention is to provide a process for tanning or retanning raw hides, raw hides waste or a non-tanned article containing collagen which improves the exhaustion of the agents. tanning or retanning and improve the fixing of tanning materials in the leather which reduces the amount of tanning agent used and the amount of pollutants released into the effluents from tanneries.
Un autre objet de la présente invention est de proposer un procédé de tannage ou de retannage de peaux brutes, de déchets de peaux brutes ou d'un article non tanné contenant du collagène qui permet de produire des cuirs tannés, en particulier des cuirs tannés au chrome dont la qualité du point de vue de leurs caractéristiques physico-chimiques (toucher doux, résistance aux produits chimiques et résistance à la chaleur) est au moins égale, voire supérieure à celle des cuirs tannés par les procédés traditionnels. Another object of the present invention is to propose a process for tanning or retanning raw skins, raw hide waste or a non-tanned article containing collagen which makes it possible to produce tanned leathers, in particular tanned leathers. chromium whose quality in terms of their physicochemical characteristics (soft touch, chemical resistance and heat resistance) is at least equal to or greater than that of leather tanned by traditional methods.
Un autre objet de la présente invention est de proposer un procédé de préparation de cuir comprenant l'étape de tannage ou de retannage selon l'invention. Another object of the present invention is to provide a process for preparing leather comprising the tanning or retannage step according to the invention.
Un dernier objet de la présente invention est de proposer de nouveaux cuirs tannés, en particulier au chrome, préparés selon le procédé de l'invention et ayant
de meilleures propriétés physico-chimiques, à savoir un ton de coloration net, une pénétration satisfaisante des colorants, une lubrification du grain, une douceur, une souplesse, une extensibilité, une flexibilité et une robustesse. Ces objectifs, parmi d'autres, sont atteints par la présente invention qui concerne un Procédé de tannage ou de retannage caractérisé en ce qu'une peau brute, un déchet de peau brute ou un article non tanné contenant du collagène est mis en contact en phase aqeuse comprenant : A final object of the present invention is to provide novel tanned leathers, in particular chromium, prepared according to the method of the invention and having better physicochemical properties, namely a clean staining tone, satisfactory dye penetration, grain lubrication, softness, flexibility, extensibility, flexibility and robustness. These objectives, among others, are achieved by the present invention which relates to a tanning or retanning process characterized in that a raw skin, a raw hide waste or a non-tanned article containing collagen is brought into contact with each other. aqueous phase comprising:
au moins un agent tannant T qui est un agent minéral, et - au moins une composition silicone E qui est susceptible de former un élastomère silicone soit à température ambiante, soit par élévation de température, et de préférence la composition silicone E se présente sous la forme d'une émulsion silicone dans eau ou sous la forme d'une dispersion aqueuse de silicone, et at least one tanning agent T which is a mineral agent, and - at least one silicone composition E which is capable of forming a silicone elastomer either at ambient temperature or by raising the temperature, and preferably the silicone composition E is under the form of a silicone emulsion in water or in the form of an aqueous silicone dispersion, and
caractérisé en ce que les composants de la composition E sont choisis de manière à ce que ladite composition puisse former un élastomère silicone par des réactions de condensation, d'hydrosilylation ou de déshydrogénocondensation soit à température ambiante, soit par élévation de température . Pour atteindre cet objectif, parmi d'autres, les inventeurs ont eu le mérite de mettre à jour de manière tout à fait surprenante et inattendue que l'association dans une étape de tannage ou de retannage d'un agent tannant et d'une composition susceptible de former un élastomère silicone soit à température ambiante, soit par élévation de température, permet d'améliorer l'épuisement des agents de tannage ou de retannage et d'améliorer la fixation des matières tannantes dans le cuir ce qui permet de diminuer la quantité d'agent tannant utilisée et la quantité de polluants rejetés dans les effluents issus de tanneries. Il est important de comprendre que lors de la formation d'un élastomère silicone, la composition silicone passe d'un état liquide (ou visqueux) avant la réticulation (c'est-à-dire que les composants n'ont pas encore réagit entre eux) à un état solide (ou élastomère) qui se traduit par un durcissement physique de la composition silicone (les composants réactifs ont réagi entre-eux). Pour se faire soit un catalyseur est mélangé aux autres espèces réactives silicones juste avant l'emploi induisant ainsi le démarrage de la réaction de
réticulation, soit l'eau est éliminée (par séchage) permettant ainsi aux espèces réactives silicones qui sont présents dans « les goutelletes » de l'émulsion ou de la dispersion de rentrer en contact les uns avec les autres de manière à pouvoir lancer la réaction de réticulation. Ainsi, au sein de la composition silicone se forme un réseau silicone par des réactions de condensation, d'hydrosilylation ou de déshydrogénocondensation suivant les composants silicones réactifs utilisés dans la composition silicone E. characterized in that the components of the composition E are chosen so that said composition can form a silicone elastomer by condensation, hydrosilylation or dehydrogenation condensation reactions at either ambient temperature or by temperature rise. To achieve this goal, among others, the inventors have had the merit of surprisingly and unexpectedly updating the association in a step of tanning or retanning a tanning agent and a composition capable of forming a silicone elastomer either at ambient temperature or by raising the temperature, makes it possible to improve the exhaustion of the tanning or retanning agents and to improve the fixing of the tanning materials in the leather, which makes it possible to reduce the quantity of tanning agent used and the quantity of pollutants released into the effluents from tanneries. It is important to understand that during the formation of a silicone elastomer, the silicone composition changes from a liquid (or viscous) state before crosslinking (i.e. the components have not yet reacted between they) to a solid state (or elastomer) which results in a physical hardening of the silicone composition (the reactive components reacted with each other). To be done either a catalyst is mixed with other reactive silicone species just before use thus inducing the start of the reaction of crosslinking, ie the water is removed (by drying) thus allowing the reactive silicone species that are present in the "goutellets" of the emulsion or dispersion to come into contact with each other so as to be able to initiate the reaction crosslinking. Thus, within the silicone composition a silicone network is formed by condensation, hydrosilylation or dehydrogenation reactions according to the reactive silicone components used in the silicone composition E.
De plus, la composition silicone E présente l'avantage de se présenter sous la forme d'une émulsion huile silicone dans eau ou d'une dispersion aqueuse de silicone évitant ainsi les problèmes inhérents à l'utilisation de tannage en phase solvant organique. In addition, the silicone composition E has the advantage of being in the form of a silicone oil in water emulsion or of an aqueous silicone dispersion thus avoiding the problems inherent in the use of organic solvent phase tanning.
Un tel accroissement de la fixation de l'agent tannant, en particulier du chrome, ou une réduction de son épuisement constitue un important avantage en ce sens que les propriétés relatives au toucher, à l'épaisseur, à la robustesse, à la résistance aux produits chimiques et à la chaleur, à la richesse et à l'absorption des colorants sont aussi améliorées. Les composants de la composition silicone E sont définis en référence à leur structure chimique initiale, c'est-à-dire celle qui les caractérise avant la formation de l'émulsion huile silicone dans eau ou de la dispersion aqueuse de silicone. Dès lors qu'ils sont en milieu aqueux, leur structure est susceptible d'être modifiée suite aux réactions d'hydrolyse et de condensation. Such an increase in the fixing of the tanning agent, in particular chromium, or a reduction in its exhaustion is an important advantage in that the properties relating to the touch, to the thickness, to the strength, to the resistance to chemicals and the heat, richness and absorption of dyes are also improved. The components of the silicone composition E are defined with reference to their initial chemical structure, that is to say the one which characterizes them before the formation of the silicone oil in water emulsion or the aqueous silicone dispersion. Since they are in an aqueous medium, their structure is likely to be modified following the hydrolysis and condensation reactions.
Les émulsions huile silicone dans eau peuvent être préparés comme suit : The silicone oil emulsions in water can be prepared as follows:
dans un réacteur tel qu'un réacteur IKA, une partie de l'eau et d'un tensioactif sont mélangés, in a reactor such as an IKA reactor, part of the water and a surfactant are mixed,
puis sont ajoutés les composants, cette incorporation étant réalisée sous agitation de manière à obtenir une émulsion huile dans eau , et en fin d'introduction et après homogénéisation, on procède à la dilution finale de l'émulsion et à l'ajout éventuel d'additifs.
Selon un autre variante, un ou plusieurs composant(s) de la composition silicone E peut (peuvent) se présenter sous la forme d'une émulsion huile dans eau avant leur addition. On procédera alors à un simple mélange des émulsions, éventuellement en milieu aqueux, de manière à contrôler la dilution finale de la composition silicone E. the components are then added, this incorporation being carried out with stirring so as to obtain an oil-in-water emulsion, and at the end of introduction and after homogenization, the final dilution of the emulsion and the optional addition of the emulsion are carried out. additives. According to another variant, one or more component (s) of the silicone composition E may be in the form of an oil-in-water emulsion before their addition. The emulsions will then be simply mixed, optionally in an aqueous medium, so as to control the final dilution of the silicone composition E.
De préférence, la composition silicone E comprend en outre au moins un polyorganosiloxane (A) ayant des motifs siloxyles identiques ou différents de formule générale (I) : Preferably, the silicone composition E further comprises at least one polyorganosiloxane (A) having identical or different siloxyl units of general formula (I):
Rn a FT Si 04 -(a+b)/2 (I) R n a FT Si 0 4 - (a + b) / 2 (I)
dans laquelle: in which:
a = 0, 1 , 2 ou 3 ; b = 0, 1 , 2 ou 3 ; et a+b <3, les symboles R1 et R2 sont identiques ou différents et représentent chacun un radical monovalent choisi parmi le groupe constitué par un alkyle ayant de 1 à 40 atomes de carbone, de préférence un alkyle ayant de 1 à 6 atomes de carbone; un cycloalkyle ayant de 3 à 8 atomes de carbone; un aryle, un alkylarylène, un arylalkylène, un groupe -OR3 avec R3= H ou un radical alkyle ayant de 1 à 40 atomes de carbone, et avec la condition que pour au moins deux motifs siloxyles. R1 ou R2 est un radical hvdroxyle -OH ou alcoxy -OR2 avec R2 étant un alkyle avant de 1 à 6 atomes de carbone. a = 0, 1, 2 or 3; b = 0, 1, 2 or 3; and a + b <3, the symbols R 1 and R 2 are identical or different and each represents a monovalent radical chosen from the group consisting of an alkyl having from 1 to 40 carbon atoms, preferably an alkyl having from 1 to 6 carbon atoms; cycloalkyl having 3 to 8 carbon atoms; an aryl, an alkylarylene, an arylalkylene, a group -OR 3 with R 3 = H or an alkyl radical having 1 to 40 carbon atoms, and with the proviso that for at least two siloxyl units. R 1 or R 2 is a hydroxyl radical -OH or alkoxy -OR 2 with R 2 being a front alkyl of 1 to 6 carbon atoms.
Il est important de noter que la présence d'au moins deux fonction réactives de type hydroxy ou alcoxy, permet une réticulation par condensation de manière à former un réseau résultant au durcissement de la composition silicone de manière à former un élastomère. It is important to note that the presence of at least two hydroxy or alkoxy reactive functional groups allows condensation curing so as to form a network resulting in curing the silicone composition to form an elastomer.
A titre de constituant préféré, le polyorganosiloxane (A) comprend les motifs loxyles suivants : As a preferred component, the polyorganosiloxane (A) comprises the following loxyl units:
M = [(OH)(R2)2Si01/2] et M = [(OH) (R 2 ) 2 SiO 1/2 ] and
D= [R3R Si02/2] D = [R 3 R Si0 2/2 ]
formules dans lesquelles:
- R2, R3 et R4 sont des radicaux, identiques ou différents, choisis parmi le groupe constitué par : les radicaux alkyles linéaires ou ramifiés en C1-C6 (tels que par exemple méthyle, éthyle, propyle, isopropyle, butyle, isobutyle, t-butyle, n-pentyle, n-hexyle), les radicaux cycloalkyles en C3-C8 (tels que par exemple cyclopentyle, cyclohexyle), les radicaux aryles enformulas in which: - R 2 , R 3 and R 4 are radicals, identical or different, selected from the group consisting of: linear or branched C1-C6 alkyl radicals (such as for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl); t-butyl, n-pentyl, n-hexyl), C 3 -C 8 cycloalkyl radicals (such as, for example, cyclopentyl, cyclohexyl), aryl radicals,
C6-C10 (tels que par exemple phényle, naphtyle) et les radicaux alkylarylènes en C6-Ci5 (tels que par exemple tolyles, xylyle). C6-C10 (such as eg phenyl, naphthyl) and alkylarylene radicals, C 6 -C 5 (such as for example tolyl, xylyl).
Le polyorganosiloxane (A) peut-être une huile polydiorganosiloxane linéaire présentant au moins deux groupements silanols SiOH par molécule et présentant une viscosité dynamique à 25° C généralement comprise entre 50mPa.s et 50 x 106 mPa.s. Toutes les viscosités dont il est question dans le présent mémoire correspondent à une grandeur de viscosité dynamique qui est mesurée, de manière connue en soi, à 25°C. The polyorganosiloxane (A) may be a linear polydiorganosiloxane oil having at least two SiOH silanol groups per molecule and having a dynamic viscosity at 25 ° C generally between 50mPa.s and 50x10 6 mPa.s. All the viscosities referred to herein correspond to a dynamic viscosity quantity which is measured, in a manner known per se, at 25.degree.
De préférence, le polyorganosiloxane (A) est réactif par une réaction de condensation ou de déshydrogénocondensation et présente par molécule au moins deux groupements silanol SiOH ou SiOR (avec R= un alkyle ayant de 1 à 6 atomes de carbone) et encore plus préférentiellement le polyorganosiloxane (A) est choisi parmi ceux de formules S1 ou S2 suivantes : Preferably, the polyorganosiloxane (A) is reactive by a condensation or dehydrogenation condensation reaction and has, per molecule, at least two silanol groups SiOH or SiOR (with R = an alkyl having from 1 to 6 carbon atoms) and even more preferentially the polyorganosiloxane (A) is chosen from those of formulas S1 or S2 below:
S1 S1
- avec n est un entier supérieur ou égal 2, R3 et R4, identiques ou différents, représentent: un alkyle ayant de 1 à 6 atomes de carbone; un cycloalkyle ayant de 3 à 8 atomes de carbone; un aryle, un alkylarylène ou un arylalkylène ; et with n being an integer greater than or equal to 2, R 3 and R 4 , which may be identical or different, represent: an alkyl having from 1 to 6 carbon atoms; cycloalkyl having 3 to 8 carbon atoms; aryl, alkylarylene or arylalkylene; and
S2
- avec 1 < f < 1500 et de préférence 10 < f < 500, S2 with 1 <f <1500 and preferably 10 <f <500,
Des exemples de polyorganosiloxane (A) les plus utiles selon l'invention, du fait de leurs disponibilités industrielles, sont ceux pour lesquelles R3 et R4 sont indépendamment choisis parmi le groupe des radicaux constitué par : un méthyle, un éthyle, un propyle, un isopropyle, un cyclohexyle, un phényle, et un 3,3,3- trifluoropropyle. De manière préférée, au moins environ 80 % en nombre de ces radicaux sont des radicaux méthyles. Le polyorganosiloxane (A) peut présenter une viscosité pouvant atteindreExamples of polyorganosiloxane (A) most useful according to the invention, because of their industrial availabilities, are those for which R 3 and R 4 are independently chosen from the group of radicals consisting of: a methyl, an ethyl, a propyl , isopropyl, cyclohexyl, phenyl, and 3,3,3-trifluoropropyl. Preferably, at least about 80% by number of these radicals are methyl radicals. The polyorganosiloxane (A) may have a viscosity that can reach
200 000 mPa.s. Pour des raisons économiques, on choisit un constituant dont la viscosité est généralement de l'ordre de 100 000 à 200 000 mPa.s. Dans le cadre de la présente invention, on préfère plus spécialement les α,ω-bis (hydroxy)polydiméthylsiloxanes. 200,000 mPa.s. For economic reasons, a component is chosen whose viscosity is generally of the order of 100,000 to 200,000 mPa.s. In the context of the present invention, α, ω-bis (hydroxy) polydimethylsiloxanes are more particularly preferred.
Dans le cadre de la présente invention, on peut spécialement utiliser les α,ω-dihydroxypolydiorganosiloxanes préparés par le procédé de polymérisation anionique décrit dans les brevets américains US 2 891 920 et US 3 294 725. In the context of the present invention, it is especially possible to use the α, ω-dihydroxypolydiorganosiloxanes prepared by the anionic polymerization process described in US Pat. Nos. 2,891,920 and 3,294,725.
Le polyorganosiloxane (A) peut aussi être choisi parmi les résines organosiliciques porteuses d'au moins deux groupes hydroxyles ou alcoxyles condensables et comportant au moins deux types de motifs siloxyles différents choisis parmi ceux de formule M, D, T et Q avec : The polyorganosiloxane (A) may also be chosen from organosilicon resins bearing at least two condensable hydroxyl or alkoxyl groups and comprising at least two different types of siloxyl units chosen from those of formula M, D, T and Q with:
- le motif siloxyle M= (R0)3SiOv2 ; the siloxyl unit M = (R 0 ) 3 SiO 2;
- le motif siloxyle D= (R0)2SiO2/2 ; - the siloxyl unit D = (R 0) 2 SiO 2/2;
- le motif siloxyle T= R°Si03/2, et - the siloxyl unit T = R o Si0 3/2, and
- le motif siloxyle Q= Si04/2j et the siloxyl unit Q = Si0 4 / 2j and
- l'un au moins de ces motifs étant un motif T ou Q, at least one of these motifs being a T or Q motif,
- formules dans lesquelles R° représente un groupement monovalent hydrocarboné ayant de 1 à 40 atomes de carbone ou un groupe -OR3 avec R3= H ou un radical alkyle ayant de 1 à 40 atomes de carbone, et ladite résine présentant une teneur pondérale en substituants hydroxyles ou alcoxy comprise entre 0,1 et 10% en poids par rapport au poids de la résine, et de préférence une teneur pondérale en
substituants hydroxyles ou alcoxy comprise entre 0,2 et 5% en poids par rapport au poids de la résine. formulas in which R ° represents a monovalent hydrocarbon group having from 1 to 40 carbon atoms or a group -OR 3 with R 3 = H or an alkyl radical having from 1 to 40 carbon atoms, and said resin having a weight content in hydroxyl or alkoxy substituents of between 0.1 and 10% by weight relative to the weight of the resin, and preferably a weight content of hydroxyl or alkoxy substituents of between 0.2 and 5% by weight relative to the weight of the resin.
Les résines organosiliciques possèdent en générale environ de 0,001 à 1 ,5 groupe OH et/ou alkoxyle par atome de silicium. Ces résines organosiliciques sont généralement préparées par co-hydrolyse et co-condensation de chlorosilanes tels que ceux de formules (R9)3SiCI, (R9)2Si(CI)2, R9Si(CI)3 ou Si(CI)4. Les radicaux R9 sont identiques ou différents et sont généralement choisis parmi les radicaux : alkyles linéaires ou ramifiés en Ci - Ce, phényle et trifluoro-3,3,3 propyle. On peut citer par exemple comme radicaux R9 alkyles, les radicaux méthyle, éthyle, isopropyle, tertiobutyle et n-hexyle. Ces résines sont des oligomères ou polymères organopolysiloxanes ramifiés bien connus et disponibles dans le commerce. Elles présentent, dans leur structure, au moins deux motifs siloxyles différents choisis parmi ceux de formule (R9)3SiOi/2 (motif M), (R9)2Si02/2 (motif D), R9Si03/2 (motif T) et S1O4/2 (motif Q), l'un au moins de ces motifs étant un motif T ou Q. La teneur pondérale en groupes OH et/ou alkoxyle étant généralement comprise entre 0,2 et 10 % en poids. Organosilicon resins generally have from about 0.001 to about 1.5 OH and / or alkoxyl per silicon atom. These organosilicon resins are generally prepared by co-hydrolysis and co-condensation of chlorosilanes such as those of formulas (R 9 ) 3 SiCl, (R 9 ) 2 Si (Cl) 2 , R 9 Si (Cl) 3 or Si (Cl ) 4 . The radicals R 9 are identical or different and are generally chosen from: linear or branched C 1 -C 6 alkyl, phenyl and 3,3,3-trifluoropropyl radicals. Examples of alkyl radicals R 9 are methyl, ethyl, isopropyl, tert-butyl and n-hexyl. These resins are branched organopolysiloxane oligomers or polymers well known and commercially available. They exhibit, in their structure, at least two different siloxyl units chosen from those of formula (R 9) 3 SiO / 2 (M unit), (R 9) 2 Si0 2/2 (D unit), R 9 Si0 3 / 2 (T unit) and S1O4 / 2 (Q unit), at least one of these units being a T or Q unit. The weight content of OH and / or alkoxyl groups is generally between 0.2 and 10% by weight. weight.
Comme exemple de résine on peut citer les résines siliciques communément appelées T(OH), DT(OH) , DQ(OH), DT(0H), MQ(0H) , MDT(0H), MDQ(0H) ou les mélanges de celles-ci, avec les motifs M et D ayant la mAme signification que ci-dessus et : As an example of a resin, mention may be made of the silicic resins commonly known as T (OH) , DT (OH) , DQ (OH) , DT (OH) , MQ (OH) , MDT (OH) , MDQ (OH) or these, with the m and D having the m me meaning as above and:
- le motif siloxyle T(0H), = (OH)(R0)SiO2 2 ; et the siloxyl unit T (OH) , = (OH) (R 0 ) SiO 2 2 ; and
- le motif siloxyle Q(OH) = (OH)Si03 2 ; Le polyorganosiloxane (A) peut-être utilisé à raison de 1 à 50 % en poids, et de préférence de 3 à 40 % en poids et mieux encore à raison de 5 à 30 % en poids par rapport au poids total de la composition E. the siloxyl unit Q (OH) = (OH) SiO 3 2 ; The polyorganosiloxane (A) may be used in a proportion of 1 to 50% by weight, and preferably 3 to 40% by weight and more preferably in a proportion of 5 to 30% by weight relative to the total weight of the composition E .
Selon un mode de réalisation particulier, la composition E comprend en outre au moins un polyorganosiloxane (B) présentant par molécule au moins deux groupements hydrogénosiiane SiH et de préférence au moins trois groupements hydrogénosiiane SiH .
A titre de polyorganosiloxanes (B) utile selon l'invention on peut citer ceux qui comportent : According to a particular embodiment, the composition E further comprises at least one polyorganosiloxane (B) having per molecule at least two hydrogenosiiane SiH groups and preferably at least three hydrogenosiiane SiH groups. As polyorganosiloxanes (B) useful according to the invention, mention may be made of those comprising:
• des motifs siloxyles de formule (11-1 ) : Siloxyl units of formula (11-1):
H dLe Si0 l^ H d L e Si0 l ^
2 (11-1) 2 (11-1)
dans laquelle : in which :
- les groupes L, identiques ou différents, représentent chacun un groupe hydrocarboné monovalent et de préférence un groupe alkyle ayant de 1 à 8 atomes de carbone inclus, éventuellement substitué par au moins un atome d'halogène, un groupes aryle et, avantageusement, un radical xylyle, tolyle ou phényle, the groups L, which are identical or different, each represent a monovalent hydrocarbon group and preferably an alkyl group having from 1 to 8 carbon atoms inclusive, optionally substituted by at least one halogen atom, an aryl group and, advantageously, a xylyl, tolyl or phenyl radical,
- d est égal à 1 ou 2, e est égal à 0, 1 ou 2 et la somme (d+e) est égale à 1 , 2 ou 3, et d is 1 or 2, e is 0, 1 or 2 and the sum (d + e) is 1, 2 or 3, and
• éventuellement des motifs siloxyles de formule (II-2): Optionally siloxyl units of formula (II-2):
LoSio i-l! L o Sio it!
(II-2) (II-2)
dans laquelle les groupements L ont la même signification que ci-dessus et g est égal à 0, 1 , 2 ou 3, in which the groups L have the same meaning as above and g is 0, 1, 2 or 3,
• et avec la condition que le polyorganosiloxane (B) comporte au moins deux motifs siloxyles (11-1 ) et de préférence au moins trois motifs siloxyles (11-1). Dans les formules (11-1 ) et (II-2), les groupes L, identiques ou différents, sont de préférence choisis parmi le groupe constitué par : un méthyle, un éthyle et un phényle. La viscosité dynamique de ce polyorganosiloxane (B) est le plus souvent au moins égale à 10 mPa.s et, de préférence elle est comprise entre 20 et 1000 mPa.s. Pour des raisons économiques, sa viscosité est de préférence inférieure à 100 mPa.s, c'est-à-dire comprise entre 10 mPa.s et 100 mPa.s. And with the proviso that the polyorganosiloxane (B) comprises at least two siloxyl units (11-1) and preferably at least three siloxyl units (11-1). In the formulas (11-1) and (II-2), the L groups, which are identical or different, are preferably chosen from the group consisting of: a methyl, an ethyl and a phenyl. The dynamic viscosity of this polyorganosiloxane (B) is most often at least 10 mPa.s and preferably between 20 and 1000 mPa.s. For economic reasons, its viscosity is preferably less than 100 mPa.s, that is to say between 10 mPa.s and 100 mPa.s.
Le polyorganosiloxane (B) peut être uniquement formé de motifs de formule (II- 1 ) ou comporter en plus des motifs de formule (II-2). Des exemples utiles de motifs siloxyles de formule (11-1 ) sont : H(CH3)2SiOi/2, H(CH3)Si02/2 et H(C6H5)Si02/2. Des exemples utiles de motifs siloxyles de formule (II-2) sont les motifs siloxyles : Si04/2,
(CH3)2Si02/2, (CH3)3SiOi/2, (CH3)Si03/2, (CH3)(CeH5)Si02/2. (CH3)2(C6H5)Si01/2 et (CH3)(C6H5)Si02/2. The polyorganosiloxane (B) may be formed solely of units of formula (II-1) or may further comprise units of formula (II-2). Useful examples of siloxyl units of formula (11-1) are: H (CH 3) 2 SiO / 2, H (CH 3) Si0 2/2 and H (C 6 H 5) Si0 2/2. Useful examples of siloxyl units of formula (II-2) are the siloxy units: Si0 4/2, (CH 3) 2Si0 2/2, (CH 3) 3 SiO / 2, (CH 3) Si0 3/2, (CH 3) (C e H 5) Si02 / 2. (CH 3 ) 2 (C 6 H 5 ) SiO 1/2 and (CH 3 ) (C 6 H 5 ) SiO 2/2 .
Des exemples de polyorganosiloxane (B) sont des composés linéaires ou cycliques comme : Examples of polyorganosiloxane (B) are linear or cyclic compounds such as:
- les diméthylpolysiloxanes à extrémités hydrogénodiméthylsilyle, dimethylpolysiloxanes with hydrogenodimethylsilyl ends,
- les copolymères à motifs (diméthyl)(hydrogénométhyl)polysiloxanes à extrémités triméthylsilyles ou hydrogénodiméthyles, copolymers with (dimethyl) (hydrogenomethyl) polysiloxane units with trimethylsilyl or hydrogenodimethyl ends,
- les copolymères à motifs (diméthyl)(hydrogénométhyl) polysiloxanes à extrémités hydrogénodiméthylsilyles, copolymers with (dimethyl) (hydrogenomethyl) polysiloxane units with hydrogenodimethylsilyl ends,
- les hydrogénométhylpolysiloxanes à extrémités triméthylsilyles, et trimethylsilyl-terminated hydrogenomethylpolysiloxanes, and
- les hydrogénométhylpolysiloxanes cycliques. cyclic hydrogenomethylpolysiloxanes.
Le polyorganosiloxane (B) peut éventuellement être un mélange d'un diméthylpolysiloxane à extrémités hydrogénodiméthylsilyle et d'un polyorganosiloxane porteur d'au moins 3 fonctions SiH (hydrogénosiloxyle). The polyorganosiloxane (B) may optionally be a mixture of a dimethylpolysiloxane with hydrogenodimethylsilyl ends and a polyorganosiloxane carrying at least 3 SiH (hydrogenosiloxyl) functional groups.
Conviennent tout particulièrement à l'invention à titre de polyorganosiloxane (B) les composés suivants :The following compounds are particularly suitable for use in the invention as polyorganosiloxane (B):
H3 H 3
H3 H 3
S3 S4 S5 S3 S4 S5
avec a, b, c, d et e représentant un nombre variant de : with a, b, c, d and e representing a number varying from:
- dans le polymère de formule S3 : 0 < a < 500 et 1 < b < 200 in the polymer of formula S3: 0 <a <500 and 1 <b <200
- dans le polymère de formule S4 : 0 < c < 500, et in the polymer of formula S4: 0 <c <500, and
- dans le polymère de formule S5 :1 < d < 200 et 1 < e < 50. in the polymer of formula S5: 1 <d <200 and 1 <e <50.
Selon un mode de réalisation avantageux, la composition E comprend en outre au moins un polyorganosiloxane (C) et/ou au moins un silane (D) comprenant chacun au moins un groupement comprenant au moins un atome d'azote et de préférence une fonction amine primaire, secondaire, tertiaire ou quaternaire. La
présence de tels composés permettre d'améliorer l'efficacité du procédé selon l'invention. According to an advantageous embodiment, the composition E further comprises at least one polyorganosiloxane (C) and / or at least one silane (D) each comprising at least one group comprising at least one nitrogen atom and preferably an amine function primary, secondary, tertiary or quaternary. The The presence of such compounds makes it possible to improve the efficiency of the process according to the invention.
Comme exemple de silane (D) selon l'invention, on peut citer le 3- aminopropyltrihydroxysilane ou le composé Silquest® VS142 commercialisé par la société Momentive Performance Materials, en solution aqueuse, qui est constitué d'un oligomère du silane décrit ci-dessous, partiellement condensé via ses fonctions SiOH : As an example of silane (D) according to the invention, mention may be made of 3-aminopropyltrihydroxysilane or the compound Silquest® VS142 sold by the company Momentive Performance Materials, in aqueous solution, which consists of a silane oligomer described below. partially condensed via its SiOH functions:
15 parties en poids par rapport au poids total de l'émulsion, de préférence à raison de 0,5 à 5 parties en poids. 15 parts by weight relative to the total weight of the emulsion, preferably in an amount of 0.5 to 5 parts by weight.
L'avantage lié à l'utilisation de ce silane particulier est qu'il peut aussi jouer le rôle de réticulant via la présence des trois fonctions réactives que sont les groupements hydroxyles et ceci tout en étant hydrosoluble. La construction du réseau silicone après réticulation de la composition (E) n'en est que facilitée. The advantage of using this particular silane is that it can also act as a crosslinker via the presence of the three reactive functions that are hydroxyl groups and this while being water soluble. The construction of the silicone network after crosslinking the composition (E) is only facilitated.
Comme exemple de polyorganosiloxane (C) on peut citer ceux qui comprennent des motifs siloxyles identiques ou différents de formule générale: As an example of polyorganosiloxane (C), mention may be made of those which comprise identical or different siloxyl units of general formula:
R3 a R b Si 04-(a+b)/2 (IN) R 3 to R b Si 0 4 - ( a + b) / 2 (IN)
dans laquelle : in which :
- a = 0, 1 , 2 ou 3, b = 0, 1 , 2 ou 3, a+b < 3, - a = 0, 1, 2 or 3, b = 0, 1, 2 or 3, a + b <3,
- les symboles R3 sont identiques ou différents et représentent chacun un radical hydrocarboné monovalent choisi parmi les radicaux alkyles ayant de 1 àthe symbols R 3 are identical or different and each represents a monovalent hydrocarbon radical chosen from alkyl radicals having from 1 to
40 atomes de carbone, les radicaux -OR5 avec R5= H, et 40 carbon atoms, the radicals -OR 5 with R 5 = H, and
- les symboles R4 sont des radicaux identiques ou différents et représentent des radicaux de formule générale (IV) : the symbols R 4 are identical or different radicals and represent radicals of general formula (IV):
-R6-N(R7)(R8) (IV) -R 6 -N (R 7 ) (R 8 ) (IV)
dans laquelle:
- le symbole R6 étant un groupement divalent hydrocarboné ayant de 1 à 40 atomes de carbone, in which: the symbol R 6 being a divalent hydrocarbon group having from 1 to 40 carbon atoms,
- le symbole R7 étant un atome d'hydrogène ou un groupement monovalent hydrocarboné ayant de 1 à 40 atomes de carbone,the symbol R 7 being a hydrogen atom or a monovalent hydrocarbon group having from 1 to 40 carbon atoms,
- le symbole R8 étant un atome d'hydrogène ou un radical de formule (V) suivante: the symbol R 8 being a hydrogen atom or a radical of formula (V) below:
-[R9-N(R10)]XR10 - [R 9 -N (R 10 )] X R 10
- le symbole R9 étant un radical divalent de formule (VI) suivante : the symbol R 9 being a divalent radical of formula (VI) below:
-[C(R10)(R10)-]y - [C (R 10 ) (R 10 ) -] y
- formules dans lesquelles 0 < x < 40, y= 1 , 2 ou 3, et le symbole R10 est un atome d'hydrogène ou un groupement monovalent - formulas in which 0 <x <40, y = 1, 2 or 3, and the symbol R 10 is a hydrogen atom or a monovalent group
hydrocarboné ayant de 1 à 40 atomes de carbone, et hydrocarbon having 1 to 40 carbon atoms, and
- au moins un motif siloxyle porteur d'un groupement R4 est présent par molécule. at least one siloxyl unit carrying an R 4 group is present per molecule.
Comme exemples de radicaux R4 utiles selon l'invention ont peut citer les radicaux suivants : Examples of radicals R 4 useful according to the invention may include the following radicals:
-CH2-NH2 -CH 2 -NH 2
-CH2-NH-C6H5 -CH 2 -NH-C 6 H 5
-CH2-NH-C6H -CH 2 -NH-C 6 H
-CH2-NH-(C2H40)j[C2H3(CH3)0]kH -CH 2 -NH- (C 2 H 4 O) j [C 2 H 3 (CH 3 ) 0] k H
-C3H6-NH2 -C 3 H 6 -NH 2
-C3H6-NH-C6H5 -C 3 H 6 -NH-C 6 H 5
-CaHe-NH-CsH -CaHe-NH-CsH
-C3H6-NH-(C2H40)j[C2H3(CH3)0] kH -C 3 H 6 -NH- (C 2 H 4 O) j [C 2 H 3 (CH 3 ) 0] k H
-C3H6-NH-(C2H4-NH)i(C2H40)j[C2H3(CH3)0]kH -C 3 H 6 -NH- (C 2 H 4 -NH) i (C 2 H 4 O) j [C 2 H 3 (CH 3 ) O] kH
-C3H6-NH-C2H4-NH2 -C 3 H 6 -NH-C 2 H 4 -NH 2
-C3H6-NH-C2H4-NH-C6H5 -C 3 H 6 -NH-C 2 H 4 -NH-C 6 H 5
-C3H6-NH-C2H4-NH-C6H -C 3 H 6 -NH-C 2 H 4 -NH-C 6 H
-C3H6-NH-C2H4-NH-(C2H40)j [C2H3(CH3)0]kH -C 3 H 6 -NH-C 2 H 4 -NH- (C 2 H 4 O) j [C 2 H 3 (CH 3) O] k H
-C3H6-NH-C3H7 -C 3 H 6 -NH-C 3 H 7
-C3H6-0-C5H4(CH3)4NH2 -C 3 H 6 -O-C 5 H 4 (CH 3 ) 4 NH 2
-CH2CH(CH3)CH2-NH-C2H4-NH2
-CH2CH(CH3)CH2-NH-C2H4-NH-C6H5 CH 2 CH (CH 3 ) CH 2 -NH-C 2 H 4 -NH 2 -CH 2 CH (CH 3) CH 2 -NH-C 2 H 4 -NH-C 6 H 5
-CH2CH(CH3)CH2-NH-C2H4-NH-C6H11 -CH 2 CH (CH 3 ) CH 2 -NH-C 2 H 4 -NH-C 6 H 11
-C3H6-NH-C2H4-NH-C2H4-NH2-C 3 H 6 -NH-C 2 H 4 -NH-C 2 H 4 -NH 2
Les indices i, j et k sont des entiers identiques ou différents ayant une valeur supérieure ou égale à 0 et inférieure ou égale à 20 et la somme i+j+k est de préférence compris entre 0 et 30. The indices i, j and k are identical or different integers having a value greater than or equal to 0 and less than or equal to 20 and the sum i + j + k is preferably between 0 and 30.
Selon un autre mode de réalisation préféré, le radical R4 est choisi parmi le groupe constitué par les radicaux suivants : -(CH2)3-NH2 et -(CH2)3-NH-(CH2)2-NH2. According to another preferred embodiment, the radical R 4 is chosen from the group consisting of the following radicals: - (CH 2 ) 3 -NH 2 and - (CH 2 ) 3 -NH- (CH 2 ) 2 -NH 2 .
Selon un autre mode de réalisation préféré, le polyorganosiloxane (C) est caractérisé en ce qu'il comportent par molécule au moins un motif siloxyle substitué par au moins un groupement fonctionnel V directement lié à un atome de silicium, ledit groupement fonctionnel V étant un groupement à fonction(s) pipéridinyle(s) stériquement encombrée(s) choisi parmi le groupe constitué par: According to another preferred embodiment, the polyorganosiloxane (C) is characterized in that it comprises, per molecule, at least one siloxyl unit substituted with at least one functional group V directly bonded to a silicon atom, said functional group V being a sterically hindered piperidinyl group (s) group (s) selected from the group consisting of:
a) des groupements de formule (I) : a) groups of formula (I):
(I) (I)
formule dans laquelle: formula in which:
• R4 est un radical hydrocarboné divalent choisi parmi le groupe constitué par : R 4 is a divalent hydrocarbon radical chosen from the group consisting of:
- les radicaux alkylènes linéaires ou ramifiés, ayant 2 à 18 atomes de carbone; linear or branched alkylene radicals having 2 to 18 carbon atoms;
- les radicaux alkylènes-carbonyles dont la partie alkylène linéaire ou ramifiée, comporte 2 à 20 atomes de carbone; alkylene-carbonyl radicals whose linear or branched alkylene part contains 2 to 20 carbon atoms;
- les radicaux alkylènes-cyclohexylènes dont la partie alkylène linéaire ou ramifiée, comporte 2 à 12 atomes de carbone et la partie cyclo-hexylène comporte un groupement OH et éventuellement 1 ou 2 radicaux alkyles ayant 1 à 4 atomes de carbone;
- les radicaux de formule R7-0-R7 dans laquelle les radicaux R7 identiques ou différents représentent des radicaux alkylènes ayant 1 à 12 atomes de carbone; alkylene-cyclohexylene radicals whose linear or branched alkylene part contains 2 to 12 carbon atoms and the cyclohexylene part comprises an OH group and optionally 1 or 2 alkyl radicals having 1 to 4 carbon atoms; the radicals of formula R 7 -O-R 7 in which the radicals R 7, which are identical or different, represent alkylene radicals having 1 to 12 carbon atoms;
- les radicaux de formule R7-0-R7 dans laquelle les radicaux R7 ont les significations indiquées précédemment et l'un d'entre eux ou les deux sont substitués par un ou deux groupement(s) -OH; radicals of formula R 7 -O-R 7 in which the radicals R 7 have the meanings indicated above and one or both of them are substituted with one or two group (s) -OH;
- les radicaux de formule R7-COO-R7 dans laquelle les radicaux R7 ont les significations indiquées précédemment; et the radicals of formula R 7 -COO-R 7 in which the radicals R 7 have the meanings indicated above; and
- les radicaux de formule R8-O-R9-0-CO-R8 dans laquelle les radicaux R8 et R9 identiques ou différents, représentent des radicaux alkylènes ayant 2 à 12 atomes de carbone et le radical R9 est éventuellement substitué par un radical hydroxyle; et the radicals of formula R 8 -OR 9 -O-CO-R 8 in which the radicals R 8 and R 9, which are identical or different, represent alkylene radicals having 2 to 12 carbon atoms and the radical R 9 is optionally substituted by a hydroxyl radical; and
• U représente -O- ou -N(R10)-, avec R10 étant un radical choisi parmi le groupe constitué par un atome d'hydrogène, un radical alkyle linéaire ou ramifié comportant 1 à 6 atomes de carbone et un radical divalent de formule (II) suivante : U represents -O- or -N (R 10 ) -, with R 10 being a radical chosen from the group consisting of a hydrogen atom, a linear or branched alkyl radical containing 1 to 6 carbon atoms and a divalent radical; of formula (II) below:
b) des groupements de formule (III):
b) groups of formula (III):
(III) (III)
formule dans laquelle: formula in which:
• R'4 est choisi parmi le groupe constitué par : R ' 4 is selected from the group consisting of:
- un radical trivalent de formule (IV) suivante: a trivalent radical of formula (IV) below:
^ CO— ^ CO-
— (CH2 ) CH - (CH 2 ) CH
m \ m
\ CO— \ CO-
(IV) (IV)
où m représente un nombre de 2 à 20, et where m represents a number from 2 to 20, and
- un radical trivalent de formule (VI) : a trivalent radical of formula (VI):
(VI) (VI)
où p représente un nombre de 2 à 20; where p represents a number from 2 to 20;
• ΙΓ représente -O- ou -N(R12)-, avec R12 étant un radical choisi parmi un atome d'hydrogène, un radical alkyle linéaire ou ramifié comportant 1 à 6 atomes de carbone; et • represents -O- or -N (R 12 ) -, with R 12 being a radical selected from a hydrogen atom, a linear or branched alkyl radical having 1 to 6 carbon atoms; and
• R5 et R6 ont les mêmes significations que celles données à propos de la formule (I); • R 5 and R 6 have the same meanings as those given about the formula (I);
Selon un mode de réalisation particulièrement préféré, le polyorganosiloxane (C) selon l'invention sont des composés de formule générale (IX) suivante :
According to a particularly preferred embodiment, the polyorganosiloxane (C) according to the invention are compounds of the following general formula (IX):
(IX) (IX)
formule dans laquelle : formula in which:
les différents motifs sont répartis de manière statistique dans la chaîne ; p représente un nombre supérieur ou égal à 0 et de préférence compris entre 1 et 2000; the different patterns are statistically distributed in the chain; p represents a number greater than or equal to 0 and preferably between 1 and 2000;
r représente un nombre supérieur ou égal à 0 et de préférence compris entre 1 et 2000; r represents a number greater than or equal to 0 and preferably between 1 and 2000;
q représente un nombre supérieur ou égal à 1 , de préférence compris entre 1 et 50 ; q represents a number greater than or equal to 1, preferably between 1 and 50;
R10 représente un radical alkyle, linéaire ou ramifié, ayant 1 à 18 atomes de carbone; R 10 represents a linear or branched alkyl radical having 1 to 18 carbon atoms;
le groupement U a la même signification que U', R11 a la même signification que R'4 et R12 a la même signification que R6 décrits ci-dessus. the group U has the same meaning as U ', R 11 has the same meaning as R' 4 and R 12 has the same meaning as R 6 described above.
Selon un mode préféré, la somme p+r est comprise entre 1 et 800. Selon un autre mode de réalisation préféré, le groupement fonctionnel V est un radical propyloxytétraméthylpipéridine de formule (X) suivante: According to a preferred embodiment, the sum p + r is between 1 and 800. According to another preferred embodiment, the functional group V is a propyloxytetramethylpiperidine radical of formula (X) below:
(X)
Selon un mode de réalisation particulier, la composition E comprend : (X) According to a particular embodiment, the composition E comprises:
- au moins un polyorganosiloxane (A) selon l'invention et tel que défini ci-dessus at least one polyorganosiloxane (A) according to the invention and as defined above
- au moins un polyorganosiloxane (B) selon l'invention et tel que défini ci-dessus, - de l'eau (F) , at least one polyorganosiloxane (B) according to the invention and as defined above, water (F),
- éventuellement au moins un tensioactif (G), - optionally at least one surfactant (G),
- éventuellement au moins un polyorganosiloxane (C) selon l'invention et tel que défini ci-dessus, et optionally at least one polyorganosiloxane (C) according to the invention and as defined above, and
- éventuellement au moins un silane (D) selon l'invention et tel que défini ci- dessus. - optionally at least one silane (D) according to the invention and as defined above.
La nature de tensioactif (G) sera facilement déterminée par l'homme du métier, l'objectif étant de préparer une émulsion stable. Les tensioactifs anioniques, cationiques, non-ioniques et zwitterioniques peuvent être employés seuls ou en mélange. The nature of surfactant (G) will be readily determined by those skilled in the art, the objective being to prepare a stable emulsion. The anionic, cationic, nonionic and zwitterionic surfactants can be used alone or as a mixture.
Il est à noter que la composition E selon l'invention peut aussi comprendre des colloïdes protecteurs tels que l'acool polyvinylique. A titre du tensioactif anionique, on peut mentionner les agents tensio-actifs suivants: It should be noted that the composition E according to the invention may also comprise protective colloids such as polyvinyl alcohol. As the anionic surfactant, mention may be made of the following surfactants:
- les alkylesters sulfonates de formule Ra-CH(S03M)-COORb, où Ra représente un radical alkyle en C8-C2o, de préférence en Ci0-Ci6, Rb un radical alkyle en C1-C6, de préférence en C1-C3 et M un cation alcalin (sodium, potassium, lithium), ammonium substitué ou non substitué (méthyl-, diméthyl-, triméthyl-, tétraméthylammonium, diméthylpiperidinium) ou dérivé d'une alcanolamine (monoéthanolamine, diéthanolamine, triéthanolamine), the alkyl ester sulfonates of formula R a -CH (SO 3 M) -COOR b , in which R a represents a C 8 -C 2 o alkyl radical, preferably C 1 -C 16 radical, R b a C 1 -C alkyl radical; -C6, preferably C 1 -C 3 and M an alkaline cation (sodium, potassium, lithium), substituted or unsubstituted ammonium (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium) or derived from an alkanolamine (monoethanolamine , diethanolamine, triethanolamine),
- les alkylsulfates de formule RcOS03M, où Rc représente un radical alkyle ou hydroxyalkyle en C10-C24, de préférence en C12- C2o, M représentant un atome d'hydrogène ou un cation de même définition que ci- dessus, ainsi que leurs dérivés éthoxylénés (OE) et/ou propoxylénés (OP), présentant de préférence de 1 à 20 motifs OE,
- les alkylamides sulfates de formule RdCONHReOS03M où Rd représente un radical alkyle en C2-C22, de préférence en C6-C20, Re un radical alkyle en C2-C3, M représentant un atome d'hydrogène ou un cation de même définition que ci-dessus, ainsi que leurs dérivés éthoxylénés (OE) et/ou propoxylénés (OP), présentant de préférence 1 à 20 motifs OE, the alkyl sulphates of formula R c OSO 3 M, in which R c represents a C 1 -C 24, preferably C 12 -C 20 , alkyl or hydroxyalkyl radical, M representing a hydrogen atom or a cation of the same definition as above, as well as their ethoxylenated (EO) and / or propoxylenated (PO) derivatives, preferably having from 1 to 20 EO units, the alkylamide sulphates of formula R d CONHR e OSO 3 M where R d represents a C2-C22 alkyl radical, preferably a C6-C20 alkyl radical, R e represents a C2-C3 alkyl radical, M represents a hydrogen atom or a cation having the same definition as above, as well as their ethoxylenated (EO) and / or propoxylenated (PO) derivatives, preferably having 1 to 20 EO units,
- les sels d'acides gras saturés ou insaturés en C8-C2 , de préférence en C14- C2o, les alkylbenzènesulfonates en C9-C20, ainsi que leurs dérivés éthoxylénés (OE) et/ou propoxylénés (OP), présentant de préférence 1 à 20 motifs OE, - les alkylbenzènesulfonates en C9-C20, les alkylsulfonates primaires ou secondaires en C8-C22, les alkylglycérol sulfonates, les acides polycarboxyliques sulfonés décrits dans GB-A-1 082 179, les sulfonates de paraffine, les N-acyl N-alkyltaurates, les mono- et dialkylphosphates, les alkyliséthionates, les alkylsuccinamates, les alkylsulfosuccinates, les monoesters ou diesters de sulfosuccinates, les N-acyl sarcosinates, les sulfates d'alkylglycosides, les polyéthoxycarboxylates, le cation étant un métal alcalin (sodium, potassium, lithium), un reste ammonium substitué ou non substitué (méthyl-, diméthyl-, triméthyl-, tétraméthylammonium, diméthylpiperidinium) ou dérivé d'une alcanolamine (monoéthanolamine, diéthanolamine, triéthanolamine). A titre de tensioactifs non-ioniques on peut citer les éthers alkyliques ou aryliques de poly(oxyde d'alkylène), l'hexastéarate de sorbitan polyoxyéthyléné, l'oléate de sorbitan polyoxyéthyléné et les éthers de cétylstéaryle et de poly(oxyde d'éthylène). A titre d'éther arylique de poly(oxyde d'alkylène), on peut mentionner les alkylphénols polyoxyéthylénés. A titre d'éther alkylique de poly(oxyde d'alkylène), on peut mentionner l'éther isodécylique de polyéthylèneglycol et l'éther triméthylnonylique de polyéthylèneglycol contenant de 3 à 15 unités d'oxyde d'éthylène par molécule. - saturated fatty acid salts or unsaturated C8-C2, preferably C 14 - C 2 o, alkylbenzenesulfonates C9-C20, and their ethoxylenated (EO) and / or propoxylenated (OP), having preferably 1 to 20 EO units, C 9 -C 20 alkylbenzenesulfonates, C 8 -C 2 primary or secondary alkylsulfonates, alkylglycerol sulfonates, sulfonated polycarboxylic acids described in GB-A-1 082 179, paraffin sulfonates , N-acyl N-alkyltaurates, mono- and dialkylphosphates, alkylisethionates, alkylsuccinamates, alkylsulfosuccinates, sulfosuccinates monoesters or diesters, N-acyl sarcosinates, alkylglycoside sulfates, polyethoxycarboxylates, the cation being a alkali metal (sodium, potassium, lithium), a substituted or unsubstituted ammonium residue (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium) or an alkanolamine derivative (monoethanolamine, diethan olamine, triethanolamine). As nonionic surfactants, mention may be made of alkyl or aryl ethers of polyalkylene oxide, polyoxyethylene sorbitan hexastearate, polyoxyethylenated sorbitan oleate and cetylstearyl ethers and polyethylene oxide ethers. ). As the polyalkylene ether aryl ether, mention may be made of polyoxyethylenated alkylphenols. As alkyl ether of polyalkylene oxide, mention may be made of polyethylene glycol isodecyl ether and polyethylene glycol trimethylnonyl ether containing from 3 to 15 ethylene oxide units per molecule.
On peut aussi citer à titre d'exemple de tensioactif : les tensioactifs fluorés ioniques, non ioniques ou amphotères et leurs mélanges, par exemple : Mention may also be made, as an example of a surfactant, of ionic, nonionic or amphoteric fluorinated surfactants and mixtures thereof, for example:
- les perfluoroalkyles, perfluoroalkyls,
- les perfluorobétaïnes, perfluorobetaines,
- les polyfluoroalcools éthoxylés,
- les polyfluoroalkyles d'ammonium, the ethoxylated polyfluoroalcohols, ammonium polyfluoroalkyls,
- les agents tensioactifs dont la partie hydrophile contient un ou plusieurs motif(s) saccharide(s) porteur(s) de cinq à six atomes de carbone et dont la partie hydrophobe contient un motif de formule Rf(CH2)n-, dans laquelle n = 2 à 20 et Rf représente un motif perfluoroalkyle de formule CmF2m+i, dans laquelle m = 1 à 10; et surfactants whose hydrophilic part contains one or more saccharide unit (s) bearing (s) of five to six carbon atoms and whose hydrophobic part contains a unit of formula R f (CH 2) n -, in which n = 2 to 20 and Rf represents a perfluoroalkyl unit of formula C m F 2 m + i, in which m = 1 to 10; and
- les polyélectrolytes présentant des groupements latéraux perfluoroalkyles gras. Par agent tensioactif fluoré, on entend, comme cela est parfaitement connu en soi, un composé formé d'une partie perfluorocarbonée aliphatique, comprenant au moins trois atomes de carbone, et une partie hydrophile, ionique, non ionique ou amphotère. La partie perfluorocarbonée d'au moins trois atomes de carbone peut représenter, soit l'ensemble, soit une fraction seulement de la partie fluorocarbonée de la molécule. Concernant ce type dé composé, on trouve dans la littérature un grand nombre de références. L'homme du métier pourra se reporter notamment aux références suivantes : polyelectrolytes having perfluoroalkyl fatty side groups. By fluorinated surfactant is meant, as is well known per se, a compound formed of an aliphatic perfluorocarbon moiety, comprising at least three carbon atoms, and a hydrophilic, ionic, nonionic or amphoteric moiety. The perfluorocarbon portion of at least three carbon atoms may represent either all or only a fraction of the fluorocarbon portion of the molecule. Regarding this type of compound, there is a large number of references in the literature. The skilled person can refer in particular to the following references:
- FR-A-2 149 519, WO-A-94 21 233, US-A-3, 194,767, l'ouvrage "Fluorinated Surfactants", Erik Kissa, Editeur Marcel Dekker Inc. Chapitre 4, notamment les Tableaux 4.1 et 4.4. - FR-A-2 149 519, WO-A-94 21 233, US-A-3, 194,767, the book "Fluorinated Surfactants", Erik Kissa, Publisher Marcel Dekker Inc. Chapter 4, including Tables 4.1 and 4.4 .
On peut citer, en particulier, les produits vendus par la société Du Pont sous la dénomination ZONYL®, par exemple FSO, FSN-100, FS-300, FSD, ainsi que les tensioactifs fluorés de dénomination FORAFAC® distribués par la société DU PONT et les produits vendus sous la dénomination FLUORAD® par la Société 3M. These include, in particular, the products sold by Du Pont under the name ZONYL ®, eg FSO, FSN-100, FS-300, FSD and fluorinated surfactants naming Forafac ® distributed by the company DU PONT and the products sold under the name FLUORAD ® by the company 3M.
Parmi ces tensioactifs, on citera, en particulier, les composés perfluoroalkylés anioniques, cationiques, non-ioniques et amphotères, et parmi eux, plus particulièrement, les tensioactifs de la classe des ZONYL® commercialisés par DU Pont, commercialisés par Du Pont respectivement sous les dénominations ZONYL® FSA, ZONYL® FSO, ZONYL® FSC et ZONYL® FSK. On peut encore préciser à leur propos :
ZONYL® FSO 100 : CAS 65545-80-4, (non-ionique) 99 à 100 %, le reste étant du 1 ,4-dioxane These surfactants include, in particular, anionic perfluoroalkyl compounds, cationic, nonionic and amphoteric surfactants, and among them, particularly, the surfactants of the class of ZONYL ® marketed by Du Pont, marketed by Du under the respective bridge ZONYL ® FSA, ZONYL ® FSO, ZONYL ® FSC and ZONYL ® FSK. We can further specify about them: ZONYL ® FSO 100: CAS 65545-80-4, (nonionic) 99 to 100%, the balance being 1,4-dioxane
ZONYL® FSN : CAS 65545-80-4, 99 à 100 %, le reste étant de l'acétate de sodium et du 1 ,4-dioxane ZONYL ® FSN: CAS 65545-80-4, 99-100%, the remainder being sodium acetate and 1,4-dioxane
ZONYL® FS-300 : CAS 65545-80-4, 40 %, le reste étant de 1 ,4-dioxane (< 0,1 %) et de l'eau ZONYL ® FS-300: CAS 65545-80-4, 40%, the remainder being 1,4-dioxane (<0.1%) and water
ZONYL®FSD : CAS 70983-60-7 30 %, (cationique), le reste étant de l'hèxylèneglycol (10 %), du chlorure de sodium (3 %) et de l'eau (57 %). ZONYL ® FSD: CAS 70983-60-7 30%, (cationic), the remainder being hexylene glycol (10%), sodium chloride (3%) and water (57%).
On peut encore citer : We can also mention:
• les perfluoroalkyl bétaïnes (amphotères) telles que celle commercialisée par DU PONT sous la dénomination FORAFAC® 1157, les polyfluoroalcools éthoxylés (non-ioniques), tels que celui commercialisé par DU PONT sous la dénomination FORAFAC 1 110 D, les sels polyfluoroalkyl d'ammonium (cationiques), tels que celui commercialisé par DU PONT sous la dénomination FORAFAC 1179 ; • perfluoroalkyl betaines (amphoteric) such as that marketed by DU PONT under the name Forafac ® 1157, ethoxylated polyfluoroalcools (nonionic) such as that marketed by DU PONT under the name Forafac 1110 D, the polyfluoroalkyl salts ammonium (cationic), such as that marketed by DU PONT under the name FORAFAC 1179;
• les agents tensioactifs dont la partie hydrophile contient un ou plusieurs motif(s) saccharide(s) contenant de 5 à 6 atomes de carbone (motifs dérivés de sucres comme le fructose, le glucose, le mannose, le galactose, le talose, le gulose, l'allose, l'altose, l'idose, l'arabinose, le xylose, le lyxose et/ou le ribose) et dont la partie hydrophobe contient un motif de formule RF(CH2)n, où n peut aller de 2 à 20, de préférence de 2 à 10 et RF représente un motif perfluoroalkyle de formule CmF2m+i avec m pouvant aller de 1 à 10, de préférence de 4 à 8, choisis parmi ceux présentant les caractéristiques définies ci-dessus ; on peut mentionner les monoesters d'acides gras perfluoroalkylés et de sucres comme le sucrose, la fonction monoester pouvant être représentée par la formule RF(CH2)nC(0), où n peut aller de 2 à 10 et RF représente un motif perfluoroalkyle de formule CmF2m+i avec m pouvant aller de 4 à 8, décrits dans JAOCS, Vol. 69, no. 1 (janvier 1992) et choisis parmi ceux présentant les caractéristiques définies ci-dessus ; et Surfactants whose hydrophilic part contains one or more saccharide unit (s) containing from 5 to 6 carbon atoms (units derived from sugars such as fructose, glucose, mannose, galactose, talose, gulose, allose, altose, idose, arabinose, xylose, lyxose and / or ribose) and whose hydrophobic part contains a unit of formula R F (CH 2 ) n , where n can from 2 to 20, preferably from 2 to 10, and R F represents a perfluoroalkyl unit of formula C m F2m + i with m possibly ranging from 1 to 10, preferably from 4 to 8, chosen from those having the characteristics defined herein. -above ; mention may be made of perfluoroalkylated fatty acid monoesters and sugars such as sucrose, the monoester function being represented by the formula R F (CH 2) n C (O), where n can range from 2 to 10 and R F represents a perfluoroalkyl unit of formula CmF2m + i with m being able to range from 4 to 8, described in JAOCS, Vol. 69, no. 1 (January 1992) and selected from those having the characteristics defined above; and
• les polyélectrolytes présentant des groupements latéraux perfluoroalkylés gras tels que les polyacrylates présentant des groupements RF(CH2)n où n
peut aller de 2 à 20, de préférence de 2 à 10 et RF représente un motif perfluoroalkyle de formule CmF2m+i avec m pouvant aller de 1 à 10, de préférence de 4 à 8, choisis parmi ceux présentant les caractéristiques définies ci-dessus ; on peut mentionner les polyacrylates présentant des groupements— CH2C7Fi5 décrits dans J. Chim. Phys. (1996) 93, 887-898 et choisis parmi ceux présentant les caractéristiques définies ci-dessus. référence, la composition E comprend : Polyelectrolytes having perfluoroalkyl fatty side groups such as polyacrylates having R F (CH 2 ) n groups where n can range from 2 to 20, preferably from 2 to 10 and R F represents a perfluoroalkyl unit of formula C m F 2 m + i with m being able to range from 1 to 10, preferably from 4 to 8, chosen from those presenting the characteristics defined above; polyacrylates having CH 2 C 7 F 5 groups described in J. Chim. Phys. (1996) 93, 887-898 and selected from those having the characteristics defined above. reference, the composition E comprises:
a) au moins un polyorganosiloxane (A) qui est une résine organosilicique porteuses d'au moins deux groupes hydroxyles ou alcoxyles condensables et comportant au moins deux types de motifs siloxyles différents choisis parmi ceux de formule M, D, T et Q avec : a) at least one polyorganosiloxane (A) which is an organosilicon resin carrying at least two condensable hydroxyl or alkoxyl groups and comprising at least two different types of siloxyl units chosen from those of formula M, D, T and Q with:
- le motif siloxyle M= (R0)3SiOi/2 ; - the siloxy unit M = (R 0) 3 SiO / 2;
- le motif siloxyle D= (R^SiO^ ; the siloxyl unit D = (R 1 SiO 2;
- le motif siloxyle T= R°Si03/2, et - the siloxyl unit T = R o Si0 3/2, and
- le motif siloxyle Q= Si04/2, et the siloxyl unit Q = Si0 4/2 , and
- l'un au moins de ces motifs étant un motif T ou Q, at least one of these motifs being a T or Q motif,
- formules dans lesquelles R° représente un groupement monovalent hydrocarboné ayant de 1 à 40 atomes de carbone ou un groupe - OR3 avec R3= H ou un radical alkyle ayant de 1 à 40 atomes de carbone, et ladite résine présentant une teneur pondérale en substituants hydroxyles ou alcoxy comprise entre 0,1 et 10% en poids par rapport au poids de la résine, et de préférence une teneur pondérale en substituants hydroxyles ou alcoxy comprise entre 0,2 et 5% en poids par rapport au poids de la résine, formulas in which R ° represents a monovalent hydrocarbon group having from 1 to 40 carbon atoms or a group - OR 3 with R 3 = H or an alkyl radical having from 1 to 40 carbon atoms, and said resin having a weight content in hydroxyl or alkoxy substituents of between 0.1 and 10% by weight relative to the weight of the resin, and preferably a weight content of hydroxyl or alkoxy substituents of between 0.2 and 5% by weight relative to the weight of the resin,
b) au moins un catalyseur (E) de la réaction de condensation ou de déshydrogénocondensation tel qu'un sel d'étain, un dérivé de la guanidine, un dérivé du fer, ou un sel ou complexe métallique du zinc, c) de l'eau (F), b) at least one catalyst (E) of the condensation or dehydrogenation condensation reaction, such as a tin salt, a guanidine derivative, an iron derivative, or a metal salt or complex of zinc; water (F),
d) éventuellement au moins un tensioactif (G), et d) optionally at least one surfactant (G), and
e) éventuellement au moins un polyorganosiloxane (C) selon l'invention et tel que défini ci-dessus, et
f) éventuellement au moins un silane (D) selon l'invention et tel que défini ci-dessus. e) optionally at least one polyorganosiloxane (C) according to the invention and as defined above, and f) optionally at least one silane (D) according to the invention and as defined above.
Comme catalyseur (E) selon l'invention, on peut citer les catalyseurs dérivés de l'étain, du fer, du zinc, du titane ou d'une guanidine éventuellement silylée. As catalyst (E) according to the invention, mention may be made of catalysts derived from tin, iron, zinc, titanium or an optionally silylated guanidine.
Comme catalyseur de condensation dérivé de l'étain, on peut utiliser les monocarboxylates et les dicarboxylates d'étain tels que l'éthyl-2 hexanoate d'étain, le dilaurate de dibutylétain, le diacétate de dibutylétain (voir le livre de NOLL "Chemistry and technology of silicone", page 337, Académie Press, 1968-2ème édition ou les brevets EP- 147 323 ou EP235049). As the tin-derived condensation catalyst tin monocarboxylates and dicarboxylates such as tin ethyl-2-hexanoate, dibutyltin dilaurate, dibutyltin diacetate can be used (see NOLL's book "Chemistry"). and technology of silicone ", page 337, Academy Press, 1968-2th edition or EP-147323 or EP235049).
(l) (L)
dans laquelle, in which,
- les radicaux R1 , identiques ou différents, représentent, indépendamment l'un de l'autre, un groupe alkyle monovalent linéaire ou ramifié, un groupement cycloalkyle, un groupe (cycloalkyl)alkyle, le cycle étant substitué ou non et pouvant comprendre au moins un hétéroatome ou un groupement fluoroalkyle, the radicals R 1 , which may be identical or different, represent, independently of each other, a linear or branched monovalent alkyl group, a cycloalkyl group or a (cycloalkyl) alkyl group, the ring being substituted or unsubstituted and which may comprise at least one minus one heteroatom or one fluoroalkyl group,
- le radical R2 représente un atome d'hydrogène, un groupement alkyle monovalent linéaire ou ramifié, un groupement cycloalkyle, un groupement alkyle substitué par un cycle, substitué ou non et pouvant comprendre au moins un hétéroatome, un groupement aromatique un groupe arylalkyle, un groupement fluoroalkyle, un groupement alkylamine ou alkylguanidine, et the radical R 2 represents a hydrogen atom, a linear or branched monovalent alkyl group, a cycloalkyl group, a substituted or unsubstituted ring-substituted alkyl group and may comprise at least one heteroatom, an aromatic group or an arylalkyl group, a fluoroalkyl group, an alkylamine or alkylguanidine group, and
- le radical R3 représente un groupement alkyle monovalent linéaire ou ramifié, un groupement cycloalkyle, un groupement alkyle substitué par un cycle, substitué ou non et pouvant comprendre au moins un hétéroatome, un groupement arylalkyle, fluoroalkyle, alkylamine ou alkylguanidine,
- lorsque le radical R2 n'est pas un atome d'hydrogène, les radicaux R2 et R3 peuvent être liés pour former un cycle aliphatique à 3, 4, 5, 6 ou 7 chaînons éventuellement substitué par un ou plusieurs substituants. II s'agit de guanidines 1 ,2,3-trisubstituées et 1 ,2,3,3-tétrasubstituées et présentent l'avantage d'être liquides, incolores, inodores et solubles dans les matrices silicones. Des exemples de ce type de catalyseurs sont décrits dans la demande de brevet internationale WO2009/118307. Par exemple, on peut citer les catalyseurs (A1) à (A6) suivants: the radical R 3 represents a linear or branched monovalent alkyl group, a cycloalkyl group, a substituted or unsubstituted ring-substituted alkyl group and may comprise at least one heteroatom, an arylalkyl, fluoroalkyl, alkylamine or alkylguanidine group, when the radical R 2 is not a hydrogen atom, the radicals R 2 and R 3 may be bonded to form a 3-, 4-, 5-, 6- or 7-membered aliphatic ring optionally substituted by one or more substituents. These are 1,2,3-trisubstituted and 1,2,3,3-tetrasubstituted guanidines and have the advantage of being liquid, colorless, odorless and soluble in silicone matrices. Examples of this type of catalyst are described in International Patent Application WO2009 / 118307. For example, the following catalysts (A1) to (A6) can be mentioned:
(A5) (A6) (A5) (A6)
Comme autres exemple de catalyseur (E) utiles selon l'invention, on peut citer la famille des guanidines de formule :
As other examples of catalyst (E) useful according to the invention, mention may be made of the family of guanidines of formula:
(II) (II)
dans laquelle, in which,
- les radicaux R1 , R2, R3, R4 ou R5 identiques ou différents, représentent, indépendamment l'un de l'autre, un groupe alkyle monovalent linéaire ou ramifié, un groupement cycloalkyle, un groupe (cycloalkyl)alkyle, le cycle étant substitué ou non et pouvant comprendre au moins un hétéroatome ou un groupement fluoroalkyle, un groupement aromatique un groupe arylalkyle, un groupement fluoroalkyle, un groupement alkylamine ou alkylguanidine, et - The radicals R 1 , R 2 , R 3 , R 4 or R 5, which are identical or different, represent, independently of each other, a linear or branched monovalent alkyl group, a cycloalkyl group or a (cycloalkyl) alkyl group. the ring being substituted or unsubstituted and may comprise at least one heteroatom or a fluoroalkyl group, an aromatic group an arylalkyl group, a fluoroalkyl group, an alkylamine or alkylguanidine group, and
- les radicaux R1 , R2, R3 ou R4 peuvent être liés deux à deux de manière à former un cycle aliphatique à 3, 4, 5, 6 ou 7 chaînons éventuellement substitué par un ou plusieurs substituants. the radicals R 1 , R 2 , R 3 or R 4 may be linked in pairs so as to form a 3-, 4-, 5-, 6- or 7-membered aliphatic ring optionally substituted with one or more substituents.
Il s'agit de guanidines pentasubstituées et présentent l'avantage d'être liquides, incolores, inodores et solubles dans les matrices silicones. They are pentasubstituted guanidines and have the advantage of being liquid, colorless, odorless and soluble in silicone matrices.
Selon un mode de réalisation particulier, les composés (A7) à (A9) suivants sont préférés: According to a particular embodiment, the following compounds (A7) to (A9) are preferred:
(A8)
(AT 8)
(A9) (A9)
Ils sont par exemple décrits dans la demande de brevet français n° FR- 0806610 déposé le 25 novembre 2008. They are for example described in the French patent application No. FR-0806610 filed November 25, 2008.
Selon un autre mode de réalisation, le catalyseur (E) est un complexe ou sel métallique du zinc de formule: According to another embodiment, the catalyst (E) is a metal complex or salt of zinc of formula:
[Zn (L1)r1 (L2)*] (III) [Zn (L 1 ) r 1 (L 2 ) *] (III)
dans laquelle: in which:
- M≥ 1 et r2≥0 et r1+r2=2, - M≥ 1 and r2≥0 and r1 + r2 = 2,
- le symbole L1 représente un ligand qui est un anion β-dicarbonylato ou l'anion énolate d'un composé β-dicarbonylé ou un anion acétylacétato dérivé d'un β-cétoester, et the symbol L 1 represents a ligand which is a β-dicarbonylato anion or the enolate anion of a β-dicarbonyl compound or an acetylacetato anion derived from a β-ketoester, and
- le symbole L2 représente un ligand anionique différent de L1. the symbol L 2 represents an anionic ligand different from L 1 .
Des exemples de ce type de catalyseurs sont décrits dans la demande internationale WO-2009/106723. Par exemple, on pourra choisir le catalyseur (E) parmi les composés suivants :Examples of this type of catalyst are described in the international application WO-2009/106723. For example, the catalyst (E) may be selected from the following compounds:
(A10): Zn(DPM)2 ou [Zn {t-Bu-acac)2] avec DPM= (t-Bu-acac) = l'anion 2,2,6,6- tétraméthyl-3,5-heptanedionato ou l'anion énolate de la 2,2,6,6-tétraméthyl-3,5- heptanedione, (A10): Zn (DPM) 2 or [Zn (t-Bu-acac) 2 ] with DPM = (t-Bu-acac) = 2,2,6,6-tetramethyl-3,5-heptanedionato anion or the enolate anion of 2,2,6,6-tetramethyl-3,5-heptanedione,
(A11): [Zn (EAA)2] avec EAA = l'anion éthyle acétoacétato ou l'anion énolate de l'éthyle acétoacétate, (A11): [Zn (EAA) 2 ] with EAA = ethyl anion acetoacetate or enolate anion of ethyl acetoacetate,
(A12): [Zn (iPr-AA^] avec iPr-AA = l'anion isopropyle acétoacétato ou l'anion énolate de l'isopropyle acétoacétate, et
(A12): [Zn (iPr-AA4) with iPr-AA = the isopropyl acetoacetate anion or the enolate anion of isopropyl acetoacetate, and
Ce catalyseur présente l'avantage d'être liquide à température ambiante (25°C) et soluble dans des solvants organiques, même dans des alcanes, et dans les huiles silicones. This catalyst has the advantage of being liquid at ambient temperature (25 ° C.) and soluble in organic solvents, even in alkanes, and in silicone oils.
De préférence, l'agent tannant T est un agent minéral, de préférence un sel de chrome. Par exemple, on peut utiliser un chlorure ou un sulfate de chrome qui, dans des conditions acides, pénètre dans la structure du cuir. Les sels de chrome forment un complexe avec des groupes carboxyliques des protéines de la peau à traiter au cours de l'étape ultérieure de basification. Lorsque l'on effectue un tannage, le traitement au chrome est préférée au traitement aux extraits végétaux, car il confère de meilleures propriétés chimiques et physiques et, de plus, il permet d'améliorer la résistance à l'hydrolyse thermique et aux micro-organismes. Preferably, the tanning agent T is a mineral agent, preferably a chromium salt. For example, chromium chloride or sulphate can be used which, under acidic conditions, penetrates into the structure of the leather. The chromium salts form a complex with carboxylic groups of the proteins of the skin to be treated during the subsequent basification step. When tanning is carried out, chromium treatment is preferred over vegetable extracts because it gives better chemical and physical properties and, in addition, it improves the resistance to thermal hydrolysis and microorganisms. organizations.
Lorsque la composition (E) est sous forme d'émulsion, elle peut-être préparée de façon conventionnelle par mise en oeuvre des méthodes classiques de l'état de la technique. L'émulsification peut être directe ou par inversion. Pour l'émulsification directe, le procédé consiste à mettre en émulsion dans une phase aqueuse contenant un tensioactif et les constituants de la composition (E). On obtient directement une émulsion huile dans eau. Puis les constituants manquants peuvent être ajoutés, soit directement à l'émulsion (cas des constituants hydrosolubles), soit ultérieurement sous la forme d'émulsion (cas des constituants insolubles dans la phase aqueuse). La granulométrie de l'émulsion obtenue précédemment peut être ajustée par les méthodes classiques connues de l'homme du métier, notamment en poursuivant l'agitation dans le réacteur pendant une durée adaptée. La préparation de la composition (E) est mise en oeuvre à température ambiante. De préférence, on limite l'élévation de température qui peut résulter des étapes de broyage ou d'agitation. Notamment, on préfère rester en deçà de 60 ou 65° C.
Il est particulièrement avantageux que l'addition de ladite composition E se fasse avant, simultanément ou juste après l'addition d'au moins une partie de l'agent tannant T lors de l'étape de tannage ou de retannage. When the composition (E) is in the form of an emulsion, it may be prepared conventionally using standard methods of the state of the art. Emulsification can be direct or by inversion. For direct emulsification, the process consists of emulsifying in an aqueous phase containing a surfactant and the constituents of the composition (E). An oil-in-water emulsion is obtained directly. Then the missing constituents can be added, either directly to the emulsion (case of water-soluble constituents), or later in the form of emulsion (case of constituents insoluble in the aqueous phase). The particle size of the emulsion obtained above can be adjusted by conventional methods known to those skilled in the art, in particular by continuing the stirring in the reactor for a suitable period. The preparation of the composition (E) is carried out at room temperature. Preferably, the temperature rise that can result from the grinding or stirring steps is limited. In particular, it is preferred to remain below 60 or 65 ° C. It is particularly advantageous that the addition of said composition E takes place before, simultaneously with or just after the addition of at least a part of the tanning agent T during the tanning or retanning step.
Ainsi un autre objet de l'invention consiste en un procédé de préparation d'un cuir comprenant une étape de tannage, de retannage ou de tannage et retannage, selon l'invention et tel que décrit ci-dessus. Thus another object of the invention is a method of preparing a leather comprising a step of tanning, retanning or tanning and retannage, according to the invention and as described above.
Ainsi, après l'étape de tannage selon l'invention, on soumet la peau à traiter à une étape de neutralisation. La neutralisation a pour objectif de donner aux peaux un pH approprié avant qu'elles ne soient soumises aux opérations de retannage, séchage et nourriture en bain (graissage) au cours de laquelle il se produit une réticulation du chrome avec des groupes carboxyliques présents dans le collagène de la peau à traiter. Cette peau tannée est connue dans la technique sous Thus, after the tanning step according to the invention, the skin to be treated is subjected to a neutralization step. The purpose of the neutralization is to give the skins an appropriate pH before they are subjected to retanning, drying and bathing (lubrication) operations, during which chromium is cross-linked with carboxylic groups present in the skin. Collagen of the skin to treat. This tanned skin is known in the art under
l'appellation "cuir bleu humide". the name "wet blue leather".
Ensuite, on soumet le cuir à l'étape de retannage standard ou selon l'invention. Cette étape de retannage permet: Then, the leather is subjected to the standard retannage step or according to the invention. This retannage step allows:
- d'améliorer le toucher des cuirs et leur donner « la main », - improve the touch of the leather and give them "the hand",
- de remplir les parties plus souples et plus distendues du cuir afin de produire des cuirs aux propriétés physiques plus uniformes et dotés d'une valeur de découpe plus économique pour le client, - to fill the softer and more distended parts of the leather in order to produce leather with more uniform physical properties and with a more economical cutting value for the customer,
- de faciliter la production de cuir à fleur corrigée, - to facilitate the production of corrected flower leather,
- d'améliorer la résistance aux alcalins et à la transpiration, et to improve resistance to alkalis and perspiration, and
- d'améliorer la propriété de mouillage des peaux, ce qui facilitera le procédé de séchage. - To improve the wetting property of the skins, which will facilitate the drying process.
Puis afin de préparer un cuir fini, on procède aux étapes classiques que sont :Then to prepare a finished leather, we proceed to the classic steps that are:
- l'étape de teinture qui a pour objectif de produire des couleurs uniformes sur toute la surface de chaque peau (les colorants types sont des colorants acides aqueux), the dyeing step which aims to produce uniform colors over the entire surface of each skin (the typical dyes are aqueous acid dyes),
- l'étape de nourriture en bain ou graissage dans laquelle les cuirs doivent être graissés pour avoir les caractéristiques spécifiques du produit et pour rétablir la
teneur en graisse perdue au cours des étapes précédentes. Les huiles utilisées sont en général des huiles d'origine animale ou végétale, ou encore des huiles synthétiques à base d'huile minérale, et - the step of bathing or greasing food in which the leather must be greased to have the specific characteristics of the product and to restore the fat content lost in the previous steps. The oils used are in general oils of animal or vegetable origin, or synthetic oils based on mineral oil, and
- l'étape de séchage qui a pour objectif de sécher le cuir tout en optimisant la qualité et le rendement surfacique. Il existe un large éventail de techniques de séchage. - the drying step which aims to dry the leather while optimizing the quality and the surface yield. There is a wide range of drying techniques.
Le procédé selon l'invention permet de conférer au cuir de meilleures propriétés, à savoir un ton de coloration net, une pénétration satisfaisante des colorants, une lubrification du grain, une douceur, une souplesse, une extensibilité, une flexibilité et une robustesse. The process according to the invention makes it possible to confer on the leather better properties, namely a clean staining tone, satisfactory dye penetration, grain lubrication, softness, flexibility, extensibility, flexibility and robustness.
Un autre avantage de l'invention est d'empêcher un important épuisement de l'agent tannant hors du cuir traité, c'est-à-dire que la quantité de l'agent tannant (en particulier le chrome) passant dans l'effluent est considérablement réduite atténuant ainsi le problème que pose la pollution par les effluents du procédé. Another advantage of the invention is to prevent a significant depletion of the tanning agent from the treated leather, that is to say that the amount of the tanning agent (in particular chromium) passing into the effluent is greatly reduced, thereby mitigating the problem of process effluent pollution.
Un autre objet de l'invention consiste en des peaux caractérisées en ce qu'elles ont été tannées ou retannées par un procédé selon l'invention et tel que décrit ci- dessus. Another subject of the invention consists of skins characterized in that they have been tanned or retanned by a process according to the invention and as described above.
Enfin, l'un des dernier objet de l'invention consiste en un cuir caractérisé en qu'il a été préparé selon le procédé de l'invention tel que décrit ci-dessus. Les exemples suivants qui illustrent l'invention témoignent des excellentes propriétés lubrifiantes des compositions de l'invention. Finally, one of the last subject of the invention consists of a leather characterized in that it has been prepared according to the method of the invention as described above. The following examples which illustrate the invention demonstrate the excellent lubricating properties of the compositions of the invention.
EXEMPLES 1) Mode opératoire pour la préparation des émulsions : EXAMPLES 1) Procedure for the preparation of the emulsions:
Les émulsions sont préparées comme suit :
Dans un réacteur IKA®, une partie de l'eau, d'un tensioactif non ionique sont mélangés. Puis, Il est ajouté à ce mélange le ou les constituants à émulsionner sous agitation de manière à obtenir une émulsion huile dans eau ; et The emulsions are prepared as follows: In an IKA ® reactor, a portion of the water, a nonionic surfactant are mixed. Then, the mixture (s) to be emulsified with stirring is added to this mixture so as to obtain an oil-in-water emulsion; and
- en fin d'introduction du ou des constituant(s) et après homogénéisation, on procède à la dilution finale de l'émulsion. - At the end of introduction of the component (s) and after homogenization, the final dilution of the emulsion is carried out.
2) Préparation de 3 compositions (E1), (E2) et (E3) selon l'invention. 2) Preparation of 3 compositions (E1), (E2) and (E3) according to the invention.
Dans ces 3 compositions, les constituants sont ajoutés sous la forme d'émulsions qui sont préparées selon le mode opératoire décrit ci-dessus. In these 3 compositions, the components are added in the form of emulsions which are prepared according to the procedure described above.
Emulsion 1 (silicone aminé) : constitué de 51% en poids d'une huile silicone aminée Bluesil® 21648 (vendue par la société Bluestar Silicones). Emulsion 1 (amino silicone): consisting of 51% by weight of a Bluesil ® 21648 amino silicone oil (sold by Bluestar Silicones).
Emulsion 2 (SiH) : constitué de 50% en poids d'un copolymère à motifs (diméthyl)(hydrogénométhyl)polysiloxanes à extrémités hydrogénodiméthyles, Emulsion 2 (SiH): consisting of 50% by weight of a copolymer with (dimethyl) (hydrogenomethyl) polysiloxane units with hydrogenodimethyl ends,
Emulsion 3 (SiOH) : constitué de 42% en poids d'une Huile silicone poly(diméthyl)siloxane α,ω-dihydroxylée, viscosité = 135000 mPa.s à 25° C. Emulsion 3 (SiOH): consisting of 42% by weight of α, ω-dihydroxylated poly (dimethyl) siloxane silicone oil, viscosity = 135000 mPa.s at 25 ° C.
Emulsion 4 : constitué de 57% en poids d'un mélange comprenant une résine silicone MDT0H, le silane Silquest® VS142 (commercialisé par la société Momentive Performance Materials) et d'une émulsion d'un catalyseur (dilaurate de dioctylétain). Emulsion 4: consisting of 57% by weight of a mixture comprising a silicone resin MDT 0H , silane Silquest ® VS142 (marketed by Momentive Performance Materials) and an emulsion of a catalyst (dioctyltin dilaurate).
Composition (E1) = mélange de 25 parties en poids de l'Emulsion 1 + 15 parties en poids de l'Emulsion 2 + 5 parties en poids de l'Emulsion 3. Composition (E1) = mixture of 25 parts by weight of Emulsion 1 + 15 parts by weight of Emulsion 2 + 5 parts by weight of Emulsion 3.
Composition (E2) = mélange de 35 parties en poids de l'Emulsion 4 + 15 parties en poids de l'Emulsion 2 + 5 parties en poids de l'Emulsion 3. Composition (E2) = mixture of 35 parts by weight of Emulsion 4 + 15 parts by weight of Emulsion 2 + 5 parts by weight of Emulsion 3
Composition (E3) = mélange de 20 parties en poids de l'Emulsion 3 + 10 parties en poids de l'Emulsion 4. Composition (E3) = mixture of 20 parts by weight of Emulsion 3 + 10 parts by weight of Emulsion 4.
3) Procédé de tannage selon l'invention : 3) Tanning process according to the invention
On prend des peaux picklées qu'on introduit dans le foulon ainsi que l'agent de tannage minéral (sulfate de chrome). On effectue trois essais pour chaque We take pickled skins that are introduced into the fuller and the mineral tanning agent (chromium sulfate). Three attempts are made for each
composition selon l'invention [(E1 ), (E2) ou (E3)] ainsi qu'un essai comparatif effectué sans addition de la composition selon l'invention. On ajoute la composition selon l'invention (dans des quantités variées en poids) juste avant, simultanément
ou juste après l'addition de l'agent de tannage. Les conditions opératoires sont celles d'une étape classique de tannage. Puis les peaux suivent les étapes classiques d'un traitement d'un cuir. 4) Procède de retannaqe selon l'invention : composition according to the invention [(E1), (E2) or (E3)] and a comparative test carried out without addition of the composition according to the invention. The composition according to the invention (in various amounts by weight) is added just before, simultaneously or just after the addition of the tanning agent. The operating conditions are those of a conventional tanning step. Then the skins follow the classic steps of a leather treatment. 4) Retannaqe process according to the invention:
On prend des peaux ayant subies une étape de tannage classique que l'on introduit dans le foulon ainsi que l'agent de tannage minéral (sulfate de chrome). Les conditions opératoires sont celles d'une étape classique de retannage. On effectue trois essais pour chaque composition selon l'invention [(E1), ou (E2) ou (E3)] ainsi qu'un essai comparatif effectué sans addition de la composition selon l'invention. On ajoute la composition selon l'invention (dans des quantités variées en poids) juste avant, simultanément ou juste après l'addition de l'agent de tannage. Puis les peaux suivent les étapes classiques d'un traitement d'un cuir. 5) Résultats : We take skins having undergone a conventional tanning step that is introduced into the fuller and the mineral tanning agent (chromium sulfate). The operating conditions are those of a conventional retannage step. Three tests are carried out for each composition according to the invention [(E1), or (E2) or (E3)] and a comparative test carried out without addition of the composition according to the invention. The composition according to the invention is added (in various amounts by weight) just before, simultaneously with or just after the addition of the tanning agent. Then the skins follow the classic steps of a leather treatment. 5) Results:
On a prélevé des échantillons du cuir et de l'effluent, pour les procédés décrits aux paragraphes 3) et 4) décrit ci-dessus. On les a analysés pour en déterminer la teneur en oxyde de chrome et on les a comparés avec les résultats obtenus selon le même procédé mais sans l'ajout des compositions selon l'invention (E1), (E2) ou (E3). On observe qu'une plus grande quantité de chrome est fixée lorsqu'on utilise le procédé selon l'invention et que la quantité de chrome passant dans l'effluent est considérablement réduite. De plus, le cuir fini présentait des propriétés supérieures concernant les caractéristiques relatives au colorant et le toucher comparativement au témoin. Leather and effluent samples were taken for the processes described in paragraphs (3) and (4) described above. They were analyzed for their chromium oxide content and compared with the results obtained according to the same method but without the addition of the compositions according to the invention (E1), (E2) or (E3). It is observed that a greater amount of chromium is fixed when using the process according to the invention and that the amount of chromium passing through the effluent is considerably reduced. In addition, the finished leather had superior properties for dye and touch characteristics compared to the control.
L'invention n'est pas limitée aux exemples décrits et représentés, car diverses modifications peuvent y être apportées sans sortir de son cadre.
The invention is not limited to the examples described and shown, since various modifications can be made without departing from its scope.
Claims
REVENDICATIONS
1 - Procédé de tannage ou de retannage caractérisé en ce qu'une peau brute, un déchet de peau brute ou un article non tanné contenant du collagène est mis en contact en phase aqeuse comprenant : 1 - Tanning or retanning process characterized in that a raw hide, raw hide waste or an untanned article containing collagen is brought into contact in an aqueous phase comprising:
au moins un agent tannant T qui est un agent minéral, et au moins une composition silicone E qui est susceptible de former un élastomère silicone soit à température ambiante, soit par élévation de température, et de préférence la composition silicone E se présente sous la forme d'une émulsion silicone dans eau ou sous la forme d'une dispersion aqueuse de silicone, et at least one tanning agent T which is a mineral agent, and at least one silicone composition E which is capable of forming a silicone elastomer either at room temperature or by raising the temperature, and preferably the silicone composition E is in the form a silicone emulsion in water or in the form of an aqueous silicone dispersion, and
caractérisé en ce que les composants de la composition E sont choisis de manière à ce que ladite composition puisse former un élastomère silicone par des réactions de condensation, d'hydrosilylation ou de déshydrogénocondensation soit à température ambiante, soit par élévation de température . characterized in that the components of composition E are chosen so that said composition can form a silicone elastomer by condensation, hydrosilylation or dehydrocondensation reactions either at room temperature or by raising the temperature.
2 - Procédé de tannage ou de retannage selon la revendication 1 caractérisé en ce que l'addition de ladite composition E se fait avant, simultanément ou juste après l'addition d'au moins une partie de l'agent tannant T lors de l'étape de tannage ou de retannage. 2 - Tanning or retanning process according to claim 1 characterized in that the addition of said composition E is done before, simultaneously or just after the addition of at least part of the tanning agent T during the tanning or retanning stage.
3 - Procédé de tannage ou de retannage selon l'une quelconque des revendications précédentes dans lequel la composition E comprend en outre au moins un polyorganosiloxane (A) ayant des motifs siloxyles identiques ou différents de formule générale (I) : 3 - Tanning or retanning process according to any one of the preceding claims in which composition E further comprises at least one polyorganosiloxane (A) having identical or different siloxyl units of general formula (I):
R1a R2b Si 0 -(a+b)/2 (I) R 1 a R 2 b If 0 -(a+b)/2 (I)
dans laquelle: in which:
a = 0, 1 , 2 ou 3 ; b = 0, 1 , 2 ou 3 ; et a+b <3, les symboles R1 et R2 sont identiques ou différents et représentent chacun un radical monovalent choisi parmi le groupe constitué par un alkyle ayant de 1 à 40 atomes de carbone, de préférence un alkyle ayant de 1 à 6 atomes de carbone; un cycloalkyle ayant de 3 à 8 atomes de carbone; un
aryle, un alkylarylène, un arylalkylène, un groupe -OR3 avec R3= H ou un radical alkyle ayant de 1 à 40 atomes de carbone, et avec la condition que pour au moins deux motifs siloxyles, R1 ou R2 est un radical hydroxyle -OH ou alcoxy -OR2 avec R2 étant un alkyle ayant de 1 à 6 atomes de carbone. a = 0, 1, 2 or 3; b = 0, 1, 2 or 3; and a+b <3, the symbols R 1 and R 2 are identical or different and each represent a monovalent radical chosen from the group consisting of an alkyl having from 1 to 40 carbon atoms, preferably an alkyl having from 1 to 6 carbon atoms; a cycloalkyl having 3 to 8 carbon atoms; A aryl, an alkylarylene, an arylalkylene, an -OR 3 group with R 3 = H or an alkyl radical having from 1 to 40 carbon atoms, and with the condition that for at least two siloxyl units, R 1 or R 2 is a hydroxyl radical -OH or alkoxy -OR 2 with R 2 being an alkyl having 1 to 6 carbon atoms.
4 - Procédé de tannage ou de retannage selon la revendication 4 dans lequel la composition E comprend en outre au moins un polyorganosiloxane (A) qui est réactif par une réaction de condensation ou de déshydrogénocondensation et qui présente par molécule au moins deux groupements silanol (SiOH), et de préférence le polyorganosiloxane (A) a pour formule : 4 - Tanning or retanning process according to claim 4 in which composition E further comprises at least one polyorganosiloxane (A) which is reactive by a condensation or dehydrogenocondensation reaction and which presents per molecule at least two silanol groups (SiOH ), and preferably the polyorganosiloxane (A) has the formula:
formule dans laquelle n est un entier supérieur ou égal 2, R3 et R4, identiques ou différents, représentent: un alkyle ayant de 1 à 6 atomes de carbone; un cycloalkyle ayant de 3 à 8 atomes de carbone; un aryle, un alkylarylène ou un arylalkylène. formula in which n is an integer greater than or equal to 2, R 3 and R 4 , identical or different, represent: an alkyl having from 1 to 6 carbon atoms; a cycloalkyl having 3 to 8 carbon atoms; an aryl, an alkylarylene or an arylalkylene.
5 - Procédé de tannage ou de retannage selon la revendication 3 ou 4 caractérisé en ce que la composition E comprend en outre au moins un polyorganosiloxane (B) présentant par molécule au moins deux groupements hydrogénosilane SiH et de préférence au moins trois groupements hydrogénosilane SiH . 5 - Tanning or retanning process according to claim 3 or 4 characterized in that composition E further comprises at least one polyorganosiloxane (B) having per molecule at least two SiH hydrogenosilane groups and preferably at least three SiH hydrogenosilane groups.
6 - Procédé de tannage ou de retannage selon la revendication 5 dans lequel le polyorganosiloxane (B) comporte : 6 - Tanning or retanning process according to claim 5 in which the polyorganosiloxane (B) comprises:
• des motifs siloxyles de formule (11-1) : • siloxyl units of formula (11-1):
4 - ljd + é) 4 - ljd + é)
H d Le SiO H d L e SiO
2 2
(ii-D (ii-D
dans laquelle : in which :
- les groupes L, identiques ou différents, représentent chacun un groupe hydrocarboné monovalent et de préférence un groupe alkyle ayant de 1 à 8 atomes de carbone inclus, éventuellement substitué
par au moins un atome d'halogène, un groupes aryle et, avantageusement, un radical xylyle, tolyle ou phényle, - the groups L, identical or different, each represent a monovalent hydrocarbon group and preferably an alkyl group having from 1 to 8 carbon atoms inclusive, optionally substituted by at least one halogen atom, an aryl group and, advantageously, a xylyl, tolyl or phenyl radical,
- d est égal à 1 ou 2, e est égal à 0, 1 ou 2 et la somme (d+e) est égale à 1 , 2 ou 3, - d is equal to 1 or 2, e is equal to 0, 1 or 2 and the sum (d+e) is equal to 1, 2 or 3,
• éventuellement des motifs siloxyles de formule (H-2): g 2 • possibly siloxyl units of formula (H-2): g 2
(II-2) (II-2)
dans laquelle les groupements L ont la même signification que ci-dessus et g est égal à 0, 1 , 2 ou 3, in which the groups L have the same meaning as above and g is equal to 0, 1, 2 or 3,
• et avec la condition que le polyorganosiloxane (B) comporte au moins deux motifs siloxyles (11-1) et de préférence au moins trois motifs siloxyles (11-1 ). • and with the condition that the polyorganosiloxane (B) comprises at least two siloxyl units (11-1) and preferably at least three siloxyl units (11-1).
7 - Procédé de tannage ou de retannage selon l'une quelconque des revendications précédentes caractérisé en ce que la composition E comprend en outre au moins un polyorganosiloxane (C) et/ou au moins un silane (D) comprenant chacun au moins un groupement comprenant au moins un atome d'azote. 7 - Tanning or retanning process according to any one of the preceding claims characterized in that the composition E further comprises at least one polyorganosiloxane (C) and/or at least one silane (D) each comprising at least one group comprising at least one nitrogen atom.
8 - Procédé de tannage ou de retannage selon la revendication 7 caractérisé en ce que le polyorganosiloxane (C) comprend des motifs siloxyles identiques ou différents de formule générale: 8 - Tanning or retanning process according to claim 7 characterized in that the polyorganosiloxane (C) comprises identical or different siloxyl units of general formula:
R3 a R4b Si 04-(a+b)/2 (III) R 3 a R 4 b If 0 4-(a+b )/ 2 (III)
dans laquelle : in which :
- a = 0, 1 , 2 ou 3, b = 0, 1 , 2 ou 3, a+b < 3, - a = 0, 1, 2 or 3, b = 0, 1, 2 or 3, a+b < 3,
- les symboles R3 sont identiques ou différents et représentent chacun un radical hydrocarboné monovalent choisi parmi les radicaux alkyles ayant de 1 à 40 atomes de carbone, les radicaux -OR5 avec R5= H, et - the symbols R 3 are identical or different and each represent a monovalent hydrocarbon radical chosen from alkyl radicals having 1 to 40 carbon atoms, the -OR 5 radicals with R 5 = H, and
- les symboles R4 sont des radicaux identiques ou différents et représentent des radicaux de formule générale (IV) : - the symbols R 4 are identical or different radicals and represent radicals of general formula (IV):
-R6-N(R7)(R8) (IV) -R 6 -N(R 7 )(R 8 ) (IV)
dans laquelle: in which:
- le symbole R6 étant un groupement divalent hydrocarboné ayant de 1 à 40 atomes de carbone,
- le symbole R7 étant un atome d'hydrogène ou un groupement monovalent hydrocarboné ayant de 1 à 40 atomes de carbone, - the symbol R 6 being a divalent hydrocarbon group having from 1 to 40 carbon atoms, - the symbol R 7 being a hydrogen atom or a monovalent hydrocarbon group having from 1 to 40 carbon atoms,
- le symbole R8 étant un atome d'hydrogène ou un radical de formule (V) suivante: - the symbol R 8 being a hydrogen atom or a radical of formula (V) following:
-[R9-N(R10)]XR10 -[R 9 -N ( R 10 ) ]
- le symbole R9 étant un radical divalent de formule (VI) suivante : - the symbol R 9 being a divalent radical of formula (VI) below:
-[C(R 0)(R10)-]y -[C(R 0 )(R 10 )-] y
- formules dans lesquelles 0 < x < 40, y= 1 , 2 ou 3, et le symbole R10 est un atome d'hydrogène ou un groupement monovalent - formulas in which 0 < x < 40, y= 1, 2 or 3, and the symbol R 10 is a hydrogen atom or a monovalent group
hydrocarboné ayant de 1 à 40 atomes de carbone, et hydrocarbon having from 1 to 40 carbon atoms, and
- au moins un motif siloxyle porteur d'un groupement R4 est présent par molécule. - at least one siloxyl unit carrying an R 4 group is present per molecule.
9 - Procédé de tannage ou de retannage selon la revendication 1 caractérisé en ce que la composition E comprend : 9 - Tanning or retanning process according to claim 1 characterized in that composition E comprises:
- au moins un polyorganosiloxane (A) tel que défini selon la revendication 3 ou 4, - at least one polyorganosiloxane (A) as defined according to claim 3 or 4,
- au moins un polyorganosiloxane (B) tel que défini selon la revendication 5 ou 6,- at least one polyorganosiloxane (B) as defined according to claim 5 or 6,
- de l'eau (F) , - water (F),
- éventuellement au moins un tensioactif (G), et - optionally at least one surfactant (G), and
- éventuellement au moins un polyorganosiloxane (C) tel que défini selon la revendication 7 ou 8, et - optionally at least one polyorganosiloxane (C) as defined according to claim 7 or 8, and
- éventuellement au moins un silane (D) tel que défini selon la revendication 7. - optionally at least one silane (D) as defined according to claim 7.
10 - Procédé de tannage ou de retannage selon la revendication 1 caractérisé en ce que la composition E comprend : 10 - Tanning or retanning process according to claim 1 characterized in that composition E comprises:
a) au moins un polyorganosiloxane (A) qui est une résine organosilicique porteuses d'au moins deux groupes hydroxyles ou alcoxyles condensables et comportant au moins deux types de motifs siloxyles différents choisis parmi ceux de formule M, D, T et Q avec : a) at least one polyorganosiloxane (A) which is an organosilicic resin carrying at least two condensable hydroxyl or alkoxyl groups and comprising at least two different types of siloxyl units chosen from those of formula M, D, T and Q with:
- le motif siloxyle = (R°)3SiOi/2 ; - the siloxyl unit = (R°) 3 SiOi/2;
- le motif siloxyle D= (R°)2Si022 ; - the siloxyl unit D= (R°)2Si0 2 2;
- le motif siloxyle T= R°Si03/2, et - the siloxyl unit T= R°Si0 3 /2, and
- le motif siloxyle Q= SÏ04/2, et
- l'un au moins de ces motifs étant un motif T ou Q, - the siloxyl unit Q= SÏ04/2, and - at least one of these patterns being a T or Q pattern,
- formules dans lesquelles R° représente un groupement monovalent hydrocarboné ayant de 1 à 40 atomes de carbone ou un groupe - OR3 avec R3= H ou un radical alkyle ayant de 1 à 40 atomes de carbone, et ladite résine présentant une teneur pondérale en substituants hydroxyles ou alcoxy comprise entre 0,1 et 10% en poids par rapport au poids de la résine, et de préférence une teneur pondérale en substituants hydroxyles ou alcoxy comprise entre 0,2 et 5% en poids par rapport au poids de la résine, - formulas in which R° represents a monovalent hydrocarbon group having from 1 to 40 carbon atoms or a group - OR 3 with R 3 = H or an alkyl radical having from 1 to 40 carbon atoms, and said resin having a weight content in hydroxyl or alkoxy substituents of between 0.1 and 10% by weight relative to the weight of the resin, and preferably a weight content of hydroxyl or alkoxy substituents of between 0.2 and 5% by weight relative to the weight of the resin. resin,
b) au moins un catalyseur (E) de la réaction de condensation ou de déshydrogénocondensation tel qu'un sel d'étain, un dérivé de la guanidine, un dérivé du fer, ou un sel ou complexe métallique du zinc b) at least one catalyst (E) for the condensation or dehydrocondensation reaction such as a tin salt, a guanidine derivative, an iron derivative, or a zinc salt or metal complex
c) de l'eau (F), c) water (F),
d) éventuellement au moins un tensioactif (G), d) optionally at least one surfactant (G),
e) éventuellement au moins un polyorganosiloxane (C) tel que défini selon la revendication 7 ou 8, et e) optionally at least one polyorganosiloxane (C) as defined according to claim 7 or 8, and
f) éventuellement au moins un silane (D) tel que défini selon la revendication 7. f) optionally at least one silane (D) as defined according to claim 7.
11 - Procédé de tannage ou de retannage selon la revendication 1 caractérisé en ce que l'agent tannant T est un sel de chrome. 11 - Tanning or retanning process according to claim 1 characterized in that the tanning agent T is a chromium salt.
12 - Peaux caractérisées en ce qu'elles ont été tannées ou retannées par un procédé selon l'une quelconque des revendications précédentes. 13 - Procédé de préparation d'un cuir comprenant une étape de tannage, de retannage ou de tannage et retannage, telle que décrite selon l'une quelconque des revendications précédentes. 12 - Skins characterized in that they have been tanned or re-tanned by a process according to any one of the preceding claims. 13 - Process for preparing leather comprising a step of tanning, retanning or tanning and retanning, as described according to any one of the preceding claims.
14 - Cuir caractérisé en qu'il a été préparé selon le procédé décrit selon la revendication 13.
14 - Leather characterized in that it has been prepared according to the process described according to claim 13.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR11/03523 | 2011-11-18 | ||
| FR1103523 | 2011-11-18 |
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| Publication Number | Publication Date |
|---|---|
| WO2013072063A1 true WO2013072063A1 (en) | 2013-05-23 |
Family
ID=47216198
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2012/004773 WO2013072063A1 (en) | 2011-11-18 | 2012-11-16 | Method for tanning or retanning rawhide, rawhide scraps, or an untanned article containing collagen |
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| Country | Link |
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| WO (1) | WO2013072063A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103509887A (en) * | 2013-10-22 | 2014-01-15 | 陕西科技大学 | Nanocomposite-chrome powder combined retanning technology for two-layered cowhide suede leather |
| CN106119442A (en) * | 2016-06-30 | 2016-11-16 | 宁波市江东林清环保科技有限公司 | A kind of preparation method of leather fat |
| CN114667356A (en) * | 2019-12-09 | 2022-06-24 | 现代牧场股份有限公司 | Leather-like material comprising melt blended collagen and thermoplastic polymer |
| US11913166B2 (en) | 2015-09-21 | 2024-02-27 | Modern Meadow, Inc. | Fiber reinforced tissue composites |
| WO2024062184A1 (en) * | 2022-09-23 | 2024-03-28 | Ctc | Hide tanning process, method for preparing leather, and detanning process |
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| CN103509887A (en) * | 2013-10-22 | 2014-01-15 | 陕西科技大学 | Nanocomposite-chrome powder combined retanning technology for two-layered cowhide suede leather |
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| US11913166B2 (en) | 2015-09-21 | 2024-02-27 | Modern Meadow, Inc. | Fiber reinforced tissue composites |
| CN106119442A (en) * | 2016-06-30 | 2016-11-16 | 宁波市江东林清环保科技有限公司 | A kind of preparation method of leather fat |
| CN114667356A (en) * | 2019-12-09 | 2022-06-24 | 现代牧场股份有限公司 | Leather-like material comprising melt blended collagen and thermoplastic polymer |
| WO2024062184A1 (en) * | 2022-09-23 | 2024-03-28 | Ctc | Hide tanning process, method for preparing leather, and detanning process |
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