CN104334746A - Composition and process for the retanning and fatliquoring of leather, and the leather prepared - Google Patents
Composition and process for the retanning and fatliquoring of leather, and the leather prepared Download PDFInfo
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- CN104334746A CN104334746A CN201380026549.1A CN201380026549A CN104334746A CN 104334746 A CN104334746 A CN 104334746A CN 201380026549 A CN201380026549 A CN 201380026549A CN 104334746 A CN104334746 A CN 104334746A
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- phosphatide
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
- C14C3/18—Chemical tanning by organic agents using polycondensation products or precursors thereof
- C14C3/20—Chemical tanning by organic agents using polycondensation products or precursors thereof sulfonated
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
- C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring
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- Oil, Petroleum & Natural Gas (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The present invention relates to compositions for the retanning and fatliquoring of pre-tanned leather, to the process of preparing such compositions, to the use of these compositions for the preparation of leather (the term ''leather'' encompassing fur skins or pelts), as well as a novel type of leather that is obtainable by the use of these compositions.
Description
The present invention relates to retanning and the stuffing composition of pretan leather, prepare the method for this composition, with the purposes (term " leather " contain fur or animal skin) of these compositions for the preparation of leather, and by using the leather of the obtainable novel type of these compositions.
Leather is the durable flexible material generated by tanned animal hide and fur.The manufacturing process of leather is divided into three basic subprocess: preparation section, tanning and half nitre process (crusting).
The present invention relates to the subprocess of half nitre process.In preparation section, prepare animal skin or fur for tanning.After trimming, soaking animal fur, except desalting and other solids, recovering humidity simultaneously, when fur is first dry.Then, the human body side of scraping method for wet skins, to remove any residual trace human body or fat, and optionally makes fur alopecia.After optional softening and acid soaking step, tanning is carried out to fur.Other possible steps that may become a part for preparation section comprise anticorrosion, liming, division, multiple liming, deliming, degreasing, frizing, bleaching and depickling.
Tanning is by soaking fur for some time in bath, making the process of preserving furs.Especially, tanning makes the protein in rawhide or fur, becomes imputrescible stable material with collagen turnover especially.By using or phytochemical, use tannin and by plant material, other compositions that such as some bark set is derivative, by using chromic salts (obtaining the so-called-blue coloured leather that wets), by using aldehyde (causing wetting-white leathers), by using syntannin (synthetic tanning agent), or other routine techniquess, carry out tanning.The product prepared in this subprocess is called as " pretan leather ".
As noted, the present invention concentrates on the subprocess of half nitre process, and especially in its chemical aspect.Half nitre process be wherein animal skin or fur thinning, the process of retanning and lubrication.Usual shading operations is included in half nitre process subprocess.Any chemical used in half nitre treating processes or add must fixation in situ.Half nitre treating processes terminates in dry and softening operation.This description of half nitre treating processes is incomplete; Half nitre process also can comprise rewetting, water squeezing, and division, shaves hair, multiple chromium process, and neutralization, fills, filling, and peeling, brightens, fixing, solidifies, and regulates, grinding, rivet clasp and polishing.
The chemical aspect of half nitre treatment process at least contains retanning (optionally after being neutralized, especially after chrome tanning) and stuffing.Usually preparing in leather by pretan animal skin, carrying out retanning and stuffing in a separate step.
The object of retanning produces collagenous network stable further.This involves the collagenous network of processing stabilization further and can comprise further tanning (such as, adopting chromium, plant, the combination of glutaraldehyde or synthetic tanning agent), when requiring special feature, such as, during perspiration resistance.Also can regulate, softening, dyeing or bleaching.
The soft leather of any kind contains the fat of overhang (such as 5-20%).Fat is the basis of leather flexibility, and it is said that flexibility is because leather fiber is separated from one another.Be coated with the fibre element dewatered by tanning with lipid layer, by certain lubrication, obtain the leather of desired softness and feel; This coating with fat is called as stuffing.Fat prevents fiber and is clamminess, and gummed or bonding, although some fiber separation is undertaken by tanning.Meanwhile, stuffing affects the physicals of leather, such as extendability, tensile strength, wettability, water-repellancy, and the perviousness of air and water vapour.
Routinely, stuffing is very complicated technique, and this depends on many factors.
A kind of such factor is the temperature of bath of liquid.Along with temperature increases, little fat particle stablizes resist coagulation more.On the other hand, more given prominence to by fixed fat on the charged group that is bonded to the animal fur processed.Usually, temperature is 60 DEG C, and low temperature is about 35 DEG C.Temperature is lower, and the absorption of fat is lower; But the distribution of fat is more even.
The pH of leather and liquid floating material adding interested further factor in resin system.The chrome leather of chrome leather and retanning causes having sufficiently high pH, to maintain charged group.The group of such as sulfate radical, sulfonate radical and phosphate radical and so on only can serve as tensio-active agent under neutral condition.Treat tanning, pH that the leather of dyeing and stuffing needs neutralization in advance to about 5.5.After stuffing, must acidifying floating matter to about 4.5 or pH lower a little, to fix all objects at fiber place.
In the leather preparation of the handwork of routine, neutralization, retanning and fixing step require to use usually about 15 or the chemical of the even higher quantity of polyvoltine compound, and these steps spend about 8-16 hour.The technique of this routine will be set forth in comparative example 2 herein.
Clearly need the quantity reducing required chemical in this area, to save water (and/or other solvents) amount required in leather preparing process, and save use energy (at using appts with in both transports).
In view of this demand, with reference to US-A-6,033,590.This United States Patent (USP) describes the composition allowing retanning simultaneously and stuffing leather or fur, thus has caused total process time in the situation of practice significantly to drop to about 5-6 hour.Especially, at US-A-6,033, it is the composition of solid that the composition described in 590 utilizes at lower than the temperature of 40 DEG C, and it comprises (a) 10-18wt% retanning agent; (b) 5-50wt% fatting agent; Optionally (c) 0-55wt% neutralizing agent; (d) be selected from carrier, tinting material, soaker, modifier and the extra optional component of modifying in auxiliary agent, wherein each is based on the gross weight of composition; The existence form of described composition makes at 10-60 DEG C, and when adding in described composition to water, its consumption causes the ratio of water and said composition at least 8:1, and described composition forms uniform mixture in water.
Suitable fatting agent be it is said " leather greasing conventional conventional reagent " and be preferably based on the fatting agent of animal tallow; Based on the fatting agent of vegetation fat; Synthetic fat liquor; Mineral oil and other petroleum chemicals.
Preferably, retanning agent, fatting agent and any other additive are used as solution or suspension or other dispersion liquid, and then mix these, then dry and spraying dry especially.
Although recognize compared with common process, key step has improvement, but find, at US-A-6,033, the composition described in 590 still has the space of improvement: the leather prepared with it still suffers swelling significantly, and gained leather hand touches or feels not soft, and extra fat liquid must be added, could supple leather be obtained; The method obtaining composition with use spraying dry is troublesome.
The object of this invention is to provide a kind of composition, it also allows in one step, but still retanning and stuffing within the shorter time period.In addition, the object of this invention is to provide the leather prepared with routine or according to US-A-6, leather prepared by the instruction of 033,590 is compared, and causes having less swelling, has compared with high-tear strength and/or the composition had compared with the leather of high tensile and method.And, expect to have the composition of the leather that causes obtaining in the method than described United States Patent (USP) supple leather more.
According to the present invention, when formed by phosphatide at least partially fatting agent time, discovery can meet one or more above-mentioned purpose.That is, according to the present invention, fatting agent can be made up of 100% phosphatide, but also useful when being accounted for total amount 10-50wt% fatting agent by phosphatide formation.The OK range of the phosphatide existed in 10-50wt% fatting agent is at least 50wt% (accounting for the weight of fatting agent) phosphatide, preferably at least 60wt%, more preferably at least 70wt%, maximum 100wt% phosphatide.
Therefore, in a first aspect, the present invention relates to the composition of retanning and stuffing pretan leather, said composition comprises:
A () accounts for the retanning agent of total composition 30-80wt%;
B () accounts for the fatting agent of total composition 10-50wt%, described fatting agent comprises at least 50wt% (accounting for the weight of fatting agent) phosphatide, preferably at least 60wt%, more preferably at least 70wt%, maximum 100wt% phosphatide; With
C () optionally, surplus reaches the non-retanning agent of 100wt% total composition and other half nitre process chemical of fatting agent.
Preferred weight range is the retanning agent of 40-70wt% (accounting for total composition) and the fatting agent of 15-40wt%.
In preferred embodiments, the phosphatide being used as (part) fatting agent is solid under the temperature of 25 DEG C (normal atmosphere and) at ambient conditions.In a more preferred embodiment, the whole fatting agents used are solid at ambient conditions.
In another preferred embodiment, retanning agent is solid at ambient conditions.
Other half nitre process chemical of non-retanning agent and fatting agent can be selected from US-A-6, and 033, the identical neutralizing agent of instruction in 590 and additive, but also contain inert fill material, and the moisture of trace.
The suitable material of these other half nitre process chemical of non-retanning agent and fatting agent is carrier, tinting material, soaker, modifier and modify auxiliary agent, an alkali metal salt of inorganic and organic monoacid, aromatic sulfonic acid and aliphatic series list-or dicarboxylic acid.Preferably, other half nitre process chemical of non-retanning agent and fatting agent are selected from complexing agent, carrier, Conventional dye, tensio-active agent, and stablizer.In further embodiment, these other optional components (c) are solid at ambient conditions.
In very favorable embodiment, composition of the present invention is solid at ambient conditions.This solids composition can be powder type.
Further, the present invention relates to the method preparing the present composition, the method comprises its component of mixing.In a preferred embodiment of the present methods, each composition is solid at ambient conditions and mixes in solid form.This embodiment can cause dry powder.In this preferred embodiment of the present invention, wherein obtain composition by the solid ingredient of the preferred powder type of mixing, do not require US-A-6,033, spraying dry in 590, the composition of described prior art by the component of mixed dissolution, these mixtures of the dry gained of subsequent spray and obtaining.Compared with using the preparation of spray-drying process in described United States Patent (USP), preferred preparation method's ratio of the present composition is easier to carry out.
Further, the present invention relates to the purposes of retanning and stuffing pretan leather, fur, fur, animal skin, leather intermediate product or non-arrangement leather composition.Or the present invention relates to the method for retanning or stuffing pretan leather, fur, fur, animal skin, leather intermediate product or non-arrangement leather, the method comprises the step process with composition according to the present invention.
When prepared by pretan leather use in leather time, composition of the present invention provides both retanning and stuffing, and cause in this preparation technology, touch with hand or soft feel and have unusual good tear strength and swelling be less than 20% and be preferably less than 18% leather.
The technician being familiar with the field that the present invention relates to is touched/feels by (with hand) and it compared with other materials/referential matter routinely, determines pliability.
The leather swelling 10 to 40% of conventional preparation, this depends on the type of pretan leather.According to US-A-6,033,590 preparation leathers show 20% to 40% swelling.By comparing the thickness (unit: mm) of leather before and after retanning and stuffing technique, measure swelling.Less swelling advantage is, before retanning and stuffing technique, less leather must be scraped, and obtains similar leather thicknesses after the process, thus after the process, causes lower refuse amount, and higher leather fiber density.
For the high-quality leather of the present invention, requirement is according to ISO 3377-1:2002, and monolateral tear strength is equal to or higher than 25N, according to ISO 3377-2:2003, bilateral tear strength is equal to or higher than 80N, and according to ISO 3376:2002, higher than the overall loading of 120N under this tensile strength.
Under the relative humidity (RH) of 40-45%RH and at the temperature of 22 DEG C, use sample " standard substance ", thus use these iso standards.
By being prepared in leather the leather that adopts composition of the present invention to obtain by pretan leather than by adopting US-A-6, the leather that the composition described in 033,590 and operation obtain is much soft.This is set forth in this paper operational example described below, wherein set forth embodiments of the invention and do not require extra ripening agent, to obtain soft leather (that is, the pliability of leather prepared by the routine that leather has description in comparative example 3), and need extra ripening agent to obtain soft leather, as use US-A-6, when the composition of 033,590 and operation.
Further, by being prepared in leather the leather that adopts composition of the present invention to obtain by pretan leather than by adopting US-A-6,033, the leather that the composition described in 590 and operation obtain is solid, this by operational example relatively in, for herein both the following tear strength that measures and tensile strength are set forth.
And, by being prepared in leather the leather that adopts composition of the present invention to obtain by pretan leather than by adopting US-A-6, the swelling much less of the leather that the composition described in 033,590 and operation obtain.
In in further, therefore the present invention relates to can be produced according to the present invention, and compared with the leather known with prior art, has the leather products of the unique combination of swelling, tear strength, tensile strength and/or pliability.
Composition and method of making the same of the present invention relative to the progressively retanning of routine and ageing process with relative to US-A-6,033, the composition described in 590 and the major advantage of preparation method have at least following:
By being prepared in leather the leather that adopts composition of the present invention to obtain by pretan leather than by adopting conventional method or by adopting US-A-6, the leather that the composition described in 033,590 and operation obtain is solid.This strength improving is measured for both stretching and tear strength.Especially, leather of the present invention has by ISO 3377-1:2002 (RH 40-45%; T=22 DEG C) the monolateral tear strength of at least 25N that measures, but in fact at least 40N and even at least 50N.In addition, it has according to ISO 3377-2:2003 (RH 40-45%; T=22 DEG C) the bilateral tear strength of at least 60N that measures, but in fact at least 70N and even at least 80N.In addition, it has according to ISO 3376:2002 (RH 40-45%; T=22 DEG C) at least 100N under this tensile strength that measures, but the overall loading of in fact at least 120N and even at least 140N.
By being prepared in leather the leather that adopts composition of the present invention to obtain by pretan leather than by adopting conventional method or by adopting US-A-6, the swelling much less of the leather that the composition described in 033,590 and operation obtain.
With US-A-6,033,590 compare, gained leather more soft (or the method for described United States Patent (USP) requires more fatting agent).
Leather preparation method of the present invention relative to the progressively retanning of routine and currying and US-A-6,033, the additional advantage of the method described in 590 is, it does not require the time many like this.Compared with the method for routine, by obtaining within the process period of much shorter being prepared in leather the leather adopting composition of the present invention to obtain by pretan leather, also same and US-A-6,033, the method of 590 is compared, and obtains temporal gain (time gain).And, obtain the saving of water and quantity of energy.
By way of parenthesis, teach in US-A-2007/021552 based on natural quasi-ester, the specific stuffing dispersion of at least one (methyl) acrylate copolymer and following emulsifier composition can produce pliability, and described emulsifier composition is containing useful maximum 12 oxyalkylated C of oxyalkylene units
6-17the mixture of-alkanol or two or more this alkanols and with at least 15 oxyalkylated C of oxyalkylene units
12-24fatty alcohol mixture.
Further, the castor-oil plant oil-base fat liquid emulsion that The Journal of the American Leather Chemis ts Associat ion 86 (1991), 159-165 describes modification in the article of the people such as Baskar can be used for preparing the lightweight leather of flexible types.
As described hereinabove, composition of the present invention requires to there is 30-80wt% retanning agent.
The retanning agent used in the present invention can be natural or synthesis source.
Suitable example is conventional compound, such as vegetable tanning agent, aromatics synthetic tanning agent, resin tanning agent, reactive tanning agent and Polymer Tanning Agent.Preferred retanning agent is those of solid at ambient temperature and pressure.
The example of suitable vegetable tanning agent is those tanning agents, preferably but be not necessarily those of solid at ambient temperature, they are obtained by plant origin and belong to by condensation tanning agent or hydrolyzable tanning agent, the group that such as chestnut extract, Touch-me-notAction Plant, Oak Tree, tara or yaruru form.
Suitable aromatics synthetic tanning agent is those compounds, and preferably but be not necessarily those of solid at ambient temperature, they can be obtained by condensation sulfonated aromatic compound and formaldehyde and/or urea.
The example being suitable for the aromatic substance of this purpose is naphthalene, biphenyl, terphenyl, phenols, cresols class, 4,4'-dihydroxy diphenylsulphone, 2-Naphthol, dihydroxy-benzene class, Resorcinol, 2, two (hydroxyphenyl) propane of 2-and diaryl ether, such as phenyl ether and dibenzyl ether, they can be sulfonated.
Especially suitable anionic aromatic synthetic tanning agent is following compound: the phenol of (I) sulfonation or the condensation product of cresols and formaldehyde, (II) condensation product of naphthene sulfonic acid and formaldehyde, (III) 4, the formaldehyde condensation products of 4'-dihydroxyl-sulfobenzide and aryl sulfonic acid or (hydroxyl) aryl sulfonic acid, (IV) containing the aromatic hydroxy compound of sulfo group and the formaldehyde condensation products of aralkyl halogen, (V) the melocol condensation product of phenols and sulfocarbolic acid class, (VI) reaction product of phenol and sulphonating agent, wherein (phenol): (SO
3) ratio be (1): (1.1-2.2), (VII) condensation product of sulfonation diaryl ether and formaldehyde, (VIII) condensation product of sulfonated biphenyls or sulfonation terphenyl and formaldehyde, (IX) 4,4 of 4'-dihydroxy diphenylsulphone and sulfonation, the condensation product of 4'-dihydroxy diphenylsulphone and formaldehyde, (X) diaryl ether sulfonic acid and 4, the formaldehyde condensation products of 4'-dihydroxy diphenylsulphone, and the formaldehyde condensation products of (XI) phenol and aryl sulfonic acid or hydroxyaryisuffonic acids.
These condensation products are free acid form, such as sulphonic form, or as salt, ammonium salt especially, lithium, potassium or especially sodium salt.
The example of suitable resin tanning agent be organic compounds containing nitrogen (they preferably but inevitable be solid at ambient temperature, such as urea, thiocarbamide, Dyhard RU 100 or trimeric cyanamide) with those cationic condensation products of formaldehyde or other simple oxygen base-compounds.
Other suitable resin tanning agents are those anionic compounds, but be not necessarily those of solid at ambient temperature, wherein such as, when nitrogenous organic compound, urea, thiocarbamide, the condensation product of Dyhard RU 100 or trimeric cyanamide and formaldehyde or other simple oxygen base-compounds or and anionic compound, such as phenols, an alkali metal salt of aromatic sulfonic acid, sulphonamide, sulfonated lignin, obtain them when sulphite or hydrosulphite condensation.
Be the condensation product that the especially preferred resin tanning agent of solid is urea and formic acid at ambient temperature, and Dyhard RU 100-Ji resin tanning agent.
The example of suitable reactive tanning agent is those reactive tanning agents, they are preferably but inevitable be solid at ambient temperature, such as polyfunctional isocyanic ester, alkyl sulfonyl chloride, the alkylsulfonate of relative high molecule mass and monomer ethylene radical derivative and acrylate derivative and polymkeric substance thereof.
The example of the retanning agent of polymerization is polyacrylic ester, and containing the multipolymer of acrylate, urethane or polybutadiene, they are preferred, but must not be solid at ambient temperature.
Above-mentioned retanning agent is well known by persons skilled in the art and commercially available in large degree.
Except retanning agent, composition of the present invention also comprises and accounts for composition 10-50wt%, with the ripening agent of preferred 15-40wt%, described ripening agent comprises the phosphatide of at least 50wt% (accounting for ripening agent weight), preferred at least 60wt%, more preferably at least 70wt%, maximum 100wt% phosphatide.
Preferred ripening agent is those of solid at ambient temperature and pressure.
The suitable phosphatide used in ripening agent contains the fatty acid ester being selected from phosphorylcholine, and those phosphatide in the fatty acid ester of the mixture of polyvalent alcohol, lipid acid and phosphorylcholine, these phosphatide are preferred, but uninevitable is solid at ambient conditions, wherein polyvalent alcohol is trivalent alcohol, dibasic alcohol or erythritol.
The example of suitable phosphatide is l-hexadecanoyl-3-glycerophosphoryl choline, N, N; N-trimethylammonium-2-(phosphonato) ethyl chloride, choline-glycerophosphate, l; 2-bis-myristoyl-3-Yelkin TTS, Phosphorylcholine disodium, Phosphorylcholine-calcium chloride; two palmitoyl-Yelkin TTS, dilauroyl-phosphatidylcholine, two oil bases-Yelkin TTS; distearyl acyl group phosphorus choline (fosfocholine); palmitoyl-oil base-Phosphorylcholine, sphingophospholipid, and ceramide etc.
The preferred embodiment of these ripening agents contains natural or synthetic phospholipid, dialkyl group Phosphorylcholine, phosphatidylethanolamine, phosphatidylinositols and Yelkin TTS.
If adoptable words, the fatting agent of fatting agent by commonly using of surplus, such as, based on animal tallow, such as fish oil, neat's foot oil, the fatting agent of lanolin or lard; Based on vegetation fat, such as Viscotrol C, the fatting agent of cocounut oil or sweet oil; Synthetic fat liquor, the chlorination of such as paraffins and the product of chlorosulphonation, Acrawax and ester oil; Formed with mineral oil and other petroleum chemicals.
These fatting agents preferably use in powder form.The surplus of the present composition, is formed by other half nitre process chemical of non-retanning agent and fatting agent as noted.These half nitre process chemical (c) can be selected from and US-A-6, and 033, the identical neutralizing agent of instruction in 590 and additive, but also contain the moisture of inert fill material and trace.The suitable material of these other half nitre process chemical of non-retanning agent and fatting agent is carrier, tinting material, soaker, modifier and modify auxiliary agent, an alkali metal salt of inorganic and organic monoacid, aromatic sulfonic acid and aliphatic series list-or dicarboxylic acid.Preferably, other half nitre process chemical of non-retanning agent and fatting agent are selected from complexing agent, carrier, Conventional dye, tensio-active agent, and stablizer.In further preferred embodiment, these other optional components (c) are solid at ambient conditions.
In further detail, suitable other components (c) this can comprise complexing agent, carrier, Conventional dye, tensio-active agent, stablizer; Be preferably solid form.
The example of this complexing agent is polyphosphoric acid salt, Trisodium Citrate, sodium-potassium tartrate and sodium oxalate.
The example of this carrier is sodium-chlor, Sodium sulfate anhydrous.min(99) (Glauber salt), sodium bicarbonate, sodium formiate, protein powder, starch, kaolin, polysaccharide, glucose or gelatin.
The example of this dyestuff is acridine dye, anthraquinone dye, triarylmethane colouring matters, triarylmethane dye, azoic dyestuff, diazol colors, metal complex dyes, nitro-dye, nitroso-dye, phthalocyanine pigment, quinone-imide dye, pyridine dye, euihodine coloring matters, Stigma Croci dyestuff, indophenol dye
piperazine dyestuff,
piperazine ketone dyes, thiazine dyes, thiazole dye, xanthene dye, fluorenes dyestuff, pyronin dyestuff, fluorone dyes and rhodamine dyes.
The example of this stablizer is oxidation inhibitor, photostabilizer and thermo-stabilizer.
These other components preferably use equally in powder form.
By mixing independent component simply in a kind of mixture, the retanning of preparation pretan leather and stuffing composition.Although this can be in solvent or solvent mixture, preferably when these are solid form, mix each component.Can at ambient temperature, namely about 10 DEG C to 40 DEG C at mix, and mixing can utilize the obtainable equipment of all kinds.
The retanning of pretan leather and stuffing composition are suitable for preparing inhomogeneous leather and fur.Use these compositions, can such as, for the preparation of the leather of all application, footwear, furniture, automobile, cloth and bag leather.
Said composition can for the preparation of leather in the machine that wet method modifies all routines that leather uses.
Said composition can be used, such as by the temperature of 10-40 DEG C, in vat, wet-white leathers sheet and the water accounting for leather dry weight 100-200wt% are put together, then the composition of the present invention accounting for leather dry weight 5-50wt% is added, at 10-40 DEG C, soak this mixture 30-100 minute subsequently, thus prepare leather.After this step, followed by adding the water accounting for 30-70 DEG C of leather dry weight 100-300wt%, with after 2-10 minute, add 0.5-3% (routine) laking agent, such as formic acid or acetic acid, then after 2-30 minute, add the laking agent of other 1-3%.After 10-60 minute, discharge liquid, and the cold water washing leather using 100-400% subsequently.
After this preparation process, optionally dry leather arranging.
By following non-limiting operational example, set forth the present invention further.The number of each component mentioned in these operational example and per-cent account for the weighing scale of total composition, wherein there are these components, just look like that other components are in the specification and in the claims the same, except as otherwise noted.
Embodiment 1
At room temperature mix the melocol condensation product (Renektan of the sulfonaphthol of 50 parts by weight of powder forms
ex Stahl Europe B.V., The Netherlands) as retanning agent, the solid Yelkin TTS of 25 parts by weight of powder forms, the sodium bicarbonate of 5 parts by weight of powder forms as carrier, obtains composition A as the kaolin of carrier and 20 parts by weight of powder forms.
Embodiment 2
At the temperature of 25 DEG C, will based on shaving weight, thickness be a slice of 1.5mm wet-white leathers is placed in suitable vat (vat) together with accounting for the water of wet-white leathers weight 150%, and add the composition A from embodiment 1 accounting for wet-white leathers weight 25wt%, and at 25 DEG C, soak this mixture 50 minutes.Then, add the water of 200wt%50 DEG C, and after five minutes, add 1.5wt% formic acid, then after 10 min, add other 1.5wt% formic acid.After 30 minutes, discharge this bath, and use 200wt% cold water washing leather subsequently.Gained leather hangs horse and toggling or vacuum-drying subsequently.
Process period total in vat is about only 2 hours.The thickness of gained leather is 1.6mm.In this technological process, therefore the thickness of leather be increased to 1.6mm from 1.5mm.This leather has soft sense of touch.
Embodiment 3 (setting forth the comparative example of conventional half nitre treatment process)
Will based on shaving weight, a slice being 1.3mm with the thickness of the identical type used in embodiment 2 wets-and white leathers is placed in vat together with the water of 30 DEG C of 200wt%.After 10 minutes, discharge this bath.Subsequently, add the water that 100wt% temperature is 30 DEG C, then add 1.5wt% glutaraldehyde, and after other 20 minutes, then add the melocol condensation product of 5wt% sulfocarbolic acid as synthetic tanning agent (Renektan
), and then after another 30 minutes, add 3wt% fish oil as fatting agent.After 20 minutes, discharge floating matter.Then, add water and the 1wt% sodium formiate of 100wt% together, after 20 minutes, then add 0.5wt% sodium bicarbonate, after 60 minutes, then add 3wt% and also containing the polyester dispersions (Corilene in the water of some vegetables oil
available from Stahl Europe B.V. Holland), after 20 minutes, then add the identical fatting agent of 8wt%, after 15 min, then add the melocol condensation product of 20wt% sulfocarbolic acid as synthetic tanning agent (Renektan
), then after 20 minutes, add 2wt% azoic dyestuff, after 50 minutes, then add the identical fatting agent of 3wt%, after 30 minutes, then add the melocol condensation product of 6wt% sulfocarbolic acid as synthetic tanning agent (Renektan
), and after 10 min, then add 4wt% tara (tara).
After process in 60 minutes, add the water that 50wt% temperature is 50 DEG C.Heat this mixture to 45 DEG C, and after 10 min, add the fatting agent that 10wt% is identical, after 60 minutes, add 1.5wt% formic acid, then after 10 min, add other 1.5wt% formic acid.After 30 minutes, discharge this bath, and use 200wt% cold water washing leather subsequently, after 10 min, then add 1wt% formic acid as laking agent.After 20 minutes, discharge liquid, and use 200wt% cold water washing leather subsequently.Gained leather hanging horse and toggling grind subsequently.
Process period total in vat is about 11 hours.The thickness of gained leather is 1.7mm.In this technological process, therefore the thickness of leather be increased to 1.7mm from 1.3mm.This leather has and pliability like the leather-like of embodiment 2.
Embodiment 4 (setting forth US-A-6, the comparative example of 033,590)
Substantially use US-A-6,033, the composition described in embodiment 7 of 590, processes based on shaving weight, and a slice being 1.3mm with the thickness of the identical type used in embodiment 2 is wet-white leathers.A slice is wet-white leathers with account for wet-white leathers weight 150% temperature 25 DEG C water together be placed in suitable vat, add the US-A-6 accounting for wet-white leathers weight 25wt%, the composition of 033,590, and at 25 DEG C, soak this mixture 50 minutes.Then, add the water of 200wt%50 DEG C, and after five minutes, add 1.5wt% formic acid, then after 10 min, add other 1.5wt% formic acid.After 30 minutes, discharge this bath, and use 200wt% cold water washing leather subsequently.Gained leather hangs horse and toggling or vacuum-drying subsequently.
Because gained leather sensation is significantly stiffer than the material obtained in embodiment 2 and 3, therefore, extra fatting agent must be added, have and the leather of similar pliability that obtains in embodiment 2 and embodiment 3 to obtain.Total process period in vat is about 2.5-3 hour.The thickness of gained leather is 1.7mm.In this technological process, therefore the thickness of leather be increased to 1.7mm from 1.3mm.
Embodiment 5
According to DIN50014, regulate after 48 hours under 23 DEG C and 50% relative humidity, to embodiment 2, the leather sheet sample obtained in embodiment 3 and embodiment 4 carries out many evaluation tests.
According to ISO 3376:2002 (RH=40-45%; T=22 DEG C), measure tensile strength, and be the leather from embodiment 2 of 1.63mm for thickness, the overall loading under this tensile strength is 240N, and average tensile strength is 8.2N/mm
2, and average elongation is 57%, and be the leather from embodiment 3 and 4 of 1.63mm for thickness, the overall loading under this tensile strength is 180N, and average tensile strength is 5.6N/mm
2, and average elongation is 41%.
According to ISO 3377-1:2002 (RH=40-45%; T=22 DEG C), measure monolateral tear strength, and be the leather from embodiment 2 of 1.7mm for thickness, monolateral tear strength is 57N, and is the leather from embodiment 3 and embodiment 4 of 1.6mm for thickness, and monolateral tear strength is 32N.
According to ISO 3377-2:2003 (RH=40-45%; T=22 DEG C), measure bilateral tear strength, with the leather from embodiment 2 for thickness being 1.63mm, for small pieces that are vertical with skeleton and parallel cutting, bilateral tear strength is respectively 82N and 92N, thus cause average bilateral tear strength to be 87N, and be the leather from embodiment 3 and embodiment 4 of 1.63mm for thickness, for small pieces that are vertical with skeleton and parallel cutting, bilateral tear strength is respectively 50N and 58N, thus causes average bilateral tear strength to be 54N.
The leather obtained in embodiment 2 is more solid than the leather obtained in embodiment 3 and embodiment 4.
Claims (15)
1. the composition of retanning and stuffing pretan leather, said composition comprises:
A () accounts for the retanning agent of total composition 30-80wt%;
B () accounts for the fatting agent of total composition 10-50wt%, it comprises the phosphatide of the weight at least 50wt% accounting for fatting agent, preferably at least 60wt%, more preferably at least 70wt%, the phosphatide of maximum 100wt%; With
C () optionally, surplus reaches the non-retanning agent of 100wt% total composition and other half nitre process chemical of fatting agent.
2. the composition of claim 1, the phosphatide being wherein used as (part) fatting agent is solid under the envrionment conditions temperature of 25 DEG C (normal atmosphere and).
3. the composition of claim 1 or 2, wherein used whole fatting agents are solid at ambient conditions.
4. the composition of any one claim aforementioned is solid form at ambient conditions, preferred powder type.
5. the composition of any one claim aforementioned, wherein the amount of retanning agent is 30-70wt%, and wherein the amount of fatting agent is 15-40wt%.
6. the composition of any one claim aforementioned, wherein retanning agent is selected from vegetable tanning agent, aromatics synthetic tanning agent, resin tanning agent, reactive tanning agent and Polymer Tanning Agent.
7. the composition of any one claim aforementioned, wherein fatting agent comprises the fatty acid ester being selected from phosphorylcholine, the phosphatide in the fatty acid ester of the mixture of polyvalent alcohol, lipid acid and phosphorylcholine, and wherein polyvalent alcohol is trivalent alcohol, dibasic alcohol or erythritol.
8. the composition of any one claim aforementioned, wherein fatting agent comprises or is selected from natural or synthetic phospholipid, dialkyl group Phosphorylcholine, phosphatidylethanolamine, phosphatidylinositols, the phosphatide in Yelkin TTS, or the mixture of these phosphatide one or more of.
9. the composition of any one claim aforementioned, wherein fatting agent is made up of phosphatide substantially.
10. the preparation method of the composition of any one claim aforementioned, the method comprises the various composition of mixing.
The method of 11. claims 10, wherein each composition is solid at ambient conditions and mixes in solid form.
Any one composition of 12. claim 1-9 is used for the purposes of retanning and stuffing pretan leather, fur, fur, animal skin, leather intermediate product or work in-process leather.
The method of 13. retannings or stuffing pretan leather, fur, fur, animal skin, leather intermediate product or work in-process leather, the method comprises in a suitable solvent, preferably in water, with any one composition one step process of claim 1-9.
The method of 14. claims 13, be placed in suitable container together with the water comprising the steps: a slice pretan leather and the temperature of the 100-200wt% accounting for leather dry weight to be 10-40 DEG C, then any one the composition of claim 1-9 accounting for the 5-50wt% of leather dry weight is added, this mixture 30-100 minute is soaked subsequently at 10-40 DEG C, add the water accounting for 30-70 DEG C of the 100-300% of leather dry weight, and after 2-10 minute, add the laking agent of 0.5-3wt%, then after 2-30 minute, add the identical or different laking agent of other 1-3wt%, after 10-60 minute, discharge liquid, and wash leather with water.
15. preferably by the obtainable leather of method of claim 13 or 14, and it has soft sense of touch and/or has high tear strength and high tensile strength.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL2008666 | 2012-04-20 | ||
| NL2008666A NL2008666C2 (en) | 2012-04-20 | 2012-04-20 | Composition and process for the retanning and fatliquoring of leather, and the leather prepared. |
| PCT/NL2013/050275 WO2013157941A1 (en) | 2012-04-20 | 2013-04-17 | Composition and process for the retanning and fatliquoring of leather, and the leather prepared |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104334746A true CN104334746A (en) | 2015-02-04 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201380026549.1A Pending CN104334746A (en) | 2012-04-20 | 2013-04-17 | Composition and process for the retanning and fatliquoring of leather, and the leather prepared |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP2839041B1 (en) |
| KR (1) | KR20150003825A (en) |
| CN (1) | CN104334746A (en) |
| BR (1) | BR112014025968A2 (en) |
| HK (1) | HK1207405A1 (en) |
| IN (1) | IN2014DN08811A (en) |
| MX (1) | MX2014012705A (en) |
| NL (1) | NL2008666C2 (en) |
| WO (1) | WO2013157941A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116102681A (en) * | 2022-10-19 | 2023-05-12 | 陕西科技大学 | Preparation method of amphoteric wet finishing material with retanning, fatliquoring and dyeing functions |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104060003B (en) * | 2014-07-10 | 2016-01-20 | 北京泛博科技有限责任公司 | A kind of fatting agent and preparation method thereof |
| CN104372112B (en) * | 2014-10-27 | 2016-04-13 | 浙江理工大学 | A kind of preparation method for cortex historical relic microemulsion fatting agent |
| CN105154596B (en) * | 2015-10-26 | 2017-03-22 | 烟台大学 | Manufacturing technology for flame-retardant, anti-yellowing and low-fogging cowhide car seat cushion leather |
| KR102490689B1 (en) * | 2021-09-15 | 2023-01-20 | (주)제이에스산업 | Manufacturing method of natural leather material having excellent washing property and easy cleaning property and natural leather material using the same |
| KR102485971B1 (en) * | 2021-09-16 | 2023-01-09 | (주)태화 | Manufacturing method of natural leather material having excellent self recovering property and scratch resistance property and natural leather material using the same |
| IT202200005300A1 (en) | 2022-03-17 | 2023-09-17 | Fgl Int S P A | Method of lubricating leather goods and lubricating product used in that method |
| IT202200015948A1 (en) * | 2022-07-27 | 2024-01-27 | Gipel S R L | PRODUCT FOR LEATHER PROCESSING |
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| US6033590A (en) * | 1996-12-20 | 2000-03-07 | Ciba Specialty Chemicals Corp. | Compositions for the preparation of leather |
| CN1802442A (en) * | 2003-05-06 | 2006-07-12 | 巴斯福股份公司 | Lubricant for the production and treatment of leather |
| CN101215612A (en) * | 2007-12-26 | 2008-07-09 | 宁波工程学院 | Method for preparing composite tan fatting agent from discarded phospholipid |
| CN101643802A (en) * | 2008-08-28 | 2010-02-10 | 济南力厚化工有限公司 | Modified phospholipid composite fat liquor and preparation thereof |
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- 2012-04-20 NL NL2008666A patent/NL2008666C2/en not_active IP Right Cessation
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- 2013-04-17 MX MX2014012705A patent/MX2014012705A/en unknown
- 2013-04-17 KR KR1020147032176A patent/KR20150003825A/en not_active Application Discontinuation
- 2013-04-17 WO PCT/NL2013/050275 patent/WO2013157941A1/en active Application Filing
- 2013-04-17 EP EP13720113.3A patent/EP2839041B1/en not_active Not-in-force
- 2013-04-17 BR BR112014025968A patent/BR112014025968A2/en not_active IP Right Cessation
- 2013-04-17 CN CN201380026549.1A patent/CN104334746A/en active Pending
-
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- 2014-10-20 IN IN8811DEN2014 patent/IN2014DN08811A/en unknown
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- 2015-08-21 HK HK15108139.8A patent/HK1207405A1/en unknown
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| US6033590A (en) * | 1996-12-20 | 2000-03-07 | Ciba Specialty Chemicals Corp. | Compositions for the preparation of leather |
| CN1802442A (en) * | 2003-05-06 | 2006-07-12 | 巴斯福股份公司 | Lubricant for the production and treatment of leather |
| CN101215612A (en) * | 2007-12-26 | 2008-07-09 | 宁波工程学院 | Method for preparing composite tan fatting agent from discarded phospholipid |
| CN101643802A (en) * | 2008-08-28 | 2010-02-10 | 济南力厚化工有限公司 | Modified phospholipid composite fat liquor and preparation thereof |
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| CN116102681A (en) * | 2022-10-19 | 2023-05-12 | 陕西科技大学 | Preparation method of amphoteric wet finishing material with retanning, fatliquoring and dyeing functions |
| CN116102681B (en) * | 2022-10-19 | 2024-01-30 | 陕西科技大学 | Preparation method of amphoteric wet finishing material with retanning, fatliquoring and dyeing functions |
Also Published As
| Publication number | Publication date |
|---|---|
| BR112014025968A2 (en) | 2017-06-27 |
| MX2014012705A (en) | 2015-09-08 |
| NL2008666C2 (en) | 2013-10-23 |
| IN2014DN08811A (en) | 2015-05-22 |
| KR20150003825A (en) | 2015-01-09 |
| EP2839041A1 (en) | 2015-02-25 |
| HK1207405A1 (en) | 2016-01-29 |
| WO2013157941A1 (en) | 2013-10-24 |
| EP2839041B1 (en) | 2016-11-02 |
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