EP0318751B1 - Agent d'apprêt pour cuir naturel et synthétique - Google Patents

Agent d'apprêt pour cuir naturel et synthétique Download PDF

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Publication number
EP0318751B1
EP0318751B1 EP88118959A EP88118959A EP0318751B1 EP 0318751 B1 EP0318751 B1 EP 0318751B1 EP 88118959 A EP88118959 A EP 88118959A EP 88118959 A EP88118959 A EP 88118959A EP 0318751 B1 EP0318751 B1 EP 0318751B1
Authority
EP
European Patent Office
Prior art keywords
leather
finishing
seasoning
cellulose acetobutyrate
agent according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP88118959A
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German (de)
English (en)
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EP0318751A2 (fr
EP0318751A3 (fr
Inventor
Leo Dr. Tork
Wolfgang Höhne
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
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Bayer AG
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Filing date
Publication date
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Publication of EP0318751A2 publication Critical patent/EP0318751A2/fr
Publication of EP0318751A3 publication Critical patent/EP0318751A3/fr
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Publication of EP0318751B1 publication Critical patent/EP0318751B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C11/00—Surface finishing of leather
    • C14C11/003—Surface finishing of leather using macromolecular compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
    • Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating

Definitions

  • the invention relates to finishing agents for leather and imitations of leather, processes for finishing leather or imitations of leather and finished leather and imitations of leather.
  • Finishes serve to improve the physical fastness of leather and imitations of leather, such as rub fastness, shock resistance and heat resistance. In addition, they give these materials a solid external appearance such as shine, smoothness and surface feel. Finishing agents for leather and imitations of leather are already known in large numbers, e.g. based on protein substances, nitrocellulose and polyurethanes.
  • thermoplastic primers if highly crosslinked polymer dispersions are used as binders when dressing the leather, or even better, if reactive binders are crosslinked on the leather using suitable polyfunctional compounds (see, for example, DE- OS 3 544 001 and DE-OS 3 711 415).
  • Primers with such strongly crosslinked polymer dispersions seal off strongly and are therefore only slightly swellable by water and solvents. The adhesion of the finishing layers is therefore problematic. Finishing agents that are to be applied to cross-linked reactive primers must therefore have particularly good adhesion to the substrate.
  • Lacquers based on collodion have good adhesion to reactive primers.
  • nitrocellulose has many valuable properties that make it suitable as a finishing agent, but also has disadvantages: low lightfastness, non-resistant to amines, not heat-resistant and extremely flammable. These disadvantageous properties make collodion varnishes unsuitable for finishing white and light-colored leathers.
  • Polyurethane paints only adhere to primers with reactive binders if they are used in the form of reactive two-component paints. Disadvantages for all PUR lacquers of both the 1- and the reactive 2-component lacquers are a leather-like, plastic-like handle and their low pigmentability; they can only be weakly pigmented, otherwise poor wet rub fastness results. PUR lacquers are therefore ruled out as highly opaque final finishes, especially for light-colored leather.
  • cellulose acetate butyrate-based paints have also been used as a finishing agent for white and pastel-colored leather.
  • the lacquers can be pigmented more strongly than PUR lacquers without poor wet fastness being observed; they are lightfast, amine-proof, resistant to yellowing up to 170 ° C and give flame-retardant residues.
  • the main disadvantages of the cellulose acetobutyrate lacquers previously used for leather finishing are their poor adhesion, their poor absorption capacity for plasticizers and their unpleasant feel. So these finishing agents do not adhere to primers that are heavily finished by hot ironing or embossing of damp leather, long, hot drying or long storage of the leather during the dressing process (holidays) or also by strong polishing effects. After all, these paints also do not adhere to primers with crosslinked reactive binders. But reactive primers are becoming more and more important because they are used to make finishes with a very good aspect and a particularly high level of authenticity.
  • the adhesion of the known finishing agents based on cellulose acetobutyrate for leather finishing is further deteriorated if pigments are added to them or inorganic matting agents, such as porous orthosilicic acid, are added to them.
  • Any type of plasticizer additive is particularly detrimental to adhesion.
  • Soft and elastic leather can be used with the lacquers currently used for leather finishing Acetobutyrates as binders are not finished, because for these types of leather to adjust the required smoothness of the finishing film such high amounts of plasticizers are required that sufficient adhesion of these finishing agents is no longer guaranteed, even on poorly finished primers.
  • the handle of finishes with acetobutyrates as binders without plasticizer additives is cold, smooth, plastic-like and absolutely foreign to leather. If plasticizers are added to these finishes, the cellulose acetobutyrate types used repel most of these products to the surface of the finish layer, causing an undesirable, sticky feel.
  • finishing layers on leather and imitations of leather with particularly good properties important for leather finishing, such as grip, gloss, toughness, low-temperature flexibility, dry and wet rub fastness, dry and wet kink resistance, good flow during spraying, but especially good adhesion
  • finishing agents the solutions of cellulose acetobutyrate types which have a butyryl content of at least 44% by weight, based on cellulose acetobutyrate, preferably 44 to 55% by weight. , particularly preferably 47 to 53% by weight, and also contain polyether siloxanes.
  • the 20% solution of the cellulose acetobutyrate in acetone used according to the invention should preferably have a viscosity of 0.1 to 40 poises at 20 ° C.
  • Such products are made by known methods, e.g. according to DE-OS 1 905 101 or DE-OS 3 244 955 (Examples 1A, 2A, 3A).
  • the cellulose acetobutyrate to be used according to the invention is produced by methods known per se, e.g. by esterification of cellulose in the form of cotton internals with acetic and butyric anhydride, in the presence of pyridine.
  • finishing agents according to the invention can also contain plasticizers, blending agents and others for finishing agents usual for leather and imitations of leather, additives, such as matting agents, pigments and other additives.
  • plasticizers come e.g. Phthalates, phosphates, esters of aliphatic dicarboxylic acids, fatty acid esters and polymeric plasticizers in question.
  • n-butyl stearate with diesters of phthalic acid are preferably used, in particular di-n-butyl phthalate, di-n-hexyl phthalate, di-n-octyl phthalate or dibenzyl phthalate in a ratio of 1: 1 to 1: 3, preferably 1: 1.2 to 1: 2.4.
  • Alcohols, ketones and acetates are suitable, in particular suitable are: acetone, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, methoxypropanol, butyl acetate, methyl and ethyl glycol acetate, methoxy and ethoxypropyl acetate, butyl glycol acetate, cyclohexanone and diacetone alcohol.
  • toluene, xylenes, isopropanol, ethanol, methyl and ethyl glycol, benzyl alcohol, diisobutyl ketone and in particular 2-ethyl-n-hexylacetate are particularly suitable as solvents or blending agents.
  • alcohols and glycols are preferred.
  • the physical properties of the finishing agents such as flow, drying speed and the like are medium boilers (methyl, ethyl glycol) or high boilers (benzyl alcohol, 2-ethyl-n-hexyl acetate) due to the amount of low boilers (isopropanol, ethanol). controllable. They are used in amounts from 0 to about 985 g / kg of finishing agent.
  • the use of other solvents is of course within the scope of the invention.
  • the components are combined with solvents and blending agents and stirred until the cellulose acetobutyrate has completely dissolved.
  • finishing agent which contains 15 to 40 g of cellulose acetobutyrate with a butyryl content of ⁇ 45% by weight per kg.
  • the polyether siloxane is preferably used in amounts of 0.5 to 20 g / kg, preferably 0.5 to 10 g / kg of finishing agent.
  • the plasticizer or the plasticizer mixture is preferably used in amounts of 0 to 100 g / kg, preferably 5 to 80 g / kg, of finishing agents. It is particularly advantageous to use a plasticizer mixture of 2 to 20 g of n-butyl stearate and 3 to 30 g of di-n-butyl phthalate and / or di-n-octyl phthalate per kg of finishing agent.
  • the preparation of white, colored and matted finishing agents can be carried out, for example, by adding only a part of the solvent / extender mixture to the cellulose acetobutyrate, the polyether siloxane and the plasticizer, so that a paint consistency which is favorable for the dispersion of the pigment is obtained becomes.
  • the mixture is stirred using a dissolver at 800 to 2000 rpm until the pigment is finely divided and, if appropriate, ground in a bead mill with cooling.
  • the remaining amount of solvent and blending agent is diluted further.
  • finishing agents are applied by spray application, by means of a casting machine, knife or roller application machine to full-grain, sanded or split leather, which has been treated with pigments and thermoplastic binders, and to imitations of leather and textile material coated with polyurethane.
  • Primers for leather finishing that can be treated with the finishing agent according to the invention are described, for example, in Ullmanns Encyklopadie der Technische Chemie, 4th edition, volume 16, pp. 161-166.
  • the finishes can also be applied in several layers, if desired, varying their composition.
  • the finished materials can be ironed and polished.
  • the finishes run particularly well, especially when spraying, and give hardly inflammable residues. They are lightfast, amine-proof and resistant to yellowing up to 170 ° C and are characterized by a very good Liability from. Thus, they adhere to primers which have been severely finished by hot ironing or long storage of the leather prior to finishing, but in particular also to primers with crosslinked reactive binders produced according to DE-OS 3 544 001 or DE-OS 3 711 415. In comparison, PUR-based finishes do not adhere to such primers if they are not reactive, but only if they are used in the form of reactive two-component paints.
  • the leather finished in this way has good properties. You own with good surface calm, high gloss and a non-sticky, smooth, natural leather handle. In addition, the dry, wet and rub-through resistance and in particular the cold flexibility are more improved than with finishes based on protein, collodion and PUR.
  • the finishes can contain large amounts of the preferred plasticizer mixtures of n-butyl stearate and esters of phthalic acid without disadvantages for adhesion and grip, the finish film can be adjusted and pigmented almost as desired in terms of hardness and elasticity.
  • the finishing agent according to the invention can thus be used for the entire broad range of leather types, from steady belt leather to soft, brisk nappa leather.
  • Pigments can be stained using a dissolver or a bead mill for a more suitable finish Viscosity, which can be controlled by the degree of dilution, is dispersed in the lacquer, or suitable, already formed pigments in paste form are used, produced, for example, according to DE-OS 2 801 817.
  • porous orthosilicic acid with a nominal particle size of 4 micrometers and a BET surface area of 260 m2 / g is used for matting, the matt effects are particularly reproducible.
  • the finishes do not show a gray break, cannot be polished back and have a natural leather handle. Furthermore, the scratch resistance of the finish is increased in this way.
  • finishing agent according to the invention result from its extraordinarily high pigmentability, without the wet rub fastness and the gloss decrease. Since the pigment / binder ratio can be greatly shifted in favor of the pigment compared to pigmented PUR varnishes, this varnish with comparable coverage layers much less than PUR varnishes, shows a finer scar throw, and in particular it sharpens the scar image while PUR varnishes smear the pore.
  • the finishing agent according to the invention can also be added to PUR paints, produced e.g. according to DE-OS 2 423 764 or DE-OS 1 694 141, in order to improve the property profile of these coating systems.
  • the flow in particular in the case of high-molecular-weight polyurethane resins, grip, rub resistance, pigmentability and in particular the aspect: the leather appears less overloaded and plastic-like.
  • the invention further relates to leather and imitations of leather finished with the finishing agents according to the invention.
  • Sanded leather, full-grain leather and split leather, which have been trimmed with pigments and thermoplastic binders (cf. W. Grassmann, Handbook for Chemicals and Leather Fabrication, Volume III / 1 and Ullmanns Encyklopedia of Technical Chemistry, 4th edition, Volume 16, p. 161-166), as well as imitations of leather and textile materials coated with polyurethane, receive 1 to 2 spraying jobs with this varnish a total of 40 to 80 g / m2.
  • the finished materials can be ironed on a hydraulic ironing machine, eg at 70 ° C / 150 bar, or on a continuous ironing machine to regulate the surface smoothness and to adjust the gloss level.
  • the finishes have a very good course during spraying, are lightfast, amine-proof and resistant to yellowing up to 170 ° C. In particular, they are characterized by very good adhesion. For example, they adhere to primers which have been severely sealed by hot ironing or long storage of the leather before being finished, in particular they adhere to crosslinked primers with reactive binders, as described in DE-OS 3 544 001 and DE-OS 3 711 415, Examples 1 to 3, can be obtained.
  • the finished leathers are characterized by a high gloss with good surface quietness and in particular by a very natural leather handle.
  • the dry, wet and rub-through resistance and especially the cold flexibility are more improved than when using finishing agents based on protein and collodion.
  • a pigment paste made according to DE-OS 2 801 817 and consisting of 3.4 g CI Pigment Red 170, 7.2 g pigment binder from DE-OS 2 801 817, are added to 1000 g of the colorless finishing varnish.
  • Example 1 and 9.4 g of cyclohexanone and homogeneously distributed in the paint by stirring.
  • the resulting intensely red-colored lacquer is applied to leather and imitations of leather that have been primed in a corresponding color, according to the above-described method.
  • the varnish greatly improves the color uniformity and also gives the materials a high-gloss, brilliant colored aspect with good physical fastness.
  • the finishing varnish can e.g. organic solutions of 1: 2 metal complex dyes can be added in a known manner.
  • the aspect of the finished leather has a favorable effect that good physical fastness properties, in particular wet, dry and rub-through resistance, can be achieved even with small amounts of paint and that, due to the high covering power of the white finish, color coats in the primer, which are associated with thermoplastic binders have been made and layers can be saved much more than the finishing jobs. For all these reasons, leathers that have been finished with this white varnish show a particularly fine grain due to the slightest stress on the leather surface.
  • Example 2 After application to leather and leather synthetics under the conditions of Example 1, a colorless matt finish is obtained which is scratch-resistant and cannot be polished back. It shows no gray opening and is characterized by a smooth, natural leather handle. Liability - even on strongly sealed primers - is integrity.
  • Example 1 the cellulose acetobutyrate used there is replaced by a cellulose acetobutyrate which is characterized by a butyryl content of 37% and a viscosity, 20% dissolved in acetone, at 20 ° C. of about 8 poises.
  • the lacquer produced according to the method of example 1 and applied to leather and imitations of leather does not adhere to strongly sealed, thermoplastic primers, in particular not to crosslinked primers with reactive binders, produced according to DE-OS 3 544 001 and DE-OS 3 711 415, examples 1 to 3 .
  • SHELLSOL TD The chemicals listed up to the SHELLSOL TD are dissolved in a kettle at room temperature with stirring. After complete dissolution, SHELLSOL TD is added all at once and stirred well for about 3 minutes. The solution of 1 g of di-n-octyl sodium sulfosuccinate in 80 g of water is then added with rapid stirring and, after the addition, stirred for a further 15 minutes. This is done by transferring it into an oil-in-water emulsion. Then 1 g of triethanolamine dissolved in 79 g of water is added with stirring and stirring is continued for a further 10 minutes. The remaining 500 g of water are finally added all at once. The pH of the finished emulsion is between 7 and 8.
  • Sanded and full-grain leather or even imitations of leather which have been prepared thermoplastic - as described in Example 1 - or coated with polyurethane, are sprayed with about 10 to 30 g / m2. After drying, the leather is ironed on a hydraulic press at approx. 70 ° C and 200 bar or the imitation leather at 80 ° C and 50 bar. A second application of 10 to 20 g / m2 is then carried out under the same application conditions Spraying machine.
  • This emulsion varnish gives the leather an extraordinarily natural leather character, especially in terms of grip and aspect, an advantage that is particularly noticeable on full-grain leather. In particular, leathers that are finished with such emulsions show a particularly fine grain throw due to the slightest load.
  • the leather With equally good physical fastness properties, in particular good adhesion to closed primers and a comparable good coverage, the leather is less stressed and therefore has a more natural effect than leather with the white lacquer from Example 2.
  • This white lacquer emulsion is particularly distinguished by the fact that the your treated leather and imitations of leather receive a very natural leather handle.
  • the chemicals listed above are dissolved in a kettle at room temperature as described in Example 5 and the clear solution by adding di-n-octyl sodium sulfosuccinate, dissolved in water, with vigorous stirring in an oil-in-water Emulsion transferred.
  • the silica is introduced into this emulsion.
  • triethanolamine dissolved in water is added and stirring is continued for a further 10 minutes.
  • the mixture is then ground 1 time in a bead mill with glass beads of 1 mm in diameter with cooling for the purpose of finely distributing the silica.
  • the remaining 500 g of water are finally added all at once.
  • the pH of the finished dispersion is between 7 and 8.
  • Example 5 After application under the conditions of Example 5 to leather and synthetic leather, the dispersion gives a non-polishable matt lacquer that is scratch-resistant, shows no gray breakage and has an exceptionally smooth handle for the strong matting.
  • the finished varnish has a very good flow and results after application to leather or imitation leather under the conditions Example 1 a glossy, highly elastic finish, which is particularly suitable as a final finish for furniture leather.
  • the wet, dry and rub-through strengths are significantly improved by the addition of the mixture according to the invention to the PUR lacquer, the handle more leather-like and the appearance less plastic.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (9)

  1. Procédé pour apprêtrer les cuirs naturels et synthétiques, caractérisé en ce que l'on utilise des solutions d'acétobutyrate de cellulose à une teneur en butyryle supérieure ou égale à 45 % en poids, par rapport à l'acétobutyrate de cellulose, et en outre un polyéther-siloxane.
  2. Procédé selon la revendication 1, caractérisé en ce que la teneur en butyryle de l'acétobutyrate de cellulose est de 45 à 55 % en poids.
  3. Procédé selon la revendication 1, caractérisé en ce que la teneur en butyryle de l'acétobutyrate de cellulose est de 47 à 53 % en poids.
  4. Procédé selon les revendications 1 à 3, caractérisé en ce que l'on utilise un polyéther-siloxane dans lequel les groupes polyéther sont reliés au polysiloxane par un pont éther ou par un groupement carbamique.
  5. Procédé selon les revendications 1 à 4, caractérisé en ce que l'on utilise un polyéther-siloxane contenant au moins deux groupements de structure
    Figure imgb0019
     dans laquelle PE représente un radical de polyéther et R répond à la formule
    Figure imgb0020
     dans laquelle R' = alkyle, cycloalkyle, alcényle, aralkyle, dialkylaminoalyle, aryle, ou alkylaryle contenant chacun jusqu'à 10 atomes de carbone,
    ou à la formule
    Figure imgb0021
     dans laquelle x = 2 à 25.
  6. Procédé selon les revendications 1 à 5, caractérisé en ce que l'on utilise en outre un plastifiant, de préférence un mélange de stéarate de n-butyle et de diester phtalique.
  7. Procédé selon les revendications 1 à 6, caractérisé en ce que l'on utilise en outre des additifs usuels.
EP88118959A 1987-11-28 1988-11-14 Agent d'apprêt pour cuir naturel et synthétique Expired - Lifetime EP0318751B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19873740440 DE3740440A1 (de) 1987-11-28 1987-11-28 Appreturmittel fuer leder und lederimitate
DE3740440 1987-11-28

Publications (3)

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EP0318751A2 EP0318751A2 (fr) 1989-06-07
EP0318751A3 EP0318751A3 (fr) 1991-01-16
EP0318751B1 true EP0318751B1 (fr) 1993-04-21

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EP88118959A Expired - Lifetime EP0318751B1 (fr) 1987-11-28 1988-11-14 Agent d'apprêt pour cuir naturel et synthétique

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US (1) US5002584A (fr)
EP (1) EP0318751B1 (fr)
JP (1) JPH01170700A (fr)
BR (1) BR8806202A (fr)
DE (2) DE3740440A1 (fr)
ES (1) ES2040818T3 (fr)

Families Citing this family (8)

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Publication number Priority date Publication date Assignee Title
DE19518948A1 (de) * 1995-05-23 1996-11-28 Hesse Gmbh & Co Wäßrige, lagerstabile Überzugsmittel
JP3561376B2 (ja) * 1996-08-20 2004-09-02 富士写真フイルム株式会社 セルロースエステル溶液の調製方法およびセルロースエステルフイルムの製造方法
DE102005040078B4 (de) * 2005-08-24 2008-11-06 Esfandiar Rahim Azar-Pey Verbund aus Ziegenleder und einem weiteren Material
DE102006039261A1 (de) 2006-08-22 2008-03-06 Lanxess Deutschland Gmbh Zugerichtetes Leder
JP5496287B2 (ja) 2011-09-15 2014-05-21 ローム アンド ハース カンパニー 皮革に使用するためのポリ（エチレンオキシド）含有低光沢水性コーティング組成物
JP5781037B2 (ja) 2011-09-15 2015-09-16 ローム アンド ハース カンパニーＲｏｈｍ Ａｎｄ Ｈａａｓ Ｃｏｍｐａｎｙ ポリ（エチレンオキシド）を含む低光沢水性コーティング組成物
CN103469598A (zh) * 2012-06-06 2013-12-25 上海日多高分子材料有限公司 一种服装革用绵羊皮添加剂的制造方法
JP6033974B1 (ja) 2016-01-18 2016-11-30 株式会社Ｓｓｋプロテクト 二液型コーティング剤及び被覆体保護方法

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Publication number Priority date Publication date Assignee Title
US2410685A (en) * 1945-10-18 1946-11-05 Eastman Kodak Co Hot melt-coating composition
DE2542767A1 (de) * 1975-09-25 1977-04-07 Kepec Chem Fab Gmbh Mittel fuer die zurichtung von leder und lederaustauschstoffen
DE3244955A1 (de) * 1982-12-04 1984-06-07 Bayer Ag, 5090 Leverkusen Waessrige silicondispersionen, verfahren zu deren herstellung und verwendung als textilbehandlungsmittel

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Publication number Publication date
DE3740440A1 (de) 1989-06-08
EP0318751A2 (fr) 1989-06-07
JPH01170700A (ja) 1989-07-05
EP0318751A3 (fr) 1991-01-16
US5002584A (en) 1991-03-26
DE3880444D1 (de) 1993-05-27
BR8806202A (pt) 1989-08-15
ES2040818T3 (es) 1993-11-01

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