EP1989333B1 - Procede et dispositif destines a disposer un revetement sur au moins un cote d'un cuir et cuir revetu obtenu par un tel procede - Google Patents

Procede et dispositif destines a disposer un revetement sur au moins un cote d'un cuir et cuir revetu obtenu par un tel procede Download PDF

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Publication number
EP1989333B1
EP1989333B1 EP06723413A EP06723413A EP1989333B1 EP 1989333 B1 EP1989333 B1 EP 1989333B1 EP 06723413 A EP06723413 A EP 06723413A EP 06723413 A EP06723413 A EP 06723413A EP 1989333 B1 EP1989333 B1 EP 1989333B1
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EP
European Patent Office
Prior art keywords
leather
superheated steam
plastic dispersion
grain
coating
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.)
Not-in-force
Application number
EP06723413A
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German (de)
English (en)
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EP1989333A1 (fr
Inventor
Philipp Schaefer
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Lanxess Deutschland GmbH
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Lanxess Deutschland GmbH
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Publication date
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Publication of EP1989333A1 publication Critical patent/EP1989333A1/fr
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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
    • 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
    • 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
    • C14C15/00—Apparatus for chemical treatment or washing of hides, skins, or leather
    • 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
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/254—Polymeric or resinous material

Definitions

  • the invention relates to a method and a device for applying a coating, preferably a base coat, to at least one, optionally on both, sides of a leather, namely on the grain side and / or on that side of the scar opposite side of a grain leather, or on a or both sides of a split leather, and a leather produced by such a process and provided with a coating, preferably a base coat.
  • a coating preferably a base coat
  • a leather and a method for producing the same has become known, in which the opposite side of the visible side of the leather is provided with a foam material, which is formed by solidification of a liquid applied, finished hollow microspheres containing plastic material by brief exposure to hot air.
  • the hot air in this case has a temperature of more than 280 ° C, preferably a temperature between 350 ° C and 650 ° C, is thus very hot and dry, which causes the leather, the natural moisture is removed, and that it shrinks and hardens.
  • the hollow microspheres become at the top of the foam equipment often destroyed. This coating can not be used as .Grundbe Anlagenung for the construction of other finishing finishes.
  • the DE 20318311 U1 discloses a full-grain leather in which imperfections in the grain layer are corrected by a plastic filling compound consisting of a solidified plastic dispersion containing hollow particles made of compact particles by supplying heat.
  • the formation of the hollow microspheres is carried out by applying pressure and heat at a temperature of at least 100 ° C.
  • this known design has the disadvantage that the leather is adversely affected at the required pressure and the applied temperature.
  • the defects formed by depressions are not completely filled by the Kunststoffüllmasse because after pressure relief, the pressure-elastic leather resets, whereas the plastic filling mass does not increase in volume, and thus the plastic filling mass is still set back on its upper side against the leather surface.
  • the grain layer of the leather must be ground so deep until the entire surface is flat, whereby the quality of the leather is impaired and this significantly decreases in value.
  • the temperature increase required for expanding the compact particles to form the hollow microspheres does not take place with economically justifiable application of pressure and heat, so that this lower region has no or only a small number of hollow microspheres. If higher temperatures are used over a relatively long period of time, although hollow microspheres are formed in this area, the leather is even more compacted, which leads to further hardening.
  • the dermis especially in the abdominal area of a cow's skin, the looseness again fully.
  • the object of the present invention is to avoid the disadvantages of known leather provided with a foam coating and to provide a leather which has a foam coating applied to at least one, optionally applied on both sides, which can be produced in an economical manner which prevents shrinkage and hardening in the formation of the foam coating and in which defects on the upper side of the leather can be eliminated without any existing grain structure being damaged by reworking the upper side.
  • the inventive method for producing such a leather that in a known preparation of the coating by applying an aqueous, containing a blowing agent containing compact particles, plastic dispersion and subsequent solidification thereof according to the invention from the thermoplastic compact particles, the hollow microspheres are formed by after solidification, the plastic dispersion containing the compact particles is subjected to the action of relaxed superheated steam at a temperature between 80 ° C and 100 ° C.
  • the pressure acting on the plastic dispersion in this case is preferably less than 0.1 bar.
  • Optimal values are achieved when the superheated steam acts on the solidified plastic dispersion in a period of less than 7 seconds, preferably less than 3 seconds.
  • thermoplastic and / or thermoelastic plastic dispersions which contain a propellant having compact particles.
  • These compact particles consist in a known manner of a thermoplastic or plastic copolymer, preferably of polyvinylidene chloride copolymer, containing as propellant, for example, isobutane, and have a size of less than 20 microns, preferably less than 10 microns.
  • a plastic dispersion which preferably contains a wetting agent and / or density-increasing additives, such as barite, they penetrate easily into the depressions on the leather surface.
  • Particularly suitable are soft plastic dispersions having a hardness of less than 70 Shore A, which are softened by the action of superheated steam.
  • the preferred viscosity of the plastic dispersion in particular when applied to the leather with a spray device or by so-called plush, is in the range between 5 seconds and 15 seconds, measured in a Ford cup with a nozzle diameter of 6 mm. If the plastic dispersion is applied to it by means of a roller rotating in opposite directions to the direction of transport of the leather in order to assist the penetration of the plastic dispersion into the depressions on the leather surface, the viscosity is between 10 and 40 seconds measured in the Ford cup with a diameter of 6 mm.
  • the applied superheated steam acts on such compact particles in addition to its heating as a vapor also softening, so that the micro hollow spheres forming therefrom can also adapt to small depressions in the leather surface and can arise there in the mentioned short period of time.
  • a significant advantage of using the method according to the invention is that the leather for the formation of the hollow microspheres from the compact particles must be subjected to no pressure load, so maintains its original thickness, so that a complete filling of wells in the leather surface is ensured and to achieve a flat Surface post-processing by partial removal of the scar layer is required.
  • the use of the method according to the invention also entails the economic advantage that most leather factories in any case have high-pressure steam generators and are therefore able to produce low-pressure steam.
  • plastic dispersion is applied.
  • the application takes place here in thin layers between 0.015 mm and 0.08 mm, either via rollers that rotate in the opposite direction to the transport direction of the leather, or preferably by spraying, because then the thin plastic dispersion better even in fine depressions from the leather surface starting deep in the leather penetrates.
  • the application can also be done manually, e.g. by the so-called plush.
  • the low-viscosity plastic dispersion penetrates particularly deeply into the finest pinholes.
  • this superheated steam supply device has at least one superheated steam line with outlet nozzles or slots directed against the solidified plastic dispersion, from which the superheated steam is sprayed onto the solidified plastic dispersion.
  • the hot steam line preferably consists of a tube with a round or angular cross-section, in which the outlet nozzles or contactors are provided, and which is connected to a hot steam source. It turned out to be proven advantageous if this tube is formed meander-shaped, wherein the individual sections extend transversely to the transport direction of the leather, and is connected at its two ends to the superheated steam source, so that the steam in the tube circulates in the circulation and thus cooling is prevented. It suffices here a low vapor pressure of less than 5 bar, preferably less than 2 bar.
  • the hot steam supply device consists of a transport device enclosing hot steam tank
  • the superheated steam is supplied via a superheated steam source, so that on the conveyor located, provided with the solidified plastic dispersion leather during the further movement in this hot steam tank with the is acted upon in this superheated steam.
  • the superheated steam supply device of a provided with the applied plastic dispersion leather supporting, circulating transport device is arranged adjacent, so that the moving past the superheated steam supply leather is continuously supplied with the superheated steam.
  • the transport device preferably consists of a plurality of spaced, parallel, circumferential plastic threads, such as polyamide or polyester threads. These threads are heat-resistant, are not destroyed by the hot steam, in contrast to the application of hot air and infrared radiation, and cause a good support of the leather.
  • this arrangement has the advantage that spaces between the threads are kept free, so that it is possible not only the top of the solidified plastic dispersion, but also on the underside, thus supply from all sides, heat through the interstices get to the leather.
  • This transport device is advantageous above all when the hot steam supply device, as mentioned, consists of a hot steam container enclosing the transport device.
  • a separate superheated steam supply device which is arranged below the transport device, to be provided, via which heat is supplied to the aqueous plastic dispersion having the compact particles through the leather.
  • a warm air duct enclosing the transport device in the direction of circulation of the transport device before and optionally also behind the hot steam supply means, can be provided, in which the warm air also through the spaces between the plastic threads can get to the leather
  • the leather produced by the process according to the invention is characterized characterized in that the superheated steam treated coating has on its surface a homogeneous, nubuck-like, recess-free appearance, such as finely grained grain leather, even having a slight nubuck writing performance, and microscopically the finest pores having an inside diameter of less than 35 has ⁇ m.
  • a leather despite its softness is not or almost not losnarbig.
  • a finish coat is applied to a basecoat prepared by the methods of the present invention, this leather exhibits an optimum appearance because many small wrinkles are formed during swaging which have the appearance of high-grade full-grain aniline leather.
  • the superheated steam treatment also improves the adhesion of the base coat to the leather and, due to the nubuck-like appearance of the surface of the base coat, a subsequently applied finish coat can also be mechanically anchored.
  • the thin, consolidated base coat increases in volume after hot steam treatment by more than 15%, preferably more than 25%.
  • recesses in the leather surface are filled flat or slightly raised.
  • the nubuck-like surface structure is preferably present over the whole surface or almost completely over the leather surface. Since in the coating predominantly closed cells formed by the hollow microspheres are present, such a leather is particularly suitable for the production of automotive components, in which the leather is drawn into molds and optionally backfoamed.
  • Fig. 1 shows the principle of the device according to the invention and Fig. 2 schematically represents an embodiment of this device.
  • Fig. 3 a particular embodiment of the hot steam supply device according to the invention is shown.
  • Fig. 4 represents a further embodiment of the device according to the invention.
  • Fig. 5 shows a section through a leather, in which holes forming pits in the grain layer have been eliminated by a known method, and Fig. 6 Such a leather whose grain layer has been treated by the method according to the invention.
  • Fig. 7 also shows, on average, a leather whose grain layer has been treated by the method according to the invention.
  • a leather 3 is supported on the in a manner not shown, known per se, for example by spraying or by roller application, preferably by a counter to the transport direction 1 rotating applicator roll, an aqueous, compact particles containing plastic dispersion was applied, which was solidified by supplying heat, for example by means of hot air.
  • the transport device 2 is made in this case suitably from a plurality of spaced, parallel polyamide or polyester threads, between which spaces are kept free. These threads are shown enlarged in the drawing. In practice, its diameter is less than 4 mm.
  • a hot steam source hot steam supply device consisting of tubes 5 of any cross-section, which are provided with outlet nozzles or slots 6, from which relaxed hot steam with no or little pressure in the direction to the solidified plastic dispersion 4 emerges.
  • the number of tubes 5 arranged one behind the other in the transporting direction 1 depends on the transport speed of the leather 3 and must be chosen such that pressurization of the solidified plastic dispersion with relaxed superheated steam is ensured in the short time required for the formation of the hollow microspheres.
  • the distance between the outlet nozzles or slots 6 and the solidified plastic dispersion 4 must be selected so that the hot steam at a temperature of at least 80 ° C impinges on the plastic dispersion.
  • hot air drying ducts 9, 10 are provided, in which over the interstices between the polyamide or polyester threads and the underside of the leather 3 warm air can be supplied.
  • the solidification of the plastic dispersion 4 applied to the leather 3 takes place before the formation of the hollow microspheres 7 from the compact particles takes place in the region of the tubes 5; in the heat-drying duct 10, the coating already having a foam structure takes place.
  • a superheated steam container 5 ' is provided, which has the transport device 2 directed outlet nozzles or slots 6'.
  • the hot steam tank 5 ' is connected to a superheated steam source, so that emerges via the outlet nozzles or slots 6' superheated steam, which passes through the spaces between the plastic threads to the leather 3, so that on the passing through this leather superheated steam formation of the hollow microspheres in the solidified plastic dispersion filled recesses of the scar layer occurs and the solidified plastic dispersion also of the bottom is foamed.
  • a hot steam tank 5 ' may also be provided, in addition to the hot steam tank 5' below the transport device 1 or without such a hot steam tank below the transport device 1.
  • Fig. 3 shows an embodiment in which the tubes 5 of the hot steam supply means are arranged meandering and connected at both ends with a superheated steam source 16 such that the superheated steam continuously circulates in the tubes 5 and undergoes no cooling, so that exposure to superheated steam at constant temperature, because the condensed water is converted back into steam.
  • the individual pipe sections in this case run transversely to the transport direction.
  • Fig. 4 shows a construction according to the invention, in which the transport device 2 passes through a hot steam tank 17 which is connected to a superheated steam source, or in which the steam is generated from demineralized water, so that the superheated steam evenly flows around the leather with the solidified plastic dispersion thereon. The spaces between the plastic threads allow this access of the superheated steam on the underside of the leather.
  • the method according to the invention also makes it possible to apply a coating to both sides of a leather, for example for the purpose of correcting defects on the grain side of a grain leather and for attaching foam equipment to the back side opposite this grain side.
  • an aqueous, compact particles-containing plastic dispersion is first applied to one side and then to the other side of the leather and allowed to solidify completely, whereupon both sides, preferably simultaneously, can be subjected to the action of relaxed superheated steam. It is then on both sides of the leather, as in Fig. 2 shown hot steam supply means provided, or it is an arrangement according to Fig. 4 used so that the formation of the hollow microspheres of the compact particles takes place simultaneously in the solidified plastic dispersion present on both sides of the leather.
  • Fig. 5 shows in cross section a leather with a leather layer 11 and a grain layer 12, which has recesses 13 formed defects.
  • these recesses 13 are filled by a solidified plastic dispersion 14, which Contains hollow microspheres.
  • These hollow microspheres are formed by compact particles contained in the plastic dispersion by application of pressure and heat.
  • the leather layer 11 is compressed, but the leather turns back after pressure relief due to its compressive elasticity, whereas the present in the wells 13 solidified plastic dispersion 14 does not change its volume.
  • FIG. 6 shows the solidified plastic dispersion 14 in the wells 13 after formation of the hollow microspheres by the action of relaxed hot steam even a slight elevation 15, which can be easily removed by a very fine sandpaper, preferably with a grain size of less than 600 / cm 2 without damaging the scar layer 12. It is also a hot ironing possible.
  • Fig. 7 is a leather 11 shown with so-called pinholes 18 shown in cross section, which extend through the grain layer 12 into the leather layer 11 and partially penetrate this leather layer 11 even completely.
  • pinholes 18 are common and depending on the existing number of pinholes, which have a diameter between 0.3 mm and 1.5 mm, the dermis is inferior to worthless.
  • the density of Kompktktteilchen is more than 1.2 g / cm 3 and is thus always higher than the density of the plastic, which is the discontinuous phase of the dispersion.
  • the manual plush can also be used to fill in the pinholes.
  • the hollow microspheres can unfold optimally in the solidified plastic dispersion which has become softer under the influence of superheated steam.
  • the advantages of the invention will also be clarified by sanding off the full grain side of leathers, either to provide a better anchorage of a finish, or to eliminate defective pits in the surface. Both result in a significant loss of value, because the leather thus produced may not be offered as full-grain leather.
  • the foamed base coat heals scar defects and creates a surface that looks like the finely grained grain side of a leather, but at full or near full, preservation of the true grain layer. Above all, the base coat forms the basis for leather with a fine textured or smooth surface.
  • Leathers with a basecoat produced according to the invention are particularly suitable for the application of an indirect method for forming a finish coat on the base coat, in which process the thin finish coat preferably having a fine-grained surface is first prepared separately on a patterned backing and then adhesively bonded to the nubuck-type primer coat becomes.
  • the hot steam is applied directly to the solidified plastic dispersion, for example via steam outlet nozzles or slots depressurized or almost without pressure, wherein the hollow microspheres can form from the compact particles.
  • the superheated steam by water is applied to the solidified plastic dispersion or on the meat side of the leather by means of a spray and then the leather with the solidified plastic dispersion is subjected to a short heat treatment, such that the thin water application in forms less than 25 sec of superheated steam.
  • the leather especially on its flesh side, moistened shortly before with a more than 90 ° C hot metal plate without pressure or with a very low pressure of a maximum of 1 kg / cm 2 are brought into contact or transported through a heated roller.

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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)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)

Claims (12)

  1. Procédé d'application d'un revêtement, de préférence d'un revêtement de base, sur au moins un côté, éventuellement sur les deux côtés, d'un cuir, à savoir sur le côté fleur et/ou sur le côté chair opposé à ce côté fleur d'un cuir fleur, ou sur un côté ou les deux côtés d'un cuir scié, une dispersion plastique aqueuse qui comporte des particules compactes contenant un agent gonflant étant appliquée sur ce ou ces côtés et laissée durcir, et des microbilles creuses étant formées à partir des particules thermoplastiques compactes par apport de chaleur, caractérisé en ce que la dispersion plastique qui contient les particules compactes est soumise à l'action d'une vapeur surchauffée détendue à une température comprise entre 80 °C et 100 °C après son durcissement.
  2. Procédé selon la revendication 1, caractérisé en ce que la vapeur surchauffée agit sur la dispersion plastique avec une pression inférieure à 0,1 bar.
  3. Procédé selon la revendication 1, caractérisé en ce que la vapeur surchauffée agit sur la dispersion plastique pendant une durée inférieure à 7 secondes, de préférence inférieure à 3 secondes.
  4. Dispositif pour l'application d'un revêtement sur au moins un côté, éventuellement sur les deux côtés, d'un cuir (3), à savoir sur le côté fleur, éventuellement poncé, et/ou sur le côté chair opposé à ce côté fleur d'un cuir fleur, ou sur un côté ou les deux côtés d'un cuir scié, muni d'un dispositif d'application pour l'application d'une dispersion plastique aqueuse (4) qui comporte des particules compactes contenant un agent gonflant sur le ou les côtés du cuir (3), et muni d'une source de chaleur qui agit sur la dispersion plastique appliquée (4) en provoquant un durcissement de celle-ci et une expansion des particules compactes pour former des microbilles creuses (7), caractérisé en ce qu'un dispositif d'apport de vapeur surchauffée (5) qui agit sur la dispersion plastique durcie est prévu.
  5. Dispositif selon la revendication 4, caractérisé en ce que le dispositif d'apport de vapeur surchauffée comporte au moins une conduite de vapeur surchauffée (5) avec des buses ou fentes de sortie (6) dirigées contre la dispersion plastique durcie.
  6. Dispositif selon la revendication 4 et 5, caractérisé en ce que la conduite de vapeur surchauffée (5) est constituée d'un tube à section ronde ou anguleuse.
  7. Dispositif selon la revendication 6, caractérisé en ce que le tube est conçu sous une forme sinueuse et est relié à ses deux extrémités à une source de vapeur surchauffée (16) (Fig. 3).
  8. Dispositif selon la revendication 4, caractérisé en ce que le dispositif d'apport de vapeur surchauffée comporte un contenant de vapeur surchauffée (17) qui entoure le dispositif de transport et qui est relié à une source de vapeur surchauffée.
  9. Dispositif selon l'une quelconque des revendications 4 à 8, caractérisé en ce que le dispositif d'apport de vapeur surchauffée est placé à côté d'un dispositif de transport (2) en circulation qui supporte le cuir (3) muni de la dispersion plastique durcie.
  10. Dispositif selon la revendication 9, caractérisé en ce que le dispositif de transport (2) est constitué de plusieurs fils plastiques en circulation, parallèles et espacés, tels que des fils de polyamide ou de polyester.
  11. Dispositif selon l'une quelconque des revendications 4 à 10, caractérisé en ce qu'un canal d'air chaud (9, 10) entourant le dispositif de transport (2) est prévu avant et éventuellement également après le dispositif d'apport de vapeur surchauffée (5, 5') dans la direction de circulation du dispositif de transport (2).
  12. Cuir, fabriqué par un procédé selon la revendication 1, caractérisé en ce que la surface du revêtement traitée avec une vapeur surchauffée détendue présente une apparence homogène, de type nubuck, sans creux.
EP06723413A 2006-02-20 2006-03-14 Procede et dispositif destines a disposer un revetement sur au moins un cote d'un cuir et cuir revetu obtenu par un tel procede Not-in-force EP1989333B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT0012606U AT8974U1 (de) 2006-02-20 2006-02-20 Verfahren und vorrichtung zum aufbringen einer beschichtung auf zumindest eine seite eines leders, und nach einem solchen verfahren hergestelltes, beschichtetes leder
PCT/EP2006/002335 WO2007095970A1 (fr) 2006-02-20 2006-03-14 Procede et dispositif destines a disposer un revetement sur au moins un cote d'un cuir et cuir revetu obtenu par un tel procede

Publications (2)

Publication Number Publication Date
EP1989333A1 EP1989333A1 (fr) 2008-11-12
EP1989333B1 true EP1989333B1 (fr) 2010-01-27

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EP06723413A Not-in-force EP1989333B1 (fr) 2006-02-20 2006-03-14 Procede et dispositif destines a disposer un revetement sur au moins un cote d'un cuir et cuir revetu obtenu par un tel procede

Country Status (11)

Country Link
US (1) US8697232B2 (fr)
EP (1) EP1989333B1 (fr)
KR (1) KR101168470B1 (fr)
CN (1) CN101379198B (fr)
AR (1) AR059582A1 (fr)
AT (2) AT8974U1 (fr)
BR (1) BRPI0621357A2 (fr)
DE (2) DE502006006066D1 (fr)
MX (1) MX2008010683A (fr)
WO (1) WO2007095970A1 (fr)
ZA (1) ZA200806892B (fr)

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DE102006039261A1 (de) * 2006-08-22 2008-03-06 Lanxess Deutschland Gmbh Zugerichtetes Leder
US20090205142A1 (en) 2006-10-11 2009-08-20 Vorlaender Otto Process for Retanning Leather Using Hollow Microspheres
DE102007011555A1 (de) 2007-03-09 2008-09-11 Lanxess Deutschland Gmbh Verfahren zum Nachgerben von Leder mit Mikrohohlkugeln
KR101360376B1 (ko) 2013-07-19 2014-02-21 홍종희 육면에 인쇄층이 형성된 가죽원단 및 가죽원단의 육면 인쇄방법
CN104307710B (zh) * 2014-09-22 2016-06-08 浙江西雅普康大制革有限公司 用于合成革加工的除气泡设备及其控制方法
JP6507587B2 (ja) * 2014-11-18 2019-05-08 凸版印刷株式会社 塗工方法及び発泡壁紙の製造方法
KR102139536B1 (ko) * 2019-05-10 2020-07-29 주식회사 노비아레텍 경량화 발포 은면피혁의 제조 방법

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US20100021722A1 (en) 2010-01-28
CN101379198A (zh) 2009-03-04
WO2007095970A1 (fr) 2007-08-30
DE202006005330U1 (de) 2006-06-08
KR101168470B1 (ko) 2012-07-26
ZA200806892B (en) 2009-10-28
CN101379198B (zh) 2011-12-14
DE502006006066D1 (de) 2010-03-18
AR059582A1 (es) 2008-04-16
AT8974U1 (de) 2007-03-15
KR20080095910A (ko) 2008-10-29
MX2008010683A (es) 2008-09-01
ATE456679T1 (de) 2010-02-15
US8697232B2 (en) 2014-04-15
BRPI0621357A2 (pt) 2011-12-06
EP1989333A1 (fr) 2008-11-12

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