US3919451A - Method for finishing leather and leather substitutes - Google Patents

Method for finishing leather and leather substitutes Download PDF

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Publication number
US3919451A
US3919451A US377885A US37788573A US3919451A US 3919451 A US3919451 A US 3919451A US 377885 A US377885 A US 377885A US 37788573 A US37788573 A US 37788573A US 3919451 A US3919451 A US 3919451A
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United States
Prior art keywords
leather
range
coating
crushed foam
latex
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US377885A
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English (en)
Inventor
Jerome F Levy
Hugo A Alps
Michael L Alderman
David A Templer
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Rohm and Haas Co
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Rohm and Haas Co
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Publication date
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Priority to US377885A priority Critical patent/US3919451A/en
Priority to CA199,875A priority patent/CA1027813A/en
Priority to IE1103/74A priority patent/IE39788B1/xx
Priority to DE19742425553 priority patent/DE2425553A1/de
Priority to IN1178/CAL/74A priority patent/IN141916B/en
Priority to AU69721/74A priority patent/AU488414B2/en
Priority to GB2578174A priority patent/GB1465618A/en
Priority to ES427247A priority patent/ES427247A1/es
Priority to PL1974172389A priority patent/PL103078B1/pl
Priority to FR7423180A priority patent/FR2236941B1/fr
Priority to SU7402039701A priority patent/SU582777A3/ru
Priority to IT24793/74A priority patent/IT1015669B/it
Priority to AR254555A priority patent/AR199844A1/es
Priority to JP7814174A priority patent/JPS5713600B2/ja
Priority to BE146368A priority patent/BE817430A/xx
Application granted granted Critical
Publication of US3919451A publication Critical patent/US3919451A/en
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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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/904—Artificial 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
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249975—Void shape specified [e.g., crushed, flat, round, etc.]
    • 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
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic

Definitions

  • ABSTRACT A process for finishing leather and leather-like material which comprises applying a foamable latex to low grade leather and leather substitutes. drying and foaming the latex coated substrate, crushing the foam coating then treating the crushed foam coated low grade leather or leather-like material with a finish coat which results in the preparation of leather and leather substitutes having improved properties over leather and leather substitutes coated in the conventional manner.
  • LIiA'IIIICR SIIBSII'IITES 'lhis invention relates to a no ⁇ cl process for line-thing leather splits. low grade corrected and full grain leathers. nonwovcn ⁇ icbs and other artifical webs applica ble to manufacture of synthetic leathers especially for shoe upper end use. pigskins. sheepskins. and other leather-like materials which yields a finished product possessing the aesthetics required by the leather trade ⁇ vhilc dramaticalh reducing the number of steps to quired in achiciing the finished product. in addition. the resulting product maintains or impro.
  • this process eliminates many steps of the conventional processes providing an economical pro cess for upgrading leather and leather substitutes. Still another advantage is the controlled buildup of thc coating which eliminates photographing.:" of the underlying substrate.
  • the fhis process also eliminates the ncccssity for impregnating the leather substrate. though we haic found that in certain situations a better product may be obtained hen impregnating is done the owrall properties ofthc sy stem are controlled by the properties of the foamable latex which allo ⁇ s one to obtain a soft. flexible. water vapor permeable coat and together nith a llnish coat of a durable resin system one obtains the desired abrasion and scuff resistance t'tl't
  • a crushed foam coating means a coating which after obtaining a cellular structure is compressed by crushing or embossing.
  • thi inrcntion prrnidcs a novel process for preparing finished leather and finished leather substitutes which coinpriscs treating various substrates including grain leather. upper leather. leather splits. reconstituted leather. leather substitutes. nonavoven webs possessing extensibility and recovery. resilcncy and other properties resembling leather and the like in the following manner:
  • a chemical blowing agent selected from 1.
  • finish coat to the crushed foam coated substrate wherein the finish coat is selected from compositions containing melamine resins. urea-formaldehyde condensates. nitrocellulose. urethanes. polyvinyl chlorides. acrylics. ce lulose acetate butyrates. nitrocellulose. modified urcthancs or mixtures thereof.
  • the preferred method comprises:
  • the following is the preferred method and comprises:
  • crushed foam coated leather substitute at a pressure in the range of from about 5 to about 2500 psi and. preferably. at a pressure in the range of from about 50 to 1000 psi at a temperature in the range of from about 150 to about 400F.. and. preferably. at a temperature in the range of from about 275 to about 325F.. and
  • embossing with a flat hydraulic or mechanical press where time in contact with the bed is easily determined.
  • actual time that the material is in contact with the roll and contact pressure are more difficult to define. Some doviations from those conditions including temperature 4 of embossing therefore would be expected.
  • the times for conducting the crushing. embossing and curing will usually vary from 0.5 to 10 seconds.
  • the time period is preferably from about 2 to about 6 seconds.
  • the preferred times are from 0.5 to 2 seconds.
  • Crushed foam coating as currently practiced in the textile industry uses mechanically generated foam which is knifed onto a continuous roll of fabric. Knife coating is an unacceptable technique for finishing leather as it results in excessive wastage of the coating material also an even coating cannot be applied to leather which leather is often of nonuniform thickness.
  • Mechanically generated foam can be applied by spray. but collapse of the foam during spraying, and the high volumetric throughput of low density foam required to achieve reasonable coating add-ons makes this a decidely unattractive prospect. Spray application of the unfoamed mixture provides inadequate surface coverage and hiding.
  • foaming can be made to occur as the coating emerges from the spray gun since it is possible to employ solvent blowing agents with a boiling point below ambient temperatures or upon oven drying of the coated substrate. Since the coating penetration will generally give better adhesion but stiffer temper. control over the final properties of the coating is now possible through selection of blowing agents having the required characteristics disclosed below.
  • the solvent might be able to foam the polymer if it were still in the polymer after the water has been driven off and more heat is applied.
  • foaming the latex There is a distinction between foaming the latex and foaming the polymer.
  • the process of generating a cellular structure by internal gas or vapor generation in a continuous polymer phase is quite different and will possess different requirements from generating a foam from a latex where the continuous (water) phase is the expanded structure which must be stabilized as a cellular network by having latex particles on the surface of the bubbles form films or struts which remain after the continuous phase has evaporated.
  • the swell ratio is defined as the volume of the swollen polymer network in a given solvent divided by the volume of the polymer sample before solvent treatment.
  • trichlorotrifiuoroethane pentane. hexane. cyclohexane. trichlorofluoromcthane. monochlorotrifluoromethane. monobromotrifluoromethane. monochlorodifluoromethane. octafiuorocyclobutane and isomers thereof.
  • the amount of blowing agent solvent employed may vary from about 3 to about percent by weight of the total weight of the formulation. In general. the solvent chosen is from about 7 to l2 percent by weight of the weight of the formulation.
  • organic chemical blowing agents include azo compounds such as azobisformamide. azobisisobutyronitrile. diazoaminobenzene and the like. N-nitroso compounds. such as N.N'- dimethyl-NN'dinitrosoterephthalamide. N.N'-dinitrosopentamethylenetetraminc and the like and sulfonyl hydrazides such as benzenesulfonylhydrazide.
  • organic chemical blowing agents include azo compounds such as azobisformamide. azobisisobutyronitrile. diazoaminobenzene and the like. N-nitroso compounds. such as N.N'- dimethyl-NN'dinitrosoterephthalamide. N.N'-dinitrosopentamethylenetetraminc and the like and sulfonyl hydrazides such as benzenesulfonylhydrazide.
  • inorganic chemical blowing agents include ammonium bicarbonate. sodium bicarbonate, sodium carbonate, hydrogen peroxide. ammonium nitrate. malonic acid and the like with ammonium bicarbonate being the preferred chemical blowing agent.
  • the quantity of foam applied will depend on the nature of the substrate and the type of print desired. A 15-30 gm./sq. ft. wet add-on would be recommended for a finely buffed impregnated split using a hair cell print since impregnation helps to seal the surface and hold out the foam system. A 60 gni./sq. ft. wet addon might be required on an unimpregnated nappy split with a deep lizard print. Add-ons in the 60 gm. range should be generally avoided except for exceptionally deep prints. The above wet add-ons are predicated on the foam being applied from a formulation containing about 50-55% polymer and will vary with polymer content.
  • the drying step is conducted at a temperature in the range of from about 120 to about 400F. Some crosslinking occurs during this step and it is necessary to prevent a large amount of crosslinking which. if it occurred at this stage would interfere with embossibility. Generally. drying temperature and time are determined by varying one then the other until the desired properties are obtained.
  • the drying time is dependent on many factors but in general dwell time in an oven ranges from 2 to 8 minutes.
  • the major concern in drying is to control the drying conditions to avoid excessive skinning of the foam which yields poorer results, and also necessitates longer drying times since it insulates and seals off the wet foam underneath.
  • the important variables which play a role in drying are temperature. residence time. add-on of foam and airflow in the oven.
  • the airflow in the oven is an important variable which can be regulated by adjusting the baffles in most ovens and in certain ovens by variation of the blower speed. It is recommended that high air velocities. while beneficial for rapid drying. do not impinge directly on the foam because this can lead to severe turbulence and skinning problems.
  • the exact degree of drying is determined subjectively. It should be dry enough so that when one runs his finger along the foam. it does not feel squishy and not too dry so that the material fails to accept a good print pattern. Laboratory data indicate that a large latitude in drying time is available between under drying and over-drying. For example. if 3 minutes is judged as the best drying time for a specific piece of equipment. l.5 minutes would probably yield an acceptable result with the only deficiency being somewhat poorer release from the plate after embossing. while a 5 minute drying interval would probably show only a slight decrease in print definition but would otherwise yield acceptable results. Print definition is exceedingly important for without it the finish will not have the authentic appearance of leather.
  • the next step comprises the single step of crushing. embossing and curing the foam coated substrate.
  • embossing and curing process steps has been eliminated.
  • the coated substrate may be subjected to some minimal pressure (eg 5 psi) if it is necessary to handle the coated substrates.
  • some minimal pressure eg 5 psi
  • the coating is slightly tacky and may delaminate if the coating is brought into contact with some other material; or piled face to face with other foam coated substrates; however. even minimal pressure will assure sufficient adhesion of the coatings.
  • the final step in the process for preparing the finished leather and finished leather substitutes comprises applying to the crushed foam coated leather substitutes a finish coat composition which is extensible and flexible containing one of the following ingredients: nitrocellulose. urethanes. polyvinyl chlorides. acrylics. cellulose acetate butyrates or a composition containing nitrocellulose and an isocyanate terminated prepolymer of an organic polyisocyanate with a polyester or polyether polyol or mixtures thereof with or without plasticizers.
  • the preferred finish coats are the Coating compositions which contain nitrocellulose and an isocyanate terminated prepolymer of an organic polyisocyanate with a polyester or polyether polyol or contain cellulose acetate butyrate.
  • the amount of nitrocellulose present in one of the preferred compositions is preferably in the range of from about 15% to about based on the total solids of the composition.
  • These preferred coating compositions are further described in the US. patent application Ser. No. l6l.987 now US. Pat. No. 3.763.061 which application is hereby incorporated by reference.
  • the finish coat should be applied so that there is approximately 1.0 gm. of solid top coat per sq. ft. of substrate in order to yield the best balance of physical properties in terms of flexibility and abrasion resistance.
  • the finish coat add-on can be controlled by the solids of the formulation. machine settings. conveyor speeds and the number of coats applied.
  • the top coat should be formulated at a urethane/nitrocellulose ratio 7 of 55M?
  • the latex coatings employed in this invention should contain a latex polymer. clay. titanium dioxide or other inert tillers and a foam stabilizer and may contain an additive for erosslinking the polymer.
  • the latex compositions that produce the foams used in the present invention are prepared from at least two of the following monomers of which at least one is a monomer which contains functional groups capable of crosslinking:
  • a an rufi-ethylcnically unsaturated acid which ineludes acrylic acid. methacrylic acid. ethacrylic acid. itaconic acid. aconitic acid. crotonic acid. citraconic acid. maleic acid. fumaric acid, rt chloroacrylic acid. cinnamic acid. mesaconie acid. and the like. Mixtures of these acids can also be used;
  • R is hydrogen or alkyl. for example. lower alkyl of from [4 carbon atoms and R is a straight. branched or cyclic chain alltyl. alltosyalkyl or alkylthioalkyl radical haying from i to 20 carbon atoms. or cycloalkyl having from 5-6 carbon atoms. such as methyl. ethyl. propyl. irbutyl. lethylhexyl. heptyl. hexyl. octyl. Z-methylhutyl. l-methylbutyl. butoxybutyl.
  • hydroxymethyl hydrosyethyi. hydroxypropyl. hydroty'butyl, hydroxypcntyl. and the like; 2.3epoxypropyl. amino lower alkyl or monoor dilower alkyl or by droxy lower alkyl substituted amino lower alkyl;
  • c. a monomer of the formula wherein R is hydrogen or methyl and R is halo such as chloro and the like; lower alkanoyloxy such as acetoxy and the like. cyano. formyl. phenyl. carbamoyl. l ⁇ '- hydroxymethyl. tolyl. methosylethyl. Z.-ldiamino-striazinyl lower alkyl. and epoxy;
  • R is hydrogen or methyl: R and R are lower alkoxy such as methoxy. ethoxy and the like or lower alkanoyloxy such as acetoxy and the like.
  • Examples ofthe specific monomers described in sub paragraphs (b) and (c) and (d) which may be employed are: methyl methacrylate. ethylmethacrylate. propyl methacrylate. isopropyl methacrylate. n-huty'l methacrylate. isobutyl methacrylate. secbutyl methacrylate. tert-butyl methacrylatc. pentyl methacrylate. isopentyl methacrylate. tert pentyl methacrylate. hexyl methacrylate. cyelohcxyl methacrylate, lethylbutyl mcthacrylate.
  • hydrosyethyl methacrylate methacrylonitrile. methox ymethyl methacrylamide. Nanethylol methacrylamide. acrolein. methacrolein. 3.4-epoxyl-butene. acrolein diethyl acetal. acrolein dimethyl acetal. allyiidcne diacetate. methallylidene diacetate. the analogs of the above methacrylic acid derivatives with other unsaturated acids such as acrylic acid and itaconic acid. such acids themselves. diearboxylic acids such as maleic acid and half esters and half amides thereof. vinyl ethers of glycols such as ethylene glycol are also included.
  • crosslinkable addition polymeri/able unsaturated monomers have reactive polar groups selected from Such groups may be included as are mutually or selfcrosslinkable. or separate crosslinking compounds such as triazineformaldehyde resin may be added.
  • Atensensitnc materials such as isocyanates should not be used in aqueous systems unless they are blocked by reaction with a phenol group which protects the isocyanate groups until subsequent heating or the use of other reaction mechanisms such as the use of calcium. zinc. or tin compound catalyst conventional in the art.
  • the preferred emulsion copolymers have a molecular weight of between about 70.000 and 2.000.000 and preferably between about 250.000 and 1.000.000 and are made by the emulsion copolymerization of the SEV eral monomers in the proper proportions.
  • Conventional emulsion polymerization techniques are described in US. Pat. Nos. 2.754.280 and 2.795.654. 'l'hus.
  • the monomers may be emulsified with an anionic. a cationic. or a nonionic dispersing agent. about 0.05 to 10 percent thereof ordinarily being used on the weight of the total monomers.
  • the acid monomer and many of the other functional or polar monomers may be soluble in water so that the dispersing agent serves to emulsify the other monomer or monomers.
  • a polymeri/atinn initiator ol the tree radical type. such as am inoniurn or potassium persull'ate. may be used alone or in conjunction itith an accelerator. such as potassium nietahisullite. or sodium thiosuilate.
  • l'rganic peroxides. such as hen /oyl peroxide and terthutyl hydropertWlitii. are also uschil initiators. lhe initiator and accel erator. commonly rettiiied to as catalyst.
  • lhe temperature may he l'roni l i lit temperature to about l4tl i 'lhe tollouing is a list ot eopolyiners uliieh may be employed in lltlr-l inwiition'.
  • ol' a hater soluhie suilactant or a coniliina tion or sin'l'actants inciewses the dispersion ol the latex emulsion and acts as a foaming aid and foam stabilizer.
  • lhcse suilaetants include the alkali metal. amino ninm or amine salts. such as the monw. di or tricthanol amines ol' the aliphatic carhoxylic acids having from 1:1 to Ill carbon atoms including namelyic acid. stearic acid and the like. ior eerniple. sodium. potassium or ammo nium stearate. sodium potassium or ammonium olcate and the like titlirr surfactants which may he employ ed together tvith those described ahove include the alkali metal salts ol aiiphatic or aikylaryl sullonic acids.
  • the prch rrcd res n are the therniosrt ones since the foam generated at" fords leather and leather substitute products more dc sirahlc in the inan lhieture ot'aud snltsetpien use tith a ni not tilitrtt". for example. dieihylene int. i rlia'in' t th lilo.
  • 'l'hc finish coat compositions can he applied to the crushed foam coated substrates by any of the tech nit ues wellknoyyn in the art. including brushing. stvahhing. spraying. cuitain coating iflou' coating). or dip coating. Among the useful techniques are those described in US. Pat. Nos. 1126.321 and 2.884.34tl.
  • One or more coats can he applied as desired. the thickness ot the coating can be varied depending on the particular purposes that the coating is to serve. The amount of the finish coat applied varies according to the type of material being coated and the ultimate finish desired. (ienerally.
  • the finish coat is applied so as to provide a deposit ol troni about til to about 5% mils dry film thickness and. preferably. from about 0.3 to about 05 mils dry tilin ll'liLiilitf. ⁇ %.
  • the coating can be cured by drying to a tack-tree state at room temperature for about Bil minutes to one hour. or by heating at a temperature ol up to ahout ltlllT. until the desired degree ot cure is effected.
  • nitrocellulose/urethane finish coat An adutntage of the nitrocellulose/urethane finish coat is that it forms a coating which has outstanding elastic recovery and [leohility and yet is tough enough to he used as a wear layer when applied to leather or leather substitute in luggage or upholstery. and in garments such as shoe: jackets and the like.
  • These characteristics of flexibility and elastic recoycry make the nitrocelluloschirethane finish coat compositions extremely valuable in the coating of thick flexible suhstrates. and particularly with those substrates having a thickness of from about 3i! mils to about ltlt) mils. which substrates are subjected to severe bending action. for example. in the coating of leather or leather substitute used in luggage. upholstery. shoes and other garments.
  • emulsion polymers are preferred.
  • polymers prepared in organic solutions eg. in ethylene glycol. ether. xylene. ethylene glycol mononiethyl ether and the like by ⁇ tc'll'kli WIi conventional means such as tree-radical initiation vii .li henzoyl peroxide or the like are also Luzeiu Solu ion polymers useful in the inven titan prel nial ly l a t' a molecular Weight oi hetivccn lillillli and i li ll llltli l the iiiimulation oi the crushed toani coating is capahlc ml a. wide ariation.
  • the following table illustrates the comptviems of he io rnulation which may be enipli a. tt l:
  • Pat is li Ti -l nniue ltcsnr.
  • ingredients can be incorptn tvd into the [train coating iorrnulation. in panoxy. till-as. olorants and waxes are added to the iorinulation in various proportions to afford products having specific desired characteristics.
  • types of fillers which may be employed include clays. mica. calcium carbonate. bentonite. silica and the like.
  • colorants which may be employed include dyestuffs made from inorganic and organic pig ments especially dispersions of the pigment in water with a dispersant and a protective colloid.
  • carbon black iron oxide pigment, anatase. titanium dioxide and the like.
  • Waxes are employed to aid in the release of the press plate.
  • These waxes are well known to those skilled in the art and include the polyethylene waxes and the like.
  • EXAMPLE I Charge Parts by Weight Copoly mcr com posed of MBA/HAN/IAQ'ZAA 100 China (lay l Ammonium Stearate (33 i I 7.0 Diethylenetriamine on Ammonium Hydro ⁇ ide (26%
  • EXAMPLE I Formulation Z Copoly rncr composed of KZ5BAHIJANJl5Ac/3AA 500.0 Clay 75.0 Ammonium Stcaratc 35.0 Diethylenctriaminc 3.5 Ammonia (28'; 10.0 Primal llroun Colorant 750 Water (155 EXAMPLE 3 Formulation 3 Copoly mer composed of XoEAllUAN/JMOA 565.5 Clay 75.0 Ammonium Stearate 35.0 Aqueous melamine formaldehyde resin l [.5 Ammonia (3)”) I 10.0 Primal White Zo-l Colorant 75.0
  • EXAMPLE 4 Charge Parts by Weight H. 65.5 NH 12W) loo Clay 75.0 Primal Blk. 1H) 75.0 Copolymer composed of 9hEAl3MOA105AA 500.0 Ammonium Stcarate 35.0
  • Examples 1 to 6 are added to the mix in the order given (the NH:; is split into two feeds; half being saved until after the melamine resin. Aerotex MW. has been added) and stirred thoroughly (Lightning mixer. Talboys mixer or Cowles dissolver). Any other melamine resin may be employed such as those sold under the following tradenames: Aerotex M-3. melamine-formaldahyde-methanol. methoxylated mel amine formaldehyde. After mixing. the formulated mix is covered to prevent skinning over.
  • EXAMPLE 7 Formulation 7 (hargc Parts by Weight Copoly mcr composed of K3llAfl-lAl ⁇ /lAcr2AA 410.5 Ammonium Stearate 15.8 Octylphenoxy polyethoxy ethanol ll.5 Acme WW Clay 7.5 Primal Black ll0 41.7 NH. (15'1') 7.0 Polyethylene Wax 23.9 Dicthylenc triaminc ll hll().0
  • the latex and non-ionic surfactants are added to a Cowles dissolver and stirred slowly. To this is added the ammonium stearate. The agitation is increased while slowly adding the remaining ingredients in the order given. After a uniform suspension is obtained. the formulation is filtered through a cheese cloth or mesh screen mesh). This material is now ready to be employed with an appropriate blowing agent. By substituting for the colorant. Primal Black H0. other suitable colorants. other formulations can be prepared in substantially the same manner.
  • EXAMPLE 8 Spraying from an Aerosol Can
  • the formulation of Example 3 70 g. trichlorofluoromethane g). and dichlorodifluoromethane (40 g.) are charged to a six ounce aerosol can with a nonbreakup nozzle.
  • the can is shaken and the contents sprayed onto l leather split and (2) paper.
  • the sprayed material begins to foam upon leaving the nozzle of the spray can since the boiling point of the propellant blowing agent is below that of ambient temperature and foaming of the coating continues on the substrate.
  • After drying. the coating on leather is simultaneously crushed.
  • embossed and cured on a Watson Stillman Press 190F.. 30 tons. 3 seconds). Density of the foam sprayed is approximately 0.007 gms./cubic centimeter.
  • the foam has a density of approximately 0.012 gm./cubic centimeter after crushing and embossing as above.
  • Example 9 Spraying with Spray Gun
  • the formulation of Example 7 is mixed with trichlorotrifluoroethane at room temperature.
  • the mixture is placed in a pressure pot (vacuum feed. 60 pounds line pressure. l5 pounds pot pressure).
  • the mixture is sprayed onto leather at approximately L3 to 1.5 ounces wet add-on per square foot.
  • the mixture foams slightly at room temperature but upon drying at 280F. the coating foams up well. Crushing. embossing and curing are accomplished simultaneously on a Watson Stillman Press at lF.. 30 tons. for 3 seconds.
  • Example 9 EXAMPLE l0 Spray Gun The experiment of Example 9 is repeated using trichlorotrifluoroethane except that the leather split employed is heated for several minutes at 280F. before applying the coating. The coating when applied to the 13 heated leather immediately foams and continues to foam during drying. Crushing embossing and curing. as in Example 9. affords a leather with an excellent pattern.
  • EXAMPLE l l Foaming Properties of Acrylic Emulsion Polymers Using Triehlorotrifluoroethanc The testing of the foaming properties of various acrylic emulsions is conducted by employing a formulation of the following composition: Latex 307.5 g; NH; (28% 5.0 g.; colorant 537.5 g. and trichlorotrifluoro ethane 35 g.
  • the formulations are sprayed with pot pressure spray equipment at l5 lbs. pot pressure and 80 lbs. line pressure.
  • the substrate used is a white cardborad paper panel l4/2 inches X 11 /2 inches. After spraying, the coating is air dried for l minute and then dried for five minutes in a forced draft oven at 280F.
  • the polymers employed were prepared from the following proportion of monomers:
  • Butadiene rubber (Hycar l57l EA ethylacrylate; BA butylacrylate; MMA mcthylmethacrylate;
  • HEMA hydroxyethyl methacrylate; AN acrylonitrile; AC acrolein.
  • MOA acrylamide/methylol acrylamide l:l and AM 2 acrylamide.
  • Step 8 Preparation of Finish Coat Composition
  • the finish coat composition is prepared by mixing RESU LTS Foam Add-on Applied Brookfield Polymer Rating (g./sq.ft. I Solids pH ⁇ "isc. (cps) Hue 1 Good 44.3 9.4 High Bluish Black I Fair-Good l4.4 44.3 9.9 336 Bluish Black 3 Fair'Uood l4.4 44.3 8.6 168 Bluish Black 4 Fair-(jootl 21.6 44.3 9.8 6-43 Bluish Black 5 Good-Yer) Good 144 43.5 10.] 660 Bluish Black 6 Fair-Good lol 44.3 l0.0 4X (ireenish Cast 7 Fair(iooil l0.2 ⁇ 37.5 10.: I636 Bluish Black 8 Fair-Good Ill 44.3 9.7 88 Green 9 (iootl l4.0 44.3 9.7 l l 300 Green 10 (iootl 19.8 44.3 9.4 360 Bluish ll ⁇ 'cr (jood 8.5 38.3
  • Step C Application The composition of Step B is applied to the leather or leather-substitute using standard spray equipment such 15 that about I .0 g, of solids per square foot of substrate is obtained.
  • Step A 97.5 parts polyt 1,3-butylene adipate ⁇ obtained by a conventional process, having a molecular weight of 5,000 and a hydroxy number of 20, is thoroughly dehy drated by sparging with nitrogen at 130 to 140C.
  • the polyester is then cooled to 106 to 108C. and 4h parts of methylene-twist-lphenylisocyanatcl is added over a period of 15 minutes.
  • the temperature of the reaction mixture is raised to 1 to l C. and mi ing is eontinued under a positive pressure of nitrogen for hours.
  • the cooled product has a viscosity of about one million poises and is a light-colored stiff gum.
  • a solution in xylene has a Gardner Holdt viscosity of Z Step B Formulation of Clear Plasticizcd Cellulose Acetate Butryate Solution
  • a solvent mixture is prepared by blending 510 parts of toluene, 170 parts of methyl ethyl ketonc, and 320 parts ethyl alcohol. To (19 parts of this solvent mixture are added 1 5 .1 parts of 3-second viscosity cellulose acetate butyrate comprising 205' butyryl and 15% aeetyl content followed by 38 parts of a linear polyester. namely, propylene glycol sebacate having a molecular weight of 8,000 and 12. l parts of a 50 percent solution in xylene of the extended polyester of Example A. The mixture is agitated until a homogeneous solution is obtained. The mixture is pale straw colored and has a viscosity of 2,100 centipoises.
  • Step C Application Twenty parts of the clear finish of Step 8 is mixed with parts of methyl ethyl ketone and l part ofa red spirit-soluble dye is added. This mixture is applied by spray-coating to a piece of crushed foam coated leather substitute at the rate of 1,0 g. solids per square foot of leather substitute. The finish is air dried and then embossed at 20 psi and 320F. for 60 seconds with a sandblasted platen. The resulting finish has a warm brown color and possesses outstanding resistance to cracking H or dulling when flexed.
  • a process for preparing finished leather and leather substitutes which comprises:
  • a process according to claim 1 for preparing finished leather and leather substitutes which comprises:
  • finish coat to the crushed foam coated substrate wherein the finish coat is selected from compositions containing nitrocellulose, urethane, polyvinyl chloride, acrylics, cellulose acetate butyrates or nitrocellulose modified urethanes or combinations thereof.
  • a process according to claim 2 for preparing finished leather which comprises:
  • Step C is con ducted at a temperature in the range of from about 180 to 270F.
  • a process according to claim 2 for preparing a finished leather substitutes which comprises:
  • Step C is conducted at a pressure in the range from about St! to i000 psi at a temperature in the range from about 275 to about FIFlz 7.
  • the poly mcric late ⁇ comprises at least 1 of the lollowing monomers ol' whieh at least one is a monomer containing a lunctional group capable ol crosslinkingi a an Etifi illlylUlliCLEli) unsaturated acid;
  • R is hydrogen or methyl; and R is halo, alkanoyloxy cyano, phenyl lormyl carbamoyl, epoxy, N-hydrosy incthylcarbamoyl tolyl mcthoxy methyl.
  • R is hydrogen or methyl; R" and R are lower alkoxy or lower allomoyloxy:
  • polymeric latex contains a monomer chosen from at least three of the following groups a ethyl acrylate or hutyl acrylate;
  • a process according to claim 2 wherein the sol 5 ⁇ Ltll blowing agent is selected from dichlorodilluoromethane. carbon tetratluoride. trichlorotritluoroethane triehlorotluoromethanci mUHOClIlUTOIFlllUOI'OIULP thane monobromotritluoromcthane monochloroditlu oromethane octalluorocyclobutane, pentane. hexane. or cyclohexancr l l.
  • the blowing agent is selected from trichlorotluoromethane or trichlorotrifluoroethane.
  • b. a monomer of the formula Ill no lll wherein R is hydrogen or alkyl and R' is a straight, branched or cyclic alkyl, alkoxyalltyl or alkyl thioalkyl radical and c a monomer of the formula wherein R is hydrogen or methyl; R and R are lower alkoxy or lower alkanoyloxy 14.
  • a crushed foam coated leather or leather substi tute wherein the crushed foam coating is prepared by the process ol claim 2 and the polymeric acrylic latex employed contains monomers chosen from at least three of the following groups:
  • a crushed foam coated leather or leather substitute wherein the crushed foam coating is prepared by the process of claim 2 and the polymeric acrylic latex employed contains monomers from at least 3 of the following groups:
  • crushed foam coated leather or leather substitute of claim 15 wherein the crushed foam coating is prepared from a copolymer having the following monomer composition: 96 ethyl acrylate/35 acrylamide/(LS acrylic acid; 96 ethyl acrylate/4(l/l acrylamide/methylolacrylamide); 94 ethyl acrylate/5.5 allyl acetoacemm! 0.5 acrylic acid; 94.5 ethyl acrylate/S hydroxyethyl methacrylate/O.5 acrylic acid; 66 ethyl acrylate/32.7
  • a shoe upper material comprising a crushed foam coated leather or leather substitute prepared by the process of claim 1 wherein the crushed foam coating is prepared from the polymeric latex of claim 13 and which crushed foam coated leather and leather substitute has a finish coat composition containing one of the following ingredients: nitrocellulose, urethanes. polyvi- 20 nyl chlorides, acrylics, cellulose acetate butyrates or a composition containing nitrocellulose and an isocyanate terminated prepolymer of an organic polyisocyanate with a polyester or polyether polyol or mixtures thereof with or without plasticizers.
  • a shoe upper material comprising a crushed foam coated leather or leather substitute prepared by the process of claim 2 wherein the crushed foam coating is prepared from the polymeric latex of claim 14 which crushed foam coated leather and leather substitute has a finish coat composition containing cellulose acetate butyrate, nitrocellulose and/or an isocyanate terminated prepolymer of an organic polyisocyanate with a polyester or polyether polyol.
  • a shoe upper material comprising a crushed foam coated leather or leather substitute prepared by the process of claim 2 wherein the crushed foam coating is prepared from the polymeric latex of claim 15 which crushed foam coated leather and leather substitute has a finish coat composition having 15-55% nitrocellulose.
  • a shoe upper material comprising a crushed foam coated leather prepared according to claim 3 wherein the crushed foam coating is prepared from the polymeric latex of claim 16 which crushed foam coated leather has a finish coat of0.1 to 8 mils dry film thickness of a composition having a l5557r nitrocellulose.
  • a shoe upper material comprising a crushed foam coated leather substitute prepared according to claim 3 wherein the crushed foam coating is prepared from the polymeric latex of claim 16 which crushed foam coated leather substitute has a finish coat of 0.] to 8 mils dry film thickness of a composition having a 15-55% nitrocellulose.
  • the shoe upper of claim 20 having a finish coat of 0.3 to 0.5 mils dry film thickness.
  • the shoe upper of claim 21 having a finish coat of ()3 to 0.5 mils dry film thickness.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
  • Paints Or Removers (AREA)
US377885A 1973-07-09 1973-07-09 Method for finishing leather and leather substitutes Expired - Lifetime US3919451A (en)

Priority Applications (15)

Application Number Priority Date Filing Date Title
US377885A US3919451A (en) 1973-07-09 1973-07-09 Method for finishing leather and leather substitutes
CA199,875A CA1027813A (en) 1973-07-09 1974-05-14 Method for finishing leather and leather substitutes
IE1103/74A IE39788B1 (en) 1973-07-09 1974-05-24 A finishing process for leather and leather substitutes
DE19742425553 DE2425553A1 (de) 1973-07-09 1974-05-27 Verfahren zum ausruesten von materialien aus leder und lederersatz
IN1178/CAL/74A IN141916B (it) 1973-07-09 1974-05-29
AU69721/74A AU488414B2 (en) 1973-07-09 1974-06-03 A method for finishing leather and leather substrates
GB2578174A GB1465618A (en) 1973-07-09 1974-06-11 Finishing process for leather and leather substitutes
ES427247A ES427247A1 (es) 1973-07-09 1974-06-14 Procedimiento para el acabado de un subtrato.
PL1974172389A PL103078B1 (pl) 1973-07-09 1974-07-02 Sposob wytwarzania wykonczonych skor lub substytutow skory
FR7423180A FR2236941B1 (it) 1973-07-09 1974-07-03
SU7402039701A SU582777A3 (ru) 1973-07-09 1974-07-03 Способ отделки натуральной или искусственной кожи
IT24793/74A IT1015669B (it) 1973-07-09 1974-07-04 Procedimento per la finitura del la pelle e dei sostituiti della pelle
AR254555A AR199844A1 (es) 1973-07-09 1974-07-05 Procedimiento para el acabado de productos de cuero y sustitutos del cuero y los productos resultantes
JP7814174A JPS5713600B2 (it) 1973-07-09 1974-07-08
BE146368A BE817430A (fr) 1973-07-09 1974-07-09 Procede pour le finissage des cuirs et de leurs succedanes

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JP (1) JPS5713600B2 (it)
AR (1) AR199844A1 (it)
BE (1) BE817430A (it)
CA (1) CA1027813A (it)
DE (1) DE2425553A1 (it)
ES (1) ES427247A1 (it)
FR (1) FR2236941B1 (it)
GB (1) GB1465618A (it)
IE (1) IE39788B1 (it)
IN (1) IN141916B (it)
IT (1) IT1015669B (it)
PL (1) PL103078B1 (it)
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US4061822A (en) * 1971-03-12 1977-12-06 Rohm And Haas Company Crushed foam coated leather and leather-like materials
US4107120A (en) * 1976-06-17 1978-08-15 Rohm And Haas Company Heteropolymer acrylic latices and textiles treated therewith
US4140827A (en) * 1977-06-29 1979-02-20 Compo Industries Inc. Imitation-leather, bias-stretching process
US4194026A (en) * 1976-03-08 1980-03-18 United Foam Corporation Method of manufacturing textured foam coatings and materials
US4491612A (en) * 1982-07-28 1985-01-01 Basf Aktiengesellschaft Finishing leather or a synthetic leather substitute
US5019422A (en) * 1989-02-27 1991-05-28 Union Oil Company Of California Method for producing a liquid impermeable, gas permeable foam barrier
US5290593A (en) * 1991-03-19 1994-03-01 Lorica S.P.A. Process for converting composite imitation leather into sheet material similar in appearance to natural leather
US5498658A (en) * 1994-11-17 1996-03-12 The B. F. Goodrich Company Formaldehyde-free latex for use as a binder or coating
US5616419A (en) * 1995-06-07 1997-04-01 Rohm And Haas Company Method of producing coating on reconstituted wood substrate
US5641564A (en) * 1992-05-28 1997-06-24 Namba Corporation Three-dimensionally formed laminate
RU2131464C1 (ru) * 1998-07-23 1999-06-10 Центральный научно-исследовательский институт кожевенно-обувной промышленности Состав для отделки натуральных кож
US6191244B1 (en) * 1997-06-20 2001-02-20 Rohm And Haas Company Polymer compositions
US20030004246A1 (en) * 2000-02-09 2003-01-02 Steffen Wache Powdery composition based on water-soluble polymers
US20030105483A1 (en) * 2000-05-09 2003-06-05 Hudson John Overton Nasal packing device
US6593446B1 (en) * 1999-09-07 2003-07-15 Hyundai Electronics Industries Co., Ltd. Organic polymer for organic anti-reflective coating layer and preparation thereof
US20030221264A1 (en) * 2002-05-30 2003-12-04 Doug Slattery Leather treatment
US20040073299A1 (en) * 2000-12-16 2004-04-15 Hudson John Overton Hemostatic device
US20060115624A1 (en) * 2004-11-29 2006-06-01 Ulf Gimm Lacquer spray can set
EP1741758A1 (de) * 2005-07-08 2007-01-10 Zellaerosol GmbH Farbzubereitung
US20070289162A1 (en) * 2006-06-16 2007-12-20 Future Chen International Co., Ltd Footwear having non-yellowing film
US20100095429A1 (en) * 2000-02-08 2010-04-22 Ansell Healthcare Products Llc Production of Gloves and Other Articles of Flexible Polymer Material
US7799048B2 (en) 2000-05-09 2010-09-21 Arthrocare Corporation Nasal packing device
US20120318136A1 (en) * 2011-06-15 2012-12-20 E. I. Du Pont De Nemours And Company Hot gas filtration media and filters
US8771374B2 (en) * 2007-09-04 2014-07-08 Basf Se Method for the production of leather, copolymers that are suitable therefor, and further uses thereof
WO2015196318A1 (zh) * 2014-06-26 2015-12-30 江苏宝泽高分子材料股份有限公司 一种合成革用变色抛光处理剂及其制备方法
US9446563B2 (en) 2012-12-11 2016-09-20 Hi-Tex, Inc. Liquid repelling coating
US20180258584A1 (en) * 2017-03-09 2018-09-13 Hyundai Motor Company High density artificial leather having excellent surface touch and method of manufacturing the same
CN113831447A (zh) * 2021-09-24 2021-12-24 江苏鼎力新材料有限公司 一种高光强韧型丙烯酸酯乳液及其制备方法
US20220033692A1 (en) * 2018-09-21 2022-02-03 Synthomer Deutschland Gmbh Contact adhesives
CN115418418A (zh) * 2022-09-26 2022-12-02 焦作隆丰皮草企业有限公司 一种剥离皮革涂饰层的方法
CN116113341A (zh) * 2020-08-07 2023-05-12 耐克创新有限合伙公司 具有带结构颜色的遮掩层的鞋类制品

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JPS60129405A (ja) * 1983-12-15 1985-07-10 Shimadzu Corp 複数の油圧アクチユエ−タの油圧回路
DE4230997A1 (de) * 1992-09-16 1994-03-24 Sandoz Ag Spritzbeständiger wässriger Schaum, dessen Herstellung und Verwendung
CN116511007A (zh) * 2023-04-21 2023-08-01 兴业皮革科技股份有限公司 一种高度耐磨的皮革涂层工艺

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Cited By (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4061822A (en) * 1971-03-12 1977-12-06 Rohm And Haas Company Crushed foam coated leather and leather-like materials
US4194026A (en) * 1976-03-08 1980-03-18 United Foam Corporation Method of manufacturing textured foam coatings and materials
US4107120A (en) * 1976-06-17 1978-08-15 Rohm And Haas Company Heteropolymer acrylic latices and textiles treated therewith
US4140827A (en) * 1977-06-29 1979-02-20 Compo Industries Inc. Imitation-leather, bias-stretching process
US4491612A (en) * 1982-07-28 1985-01-01 Basf Aktiengesellschaft Finishing leather or a synthetic leather substitute
US5019422A (en) * 1989-02-27 1991-05-28 Union Oil Company Of California Method for producing a liquid impermeable, gas permeable foam barrier
US5290593A (en) * 1991-03-19 1994-03-01 Lorica S.P.A. Process for converting composite imitation leather into sheet material similar in appearance to natural leather
US5641564A (en) * 1992-05-28 1997-06-24 Namba Corporation Three-dimensionally formed laminate
US5971730A (en) * 1992-05-28 1999-10-26 Namba Corporation Apparatus for making formed laminate
US5498658A (en) * 1994-11-17 1996-03-12 The B. F. Goodrich Company Formaldehyde-free latex for use as a binder or coating
US5616419A (en) * 1995-06-07 1997-04-01 Rohm And Haas Company Method of producing coating on reconstituted wood substrate
US5635248A (en) * 1995-06-07 1997-06-03 Rohm And Haas Company Method of producing coating on reconstituted wood substrate
US5741823A (en) * 1995-06-07 1998-04-21 Rohm And Haas Company Polymerized latex emulsion suitable for producing coating on reconstituted wood substrate
US6300409B2 (en) 1997-06-20 2001-10-09 Rohm And Haas Company Polymer compositions
US6191244B1 (en) * 1997-06-20 2001-02-20 Rohm And Haas Company Polymer compositions
US6225242B1 (en) * 1997-06-20 2001-05-01 Rohm And Haas Company Polymer compositions
RU2131464C1 (ru) * 1998-07-23 1999-06-10 Центральный научно-исследовательский институт кожевенно-обувной промышленности Состав для отделки натуральных кож
US6593446B1 (en) * 1999-09-07 2003-07-15 Hyundai Electronics Industries Co., Ltd. Organic polymer for organic anti-reflective coating layer and preparation thereof
US8192834B2 (en) * 2000-02-08 2012-06-05 Ansell Healthcare Products Llc Production of gloves and other articles of flexible polymer material
US20100095429A1 (en) * 2000-02-08 2010-04-22 Ansell Healthcare Products Llc Production of Gloves and Other Articles of Flexible Polymer Material
US20030004246A1 (en) * 2000-02-09 2003-01-02 Steffen Wache Powdery composition based on water-soluble polymers
US20030105483A1 (en) * 2000-05-09 2003-06-05 Hudson John Overton Nasal packing device
US8137375B2 (en) 2000-05-09 2012-03-20 Arthrocare Corporation Nasal packing device
US20100324534A1 (en) * 2000-05-09 2010-12-23 Arthrocare Corporation Nasal packing device
US7799048B2 (en) 2000-05-09 2010-09-21 Arthrocare Corporation Nasal packing device
US20040073299A1 (en) * 2000-12-16 2004-04-15 Hudson John Overton Hemostatic device
US7001435B2 (en) * 2002-05-30 2006-02-21 Automotive Technology, Inc. Leather treatment
US7288119B2 (en) 2002-05-30 2007-10-30 Automotive Technology, Inc. Leather treatment
US20060042018A1 (en) * 2002-05-30 2006-03-02 Automotive Technology, Inc. Leather treatment
US20030221264A1 (en) * 2002-05-30 2003-12-04 Doug Slattery Leather treatment
US20060115624A1 (en) * 2004-11-29 2006-06-01 Ulf Gimm Lacquer spray can set
EP1741758A1 (de) * 2005-07-08 2007-01-10 Zellaerosol GmbH Farbzubereitung
US20070289162A1 (en) * 2006-06-16 2007-12-20 Future Chen International Co., Ltd Footwear having non-yellowing film
US8771374B2 (en) * 2007-09-04 2014-07-08 Basf Se Method for the production of leather, copolymers that are suitable therefor, and further uses thereof
US20120318136A1 (en) * 2011-06-15 2012-12-20 E. I. Du Pont De Nemours And Company Hot gas filtration media and filters
US9446563B2 (en) 2012-12-11 2016-09-20 Hi-Tex, Inc. Liquid repelling coating
WO2015196318A1 (zh) * 2014-06-26 2015-12-30 江苏宝泽高分子材料股份有限公司 一种合成革用变色抛光处理剂及其制备方法
US20180258584A1 (en) * 2017-03-09 2018-09-13 Hyundai Motor Company High density artificial leather having excellent surface touch and method of manufacturing the same
CN108570857A (zh) * 2017-03-09 2018-09-25 现代自动车株式会社 具有优异表面触感的高密度人造皮革及其制造方法
US20220033692A1 (en) * 2018-09-21 2022-02-03 Synthomer Deutschland Gmbh Contact adhesives
US12018184B2 (en) * 2018-09-21 2024-06-25 Synthomer Deutschland Gmbh Contact adhesives
CN116113341A (zh) * 2020-08-07 2023-05-12 耐克创新有限合伙公司 具有带结构颜色的遮掩层的鞋类制品
CN113831447A (zh) * 2021-09-24 2021-12-24 江苏鼎力新材料有限公司 一种高光强韧型丙烯酸酯乳液及其制备方法
CN115418418A (zh) * 2022-09-26 2022-12-02 焦作隆丰皮草企业有限公司 一种剥离皮革涂饰层的方法

Also Published As

Publication number Publication date
IE39788L (en) 1975-01-09
IN141916B (it) 1977-04-30
PL103078B1 (pl) 1979-05-31
IE39788B1 (en) 1979-01-03
JPS5036603A (it) 1975-04-05
JPS5713600B2 (it) 1982-03-18
FR2236941B1 (it) 1976-12-24
ES427247A1 (es) 1976-07-16
BE817430A (fr) 1975-01-09
DE2425553A1 (de) 1975-03-27
SU582777A3 (ru) 1977-11-30
FR2236941A1 (it) 1975-02-07
CA1027813A (en) 1978-03-14
GB1465618A (en) 1977-02-23
AR199844A1 (es) 1974-09-30
IT1015669B (it) 1977-05-20
AU6972174A (en) 1975-12-04

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