EP1537186A1 - Adhesif thermofusible sans solvant, son utilisation pour fixer une couche de cuir polaire sur un substrat non polaire, et articles en cuir produits au moyen dudit adhesif - Google Patents

Adhesif thermofusible sans solvant, son utilisation pour fixer une couche de cuir polaire sur un substrat non polaire, et articles en cuir produits au moyen dudit adhesif

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Publication number
EP1537186A1
EP1537186A1 EP03766313A EP03766313A EP1537186A1 EP 1537186 A1 EP1537186 A1 EP 1537186A1 EP 03766313 A EP03766313 A EP 03766313A EP 03766313 A EP03766313 A EP 03766313A EP 1537186 A1 EP1537186 A1 EP 1537186A1
Authority
EP
European Patent Office
Prior art keywords
weight
polar
hot melt
parts
melt adhesive
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.)
Withdrawn
Application number
EP03766313A
Other languages
German (de)
English (en)
Inventor
Caroline Rita Nicole Maes
Eddy Verheyden
Philippe Vosters
Xavier Muyldermans
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.)
Kraton Polymers Research BV
Original Assignee
Kraton Polymers Research BV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kraton Polymers Research BV filed Critical Kraton Polymers Research BV
Priority to EP03766313A priority Critical patent/EP1537186A1/fr
Publication of EP1537186A1 publication Critical patent/EP1537186A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/006—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/006—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof

Definitions

  • the present invention relates to a solvent-free hot melt adhesive composition for bonding a polar leather layer to a non-polar substrate, its use, a process of bonding a polar leather layer to a non-polar substrate using the solvent- free, hot melt composition and to composed leather articles, wherein the polar leather and non-polar substrate have been bonded by the solvent-free hot melt adhesive composition.
  • the invention relates to a solvent- free, hot melt adhesive composition for bonding footwear components, comprising at least one polar leather layer and at least one non-polar substrate, its use, the process of bonding footwear components, using the solvent-free hot melt adhesive composition, and to footwear, composed of a polar leather component and an non-polar substrate component that have been bonded by the solvent-free hot melt adhesive composition.
  • Adhesive compositions for bonding footwear are known. Such compositions were up to now comprising significant amounts of organic solvents. Due to the still increasing pressure from health, safety and environmental authorities said organic solvents have to be eliminated.
  • alternative adhesive compositions which are suitable for bonding highly non-polar footwear components, such as synthetic polymeric shoe soles to polar components such as leather uppers, are limited.
  • the conventional bonding technology requires a pre-treatment of the surface of the non-polar substrates to be bonded with a primer, in order to reach an adequate bonding. This is particularly essential when using highly non-polar synthetic footwear components, made from e.g. polyolefins or styrenic block copolymers and in particular hydrogenated styrenic block copolymers e.g. KRATON ® G-2705 block copolymer compositions.
  • Said process was carried out by using automatic machines and comprised the following operating phases carried out either in sequence or simultaneously (a) hot application of a low consistency layer (1) of an adhesive along the outer perimeter band of footwear uppers, innersoles or soles;
  • An object of the present invention is therefore to provide said solvent-free adhesive composition aimed at.
  • Another object of the present invention is to provide a process for the manufacturing of composed products, comprising a polar leather component bonded to a non-polar synthetic or polymeric substrate component, and using said solvent-free adhesive composition.
  • the invention relates to a solvent-free, hot melt adhesive composition to be used for bonding a polar leather layer to a non-polar substrate, comprising: (a) a block copolymer, comprising at least one acid functionalized, selectively hydrogenated inner block predominantly derived from a conjugated diene which block has been functionalized by acid grafting, and at least two terminal blocks, predominantly derived from a vinylarene; (b) a hydrogenated hydrocarbon tackifying resin, with a softening point lower than 140°C.
  • melt flow improving poly (alkylene) resin which has been functionalized, in a weight proportion of from
  • non-polar substrates are compositions comprising inter alia: vinylarene/conjugated diene block copolymers such as KRATON ® D copolymers ; hydrogenated vinylarene/conjugated diene block copolymers such as KRATON ® G copolymers; vinylarene/conjugated diene random copolymers; natural rubbers, poly (vinylarene) ; polyolefin; EVA copolymer; and/or mixtures thereof; to which optionally oils and other auxiliaries have been added.
  • vinylarene/conjugated diene block copolymers such as KRATON ® D copolymers
  • hydrogenated vinylarene/conjugated diene block copolymers such as KRATON ® G copolymers
  • vinylarene/conjugated diene random copolymers such as natural rubbers, poly (vinylarene) ; polyolefin; EVA copolymer
  • component (a) of the composition of the present invention can be used in principle block copolymers ABA, ABABA, ABA', ABA'BA, A'BABA' or radical block copolymers (AB)nX, wherein the blocks A and A' represent a poly (vinylarene) block, wherein block (s) B represent a selectively hydrogenated poly (conjugated diene) block, which has been functionalized, wherein n is in the range of from 3 to 6, and X is the residue of a coupling agent.
  • Said functionalization is preferably performed by grafting with an ethylenically unsaturated mono carboxylic acid or di carboxylic acid, such as acrylic acid, methacrylic acid, maleic acid or maleic anhydride.
  • an ethylenically unsaturated mono carboxylic acid or di carboxylic acid such as acrylic acid, methacrylic acid, maleic acid or maleic anhydride.
  • the hydrogenated copolymer is grafted with maleic anhydride to give from 1 to 10 wt% bound graft, preferably from 1 to 5 wt% and more preferably from 1 to 3 wt%.
  • block copolymers A and A' may comprise in addition to the main vinylarene monomer units minor amounts of structurally related or non related comonomers such as other styrene derivatives or conjugated diene in amounts of 'less than 20 wt% and preferably less than 10 wt%, relative to the weight of the complete (co) polymer block and in analogy that the blocks B may comprise in addition to the main conjugated diene monomer units, the same minor amounts of structurally related or non related comonomers such as other conjugated diene or vinylarene comonomers .
  • Preferred block copolymers to be used as component (a) are ABA' triblock copolymers comprising an elastomeric block portion B and a thermoplastic block portions A and A' which may be the same or different.
  • the thermoplastic, hard blocks A and A' are derived from monomers such as styrene, alpha- methyl styrene, other styrene derivatives such as ortho, meta and para methyl styrene, o-, m- , p-ethyl styrene, o-, m- , p- methoxy styrene, o- , m- , p-isopropyl styrene, p-tert butyl styrene or mixtures thereof .
  • thermoplastic hard blocks A and A' are composed of styrene, optionally mixed with minor amounts of alpha-methyl styrene or paramethyl styrene (amounts of at most 15 wt%, relative to the weight of the block (s) A and A', and has a number average molecular weight of from 4000 to 20.000, preferably from 5000 to 10.000 and most preferably from 6.000 to 9.000.
  • the hard block portions A comprise from 20 to 50 % and more preferably from 25 to 40 % of the total weight of the block copolymer.
  • the B block (s) have to be regarded as a soft block, which is derived from conjugated diene monomers of from 4 to 6 carbon atoms or linear alkene monomers of from 2 to 6 carbon atoms.
  • Suitable diene monomers include 1, 2-butadiene, 2-methyl-1, 3-butadiene, 2-methyl-l, 3-pentadiene, 1,3- octadiene, 1 , 3-pentadiene and the like.
  • Suitable alkene monomers include ethylene, propylene, butylenes and the like.
  • the soft block portion B preferably comprises a substantially amorphous polyolefin such as ethylene/propylene polymers, ethylene/butylenes polymers, polybutadiene, polyisoprene or mixtures thereof.
  • the soft block (s) B have been derived from butadiene or isoprene and have been selectively hydrogenated in the initially prepared complete block copolymer. This means that the blocks B have been hydrogenated for more than 90 % of the originally present ethylenical unsaturation, whereas the aromatic unsaturation has remained intact for more than 90 % .
  • the proportion of 1,2 polymerized butadiene units is in the range of from 30 to 80 % and more preferably from 35 to 70 %.
  • the number average molecular weight of the soft block (s) B is typically from 10.000 to 90.000 and preferably from 20.000 to 60.000.
  • the soft block(s) B portion comprises from 20 to 80 % by weight and preferably from 40 to 70 wt%, relative to the weight of the total weight of the block copolymer.
  • a most preferred block copolymer to be used as component (a) of the' adhesive composition of the present invention is the commercially available KRATON ® FG 1901 block copolymer, a selectively hydrogenated styrene-butadiene-styrene block copolymer having a styrene content of about 30 wt% and end blocks of about 7300 molecular weight, which selectively hydrogenated poly (butadiene) polymer block is grafted with maleic anhydride to give 1.5-2 wt% bound graft and the initial poly (butadiene) block has a vinyl content of about 40%.
  • the component (b) is actually blended with the block copolymer component (a) to provide tack.
  • hydrogenated hydrocarbon tackifying resins which may be suitable applied in the adhesive compositions of the present invention are hydrogenated rosin esters, and more in particular the glycerol ester of hydrogenated rosin or pentaerythritol ester of hydrogenated rosin (e.g. FORALTM 85E, FORALYNETM 85E, or FORALTM 105) or hydrogenated hydrocarbon resins (e.g., such as REGALITETM R resins or ARKON M resins or ESCOREZTM 5000 series or STABILITETM resins) .
  • diglycerol ester of highly hydrogenated resin is used as component (b) and more preferably in an amount of from 70 to 100 PHR.
  • an aromatic hydrocarbon resin As resin, which is compatible with resinous terminal block portions of the block copolymer (component c) , an aromatic hydrocarbon resin can be used.
  • Useful resins include coumarone-indene resins, poly (alpha-methyl styrene) resins, poly styrene resins or vinyl toluene- (alpha-methyl styrene) copolymers.
  • aromatic hydrocarbon resins useful in the adhesive composition of the present invention are AMOCO 18 series resins, KRISTALEXTM series resins (e.g.
  • KRISTALEXTM F100 or 3115 which are composed of alpha-methyl styrene (EASTMAN)
  • PICCOTEXTM series resins which are composed of alpha-methyl styrene and vinyl toluene (EASTMAN)
  • component (d) can be used homopolymers of propylene or one or more crystalline copolymers of propylene, which contain 50 wt% or more propylene (e.g. ADFLEXTM copolymers, i.e. copolymers made of propylene and a further olefin by the CATALLOYTM process) , or mixtures of the hereinbefore mentioned (co) polymers, which have been acid grafted and preferably with maleic acid or maleic anhydride.
  • propylene (co) polymer is included more preferably in amounts of 5 to 20 parts by weight per 100 parts by weight of block copolymer.
  • Preferred propylene copolymers which are applied are PP QESTRONTM KA 802A, PP QESTRONTM 805A, which are maleic anhydride grafted heterophasic PP copolymers of BASELL .
  • component (e) can be used stabilizers which are known from e.g. US Pat No 4,835,200. More in particular phenolic antioxidant (IRGANOXTM) , benzotriazole ultraviolet inhibitor (TINUVINTM P) and a hindered amine ultraviolet inhibitor (TINUVINTM 770) can be used to stabilize the formulation against degradation.
  • IRGANOXTM phenolic antioxidant
  • TINUVINTM P benzotriazole ultraviolet inhibitor
  • TINUVINTM 770 hindered amine ultraviolet inhibitor
  • hindered phenols and more preferred less volatile hindered phenols such as tetrakis [methylene 3 , 5-di-tert-butyl-4-hydroxy hydro cinnamate) ] methane (IRGANOXTM 1010 antioxidant) or 2(3,5-di- tert-butyl-4-hydroxy) 4,6-bis (N octylthio) 1, 3 , 3-triazine (IRGANOXTM 565 antioxidant) .
  • TINUVINTM P and IRGANOXTM 1010 are known to show synergistic effect in polymer stabilization.
  • the solvent-free, hot melt adhesive composition provide excellent bonding when applied at 230 to 260°C and satisfactory adhesion at 200°C, especially when using preheated polymer substrates.
  • the bonded polar leather - non-polar synthetic material composites do not show any break upon repeatedly bending contrary to the composites made by using prior hot melt adhesive compositions. Therefore the adhesive compositions of the present invention have been found to provide attractive flexing endurance or resistance to flexing to footwear.
  • another aspect of the present invention is formed by the use of hereinbefore specified solvent-free, hot melt adhesive compositions for bonding a polar leather layer to a non-polar substrate.
  • said use relates to the bonding of shoe components and components of other formed leather articles such as suitcases, sporting articles and fashion articles, formed from a leather component and a synthetic polymeric non-polar component. More in particular said use relates to the bonding of shoe uppers and soles .
  • the shoe uppers are made of leather and the shoe soles are made of a non-polar polymeric material .
  • the shoe soles are made from vinylarene/- conjugated diene block copolymers; hydrogenated vinylarene/- conjugated diene block copolymers; vinylarene/conjugated diene random copolymers; natural rubbers, poly (vinylarene) ; polyolefin; EVA copolymer; and/or mixtures thereof; to which optionally oils and other auxiliaries have been added.
  • the present invention is also relating to a process for bonding a polar leather layer to a non-polar synthetic polymeric layer, and more preferably shoe components, by the use of the hereinbefore specified adhesive compositions of the invention. Such process may, and preferably is automated.
  • Another aspect of the present invention is formed by the composed formed articles, such as shoes, handbags suitcases, derived from a polar leather component and a non-polar synthetic component, which have been bonded to each other with a hereinbefore defined adhesive composition.
  • Example 1 The invention is further illustrated by the following examples, however without restricting its scope to these specific embodiments.
  • Example 1 The invention is further illustrated by the following examples, however without restricting its scope to these specific embodiments.
  • Non-polar compounds were used, composed of a linear triblock SEBS-type copolymer, a polypropylene homopolymer, a paraffinic extender oil, and an antioxidant.
  • the triblock copolymer was based on styrene and ethylene/butylene having a bound styrene content of 33 wt% (KRATON ® G 1651) .
  • the polypropylene homopolymer (PM 6100, BASELL) had a melt flow rate of 35 g/10 min (230°C/2.16 kg) and was used in a proportion of 34 PHR (parts by weight per 100 parts by weight of block copolymer) .
  • PRIMOLTM (EXXON) was used as paraffinic extender oil in a proportion of 100 PHR.
  • antioxidant IRGANOXTM 1010 antioxidant (pentaerythryl tetrakis 3-3,5-di- butyl-4-hydroxyphenylpropionate) and IRGANOXTM P5800 antioxidant (dilauryl thiodipropianate) were used in a proportion of 0.01 to 1 PHR.
  • the non-polar compounds were bonded to leather uppers using several solvent-free, hot melt adhesive compositions according to the present invention which have been composed as listed in Table 1. All solvent-free, hot melt adhesive compositions were prepared using a MARISTM 30VI, 30 mm corotating twin screw extruder.
  • the gravimetric feeders one for the polymer and two for the resin, were equipped with a vibration tray.
  • the processing of hot melts began with pre-blending the polymer, the polypropylene if any and antioxidant.
  • the pre-blend was added to the extruder via the first feeding port .
  • part of the resins (1/3 to % of the total amount of resin) was added.
  • the hot melt strand was cut on a GALATM granulator with a die plate temperature of 130°C and a speed of 1500 rpm and cooled by water.
  • a hot melt dispenser equipped with a 2 mm thick slit die (10 mm wide) , was used to manually apply a hot melt layer onto non-primed compound test bars.
  • the hot melt application temperatures varied from 260° to 200°C.
  • the adhesive application and bonding operation (including the positioning of the test bar onto the leather strap and time till applying full pressure) was kept as short as possible to prevent the hot melt from cooling down and as such keep the hot melt viscosity as low as possible.
  • test bars and leather straps were immediately pressed for 15 seconds at 12 kg/cm 2 .
  • pressure on the test assembly it was necessary to apply pressure on the test assembly until the bond had built up sufficient strength to avoid separation upon removal from the press .
  • T-peel testing was carried out according to the SATRA AMI 180°C T-peel test after storing the samples to be tested for at least 24 hours in a standard controlled environment at 21°C and 65 % relative humidity.
  • the Peel tests were carried out using the ZWICKTM tensile tester and at a rate of 100 mm/sec until a bond length of 30 mm had been peeled. All results listed were obtained using a total of four test assemblies.
  • the solvent-free hot melt adhesives according to the present invention outperformed solvent-based primer/PU adhesive or KRATON contact adhesive applied from solution.
  • the preparation of the test materials and testing was carried out in the same way as described in example 1.
  • Compound 2 As non-polar compound, Compound 2 was used comprising KRATONTM as SEBS-type polymer; PM 6100 as polypropylene homopolymer in a weight proportion of 100 PHR, PRIMOLTM 352 oil in a weight proportion of 180 PHR.
  • HALOSOLTM is a solvent (ethyl acetate) based halogenation primer for promoting adhesion to thermoplastic elastomeric substrates (KOMMERLING/GmbH) . The results have been listed in Table 2.
  • Table 3 shows that adhesion/peel strength of KRATON FG- 1901 based hot melt formations according to the present invention, compared to those obtained using the MONTELL reference adhesive composition at different application temperatures.
  • Compound 1 is identical to the non-polar compound of Example 1.
  • Compound 3 is composed of KRATON ® D- 4274 and KRATON ® D-1101 in an 100:42 weight ratio
  • D-4274 is an oil extended branched block copolymer based on styrene and butadiene, with bound styrene in the neat polymer of 49 % mass, a hardness of 82 Shore A and a Melt Flow Ratio (200°C/5 kg) of 20 g/10 min
  • D-1101 is a clear linear block copolymer based on styrene and butadiene, with bound styrene of 31 % mass, a hardness of 72 Shore A and a Melt Flow Ratio (200°C/5 kg) ⁇ lg/10 min)
  • POLYSTYROL 473 D an easy flowing high impact grade of polystyrene with a Melt Flow Ratio
  • KD-28 as paraffinic extender oil (SHELL CHEMICALS LTD) in an amount of 0 to 25 PHR; IRGANOXTM 565, 2(3,5-di tet butyl-4-hydroxy) 4,6 bis (N-octylthio) 1, 3 , 5 triazine antioxidant, CIBA-GEIGY AG) in an amount of from 0.01 to 0.1 PHR.
  • the solvent-free hot melt compositions according to the present invention provide satisfactory adhesion, meeting the industry requirement and outperform the MONTELL (Montell Technology Company BV) hot melt adhesive composition according to EP-0822244A1, relating to the bond strengths and hot melt application temperature, when tested according to the preparation and testing in the same way as described in Example 1.
  • 260 °C seemed to be the minimum application temperature at which satisfactory non-polar styrenic block copolymer/leather bonds can be made, using the MONTELL hot melt, whereas at 230°C unacceptable poor adhesion (peel strengths ⁇ 1.5 N/mm was found, and at 200°C we even failed to apply a fine layer of the Montell hot melt onto the substrates to be joined.
  • the hot melt adhesive formulations of the present invention provided adequate adhesion when applied at 260-230°C and satisfactory adhesion at 200°C, especially when using preheated polymer substrates.
  • Adhesion may be often improved when the hot melt adhesive composition of the invention is applied on preheated (5) or mechanically roughed (6) non-polar substrates.
  • the hot melt adhesives of the present invention could withstand sold and warm climate conditions. After accelerated heat and cold aging test, adhesion close to the requirement was found. This was not the case for the MONTELL- hot melt since poor initial cold or heat aged values were seen ( ⁇ 2 N/mm) . Table 7
  • the KRATON hot melt could also be used to bond a wider range of polyolefinic substrates to leather, including SBC compounds, as well as ENGAGETM substrates (Compound 4) and cross linked EVA substrates (Compound 5) .

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention a trait à une composition adhésive thermofusible sans solvant, qui est destinée à fixer une couche de cuir polaire sur un substrat non polaire. Ladite composition contient : (a) un copolymère bloc comprenant au moins un bloc interne fonctionnalisé par l'acide et sélectivement hydrogéné, qui est dérivé principalement d'un diène conjugué, ledit bloc ayant été fonctionnalisé par une greffe d'acide, et au moins deux blocs terminaux, dérivés principalement d'un vinylarène ; (b) une résine poisseuse à base d'hydrocarbures hydrogénée, présentant un point de ramollissement inférieur à 140 °C, et dont la proportion en poids est comprise entre 30 et 150 PHR (parties en poids de résine poisseuse pour 100 parties en poids de copolymère bloc ; (c) une résine compatible avec les blocs formés principalement de poly(vinylarène), présentant un point de ramollissement inférieur à 140 °C, et dont la proportion en poids est comprise entre 10 et 80 PHR ; (d) éventuellement une résine de poly(alkylène) qui a été fonctionnalisée, dont la proportion en poids est comprise entre 0 et 30 parties PHR ; et (e) des stabilisants et/ou des auxiliaires supplémentaires, dont la proportion en poids est comprise entre 0,1 et 1 partie PHR. L'invention concerne également l'utilisation de ladite composition pour fixer une couche de cuir polaire sur un substrat non polaire, ainsi que des articles en cuir formés au moyen de ladite composition adhésive.
EP03766313A 2002-07-26 2003-07-23 Adhesif thermofusible sans solvant, son utilisation pour fixer une couche de cuir polaire sur un substrat non polaire, et articles en cuir produits au moyen dudit adhesif Withdrawn EP1537186A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP03766313A EP1537186A1 (fr) 2002-07-26 2003-07-23 Adhesif thermofusible sans solvant, son utilisation pour fixer une couche de cuir polaire sur un substrat non polaire, et articles en cuir produits au moyen dudit adhesif

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP02016728 2002-07-26
EP02016728A EP1384768A1 (fr) 2002-07-26 2002-07-26 Adhésif thermofusible exempte de solvant, leur utilisation au collage du cuir polaire sur des surfaces pas polaires, et articles produit avec l'adhésif
PCT/EP2003/008261 WO2004013247A1 (fr) 2002-07-26 2003-07-23 Adhesif thermofusible sans solvant, son utilisation pour fixer une couche de cuir polaire sur un substrat non polaire, et articles en cuir produits au moyen dudit adhesif
EP03766313A EP1537186A1 (fr) 2002-07-26 2003-07-23 Adhesif thermofusible sans solvant, son utilisation pour fixer une couche de cuir polaire sur un substrat non polaire, et articles en cuir produits au moyen dudit adhesif

Publications (1)

Publication Number Publication Date
EP1537186A1 true EP1537186A1 (fr) 2005-06-08

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EP02016728A Withdrawn EP1384768A1 (fr) 2002-07-26 2002-07-26 Adhésif thermofusible exempte de solvant, leur utilisation au collage du cuir polaire sur des surfaces pas polaires, et articles produit avec l'adhésif
EP03766313A Withdrawn EP1537186A1 (fr) 2002-07-26 2003-07-23 Adhesif thermofusible sans solvant, son utilisation pour fixer une couche de cuir polaire sur un substrat non polaire, et articles en cuir produits au moyen dudit adhesif

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EP02016728A Withdrawn EP1384768A1 (fr) 2002-07-26 2002-07-26 Adhésif thermofusible exempte de solvant, leur utilisation au collage du cuir polaire sur des surfaces pas polaires, et articles produit avec l'adhésif

Country Status (5)

Country Link
EP (2) EP1384768A1 (fr)
CN (1) CN1290957C (fr)
AU (1) AU2003253333A1 (fr)
TW (1) TWI248461B (fr)
WO (1) WO2004013247A1 (fr)

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Publication number Priority date Publication date Assignee Title
US7141621B2 (en) 2002-02-07 2006-11-28 Kraton Polymers U.S. Llc Gels from controlled distribution block copolymers
EP1582563A1 (fr) * 2004-03-31 2005-10-05 KRATON Polymers Research B.V. Compositions de copolymère bloc styrène hydrogéné à propriétés de surmoulage à haute température améliorées
EP2697304A2 (fr) * 2011-04-15 2014-02-19 Cray Valley USA, LLC Additif pour adhésifs thermofusibles pouvant être enlevés par traitement caustique et formulation le contenant
JP6154725B2 (ja) * 2013-10-24 2017-06-28 ヘンケルジャパン株式会社 ホットメルト接着剤
CN114277581A (zh) * 2021-12-27 2022-04-05 陈永裕 一种合成皮革及其制备方法

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AU2003253333A1 (en) 2004-02-23
TWI248461B (en) 2006-02-01
CN1678707A (zh) 2005-10-05
EP1384768A1 (fr) 2004-01-28
TW200415221A (en) 2004-08-16
WO2004013247A1 (fr) 2004-02-12
CN1290957C (zh) 2006-12-20

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