EP0915942A1 - Compositions adhesives thermofusibles a base de polydiene hydroxyle - Google Patents

Compositions adhesives thermofusibles a base de polydiene hydroxyle

Info

Publication number
EP0915942A1
EP0915942A1 EP98928371A EP98928371A EP0915942A1 EP 0915942 A1 EP0915942 A1 EP 0915942A1 EP 98928371 A EP98928371 A EP 98928371A EP 98928371 A EP98928371 A EP 98928371A EP 0915942 A1 EP0915942 A1 EP 0915942A1
Authority
EP
European Patent Office
Prior art keywords
copolymer
ethylene
diisocyanate
hot
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Withdrawn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
EP98928371A
Other languages
German (de)
English (en)
French (fr)
Inventor
Jean Lebez
Jean-Jacques Flat
Jean-Michel Pierrot
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.)
Arkema France SA
Original Assignee
Elf Atochem SA
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 Elf Atochem SA filed Critical Elf Atochem SA
Publication of EP0915942A1 publication Critical patent/EP0915942A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/69—Polymers of conjugated dienes
    • C08G18/698—Mixtures with compounds of group C08G18/40
    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • 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
    • C09J149/00—Adhesives based on homopolymers or copolymers of compounds having one or more carbon-to-carbon triple bonds; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C08G2170/20—Compositions for hot melt adhesives

Definitions

  • the present invention relates to hot melt adhesive compositions based on hydroxylated polydiene and more particularly hot melt adhesive compositions (HMA) in the form of a polymer containing free isocyanate functions, said polymer results from the reaction of a polyisocyanate (A), d polydiene polyol (B) and an ethylene copolymer (C) containing hydroxyl functions.
  • the polydiene polyol is a hydroxytelechelic polybutadiene and the copolymer (C) is either an ethylene-vinyl acetate copolymer (hydroxyethyl (meth) acrylate) or an ethylene- (meth) acrylate copolymer. hydroxyethyl alkyl- (meth) acrylate.
  • This composition generally associated with a sticky resin makes it possible to produce bondings resistant to high temperature after crosslinking of the free NCO functions usually under the effect of atmospheric humidity.
  • hot-melt adhesives hot-melts adhesives or HMA
  • HMA hot-melts adhesives
  • thermoplastic resin solid at room temperature
  • HMA hot-melts adhesives
  • These adhesives are fluidized when hot, the bonding of the surfaces to be bonded being ensured when the adhesive becomes rigid again on cooling.
  • These hot-melt adhesives generally result from the combination of three basic constituents: a thermoplastic resin, a sticky resin (tackifier) and a wax, to which additives such as stabilizer, filler, plasticizers and others can be combined.
  • the best known basic thermoplastic resins are polyamides, atactic polypropylene, ethylene-vinyl acetate (EVA) copolymers and ethylene- (meth) alkyl acrylate copolymers.
  • EVA ethylene-vinyl acetate
  • ethylene- (meth) alkyl acrylate copolymers In the current state, these hot-melt adhesives have good adhesive properties, but have the drawback of showing poor heat resistance, resistance hardly exceeding 60 to 80 ° C.
  • polyurethane hot-melt adhesives has been developed. These products are prepared in a conventional manner by reaction of polyisocyanate on polyols of polyester type, at least one of which is solid at room temperature. These adhesives are applied at high temperature in the molten phase. They have the disadvantage of being incompatible with sticky resins (tackifiers) which greatly limits the possibilities of formulation. This then results in an ability to bond limited to certain well defined supports. In addition, these products have open times of the order of a few minutes, which is too long for certain high speed applications.
  • the open time of a hot-melt adhesive is the time available for bonding, between the time when the adhesive is applied in the molten state on the first support to be bonded and the time when the hot-melt adhesive is no longer enough. fluid to allow the second support to be assembled correctly.
  • Another type of crosslinkable hot-melt adhesive has been developed from ethylene-hydroxylated vinyl acetate copolymers reacting with a polyisocyanate blocked in stoichiometric quantity, as described in European patent EP 294 271. These hot-melt adhesives, compatible with sticky resins ( tackifying), have good adhesive properties, but have the disadvantage of requiring subsequent heat treatments at temperatures of at least 140 ° C for several minutes to ensure their good crosslinking.
  • EP 380 379 describes crosslinkable hot-melt adhesive compositions in the form of a prepolymer containing free isocyanate functions, said prepolymer results from the reaction of a copolymer of ethylene and vinyl acetate containing hydroxyl functions with a polyisocyanate.
  • This prior art describes the copolymers obtained by direct copolymerization of ethylene, vinyl acetate and hydroxyethyl acrylate as well as the ethylene-vinyl acetate-vinyl alcohol copolymers obtained by partial hydrolysis of ethylene-acetate copolymers vinyl.
  • EP 600767 is similar to the previous ones, but a primary alcohol (dodecanol) is added to the ethylene-vinyl acetate-hydroxyethyl acrylate copolymer.
  • the essential difference in composition between these prior arts and the present invention is therefore the joint use of polydiene polyol and of a hydroxylated copolymer (C) to react on the polyisocyanate instead of only EVA-HEA (ethylene-vinyl acetate copolymer -hydroxyethyl acrylate) or instead of EVA-HEA and dodecanol.
  • EVA-HEA ethylene-vinyl acetate copolymer -hydroxyethyl acrylate
  • dodecanol ethylene-vinyl acetate copolymer -hydroxyethyl acrylate
  • the fluidity index is designated by Ml (Meit Index) or MFI (Meit Flow Index), - after preparation, give an HMA which has a lower viscosity especially if one starts with an EVA-HEA of low MFI, therefore allowing to use HMA at a lower temperature (110-140 ° C),
  • EP 293602 describes hot melt adhesive compositions comprising (i) the reaction product of a polyisocyanate with a polyol and (ii) a thermoplastic polymer such as an EVA (ethylene-vinyl acetate copolymer) or a SEBS (styrene block copolymer) ethylene / butene-styrene).
  • EVA ethylene-vinyl acetate copolymer
  • SEBS styrene block copolymer
  • the polyisocyanate (A) is generally chosen from aliphatic, cycloaliphatic or aromatic polyisocyanates well known to those skilled in the art, as well as mixtures of these compounds.
  • aliphatic polyisocyanates mention may be made of hexamethylene diisocyanate (HDI), trimethyl hexamethylene diisocyanate (HMDI), ethylene diisocyanate, ethylidene diisocyanate, propylene diisocyanate, butylene diisocyanate, dichlorohexamethylene diisocyanate, furfurylidene diisocyanate and mixtures as well as the derivatives (dimer, trimer, biuret, allophanate) of these compounds.
  • HDI hexamethylene diisocyanate
  • HMDI trimethyl hexamethylene diisocyanate
  • ethylene diisocyanate ethylidene diisocyanate
  • propylene diisocyanate propylene
  • cycloaliphatic polyisocyanates examples include isophorone diisocyanate (IPDI), cyclopentylene-1, 3-diisocyanate, cyclohexylene-1, 4-diisocyanate, cyclohexylene-1, 2-diisocyanate and mixtures and derivatives (dimer, trimer, biuret, allophanate) of these compounds.
  • IPDI isophorone diisocyanate
  • cyclopentylene-1 3-diisocyanate
  • cyclohexylene-1 4-diisocyanate
  • 2-diisocyanate 2-diisocyanate
  • mixtures and derivatives dimer, trimer, biuret, allophanate
  • aromatic polyisocyanates examples include 4,4'-diphenylmethane (MDI) and its isomers, in particular 2,4'- and 2,2'- diphenylmethane diisocyanate, toluene diisocyanate (TDI) and its isomers, in particular 2,4- and 2,6-toluene diisocyanate, 2,2-diphenylpropane-4,4'- diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, xylene diisocyanate, 1 , 4-naphthalene diisocyanate, 1,5-naphthylene diisocyanate, azobenzene-4,4'-diisocyanate, diphenyl sulfone-4,4'-diisocyanate, 1-chlorobenzene-2,4-diisocyanate, 4, 4'4 "-triisocyanato-triphen
  • diisocyanates are used and more particularly MDI and its isomers, TDI and its isomers, HDI, IPDI and their derivatives.
  • polydien polyols (B) which can be used according to the present invention
  • hydroxytelechelic conjugated diene oligomers which can be obtained by various processes such as the radical polymerization of conjugated diene having from 4 to 20 carbon atoms in presence of a polymerization initiator such as hydrogen peroxide or an azo compound such as azobis-2,2 '[methyl-2, N- (hydroxy-2ethyl) propionamide] or the anionic polymerization of conjugated diene having from 4 to 20 carbon atoms in the presence of a catalyst such as naphthalene dilithium.
  • a polymerization initiator such as hydrogen peroxide or an azo compound such as azobis-2,2 '[methyl-2, N- (hydroxy-2ethyl) propionamide]
  • a catalyst such as naphthalene dilithium
  • the conjugated diene of the polydiene-polyol is chosen from the group comprising butadiene, isoprene, chloroprene, pentadiene-1, 3, cyclopentadiene.
  • the number-average molar mass of the polyols which can be used can vary from 500 to 15,000 and preferably from 1000 to
  • a polydiene polyol based on butadiene is preferably used.
  • the polydiene polyol comprises 70 to 85% by mole, preferably 75% of units. and 15 to 30% preferably 25% of patterns
  • copolymers of conjugated diene and of vinyl and acrylic monomer such as styrene or acrylonitrile.
  • the OH index expressed in meq / g is between 0.5 and 5, their viscosity is between 500 and 100,000 mPa.s at 30 ° C.
  • polystyrene-polyols By way of illustration of polydien-polyols, mention will be made of polybutadienes with hydroxyl endings sold by the company ELF ATOCHEM S.A. under the names Poly Bd®R45 HT and Poly Bd®R20 LM.
  • the polymer of the invention can also comprise a chain extender.
  • chain extender currently denotes compounds carrying at least two reactive functions with the isocyanate functions.
  • the chain extender can be chosen from polyols. Their molecular mass can be between 62 and 500. By way of illustration of such compounds, mention may be made of ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1, 4-butanediol, 1, 6 -hexanediol, 2-ethyl-1, 3-hexanediol, N, N bis (2-hydroxypropyl) aniline, 3-methyl-1, 5-pentanediol and the mixture of at least two of the above-mentioned compounds. Polyamines can also be used as chain extenders. Their molecular mass can be between 60 and 500.
  • polystyrene resin By way of illustration of such polyamines, mention will be made of ethylene diamine, diphenyl methane diamine, isophoronediamine, hexamethylenediamine, diethyltoluenediamine.
  • One part by weight of one or more abovementioned chain extenders can be used per 100 parts by weight of polydiene polyol (B) used and preferably 5 to 30 parts by weight.
  • the hydroxyl functions of the copolymer (C) can be provided: - by grafting or by copolymerization of an unsaturated monomer having at least one hydroxylated function;
  • the hydroxyl-functional monomer can be, for example, allyl alcohol, N-hydroxymethyl acrylamide, 2-hydroxyethyl (meth) acrylate.
  • HSA HEMA
  • PEG polyethylene glycol
  • PPG polyoxypropylene glycol
  • PEG polyoxytetramethylene glycol
  • the unsaturated monomer can also be a carboxylic acid or an anhydride, for example (meth) acrylic acid and maleic anhydride. These acids or anhydrides are then neutralized with a diol such as ethylene glycol, PEG, PPG or PTMG.
  • a diol such as ethylene glycol, PEG, PPG or PTMG.
  • the hydroxylated function can also be produced by hydrolysis of a vinyl ester of saturated carboxylic acid such as vinyl acetate or propionate.
  • the copolymer (C) is advantageously a copolymer of ethylene, of an unsaturated carboxylic acid ester and of an unsaturated monomer having at least one hydroxyl function or a copolymer of ethylene, of a vinyl ester of carboxylic acid saturated and of an unsaturated monomer having at least one hydroxylated function.
  • alkyl (meth) acrylates alkyls having from 1 to 24 carbon atoms, in particular methyl, ethyl (meth) acrylates, n-butyl, isobutyl, 2-ethylhexyl.
  • the copolymer (C) is obtained by direct copolymerization (as opposed to grafting).
  • the copolymer (C) advantageously contains 40 to 95% by weight of ethylene, 4 to 40% of comonomer and 1 to 15% of monomer containing minus a hydroxylated function.
  • the meit index of the copolymer (C) according to ASTM D 1238-73 is advantageously between 1 and 1000 (g / 10 min).
  • the copolymer (C) preferably contains from 10 -3 to 45 10 -2 mole OH per 100 g of copolymer.
  • the copolymer (C) can be diluted in a polymer (C1) not containing a hydroxyl function and being neutral with respect to these hydroxyl functions.
  • (C1) can be a homo or copolymer polyethylene, a copolymer of ethylene and an unsaturated carboxylic acid ester, a copolymer of ethylene and a vinyl ester of saturated carboxylic acid, a styrene block copolymer -butadiene-styrene (SBS), a styrene-isoprene-styrene block copolymer (SIS) or these hydrogenated block copolymers (SEBS).
  • SBS styrene block copolymer -butadiene-styrene
  • SIS styrene-isoprene-styrene block copolymer
  • SEBS hydrogenated block copolymers
  • free isocyanate functions remain.
  • the content of free NCO functions is between 1 to 10% by weight of free NCO functions, relative to the total weight of the adhesive. Preferably, this content is from 1 to 5%. This content makes it possible to achieve a good compromise between the speed of crosslinking of the adhesive (after bonding) and its stability when hot (before bonding).
  • the polymer is prepared in the presence of a chain-limiting monoalcohol (D) which can have tackifying properties.
  • D chain-limiting monoalcohol
  • compositions according to the present invention can also contain:
  • tackifying resins are aliphatic or aliphato-aromatic (including natural or synthetic terpene resins) and generally do not contain a reactive function with isocyanates. However, it would not depart from the scope of the invention if a polyfunctional hydroxylated tackifying resin were used provided that it is taken into account in the NCO / OH ratio and that the viscosity of the compositions of the invention is compatible with their use,
  • G additives such as plasticizers, fillers, stabilizers that are chemically neutral with respect to isocyanates.
  • Tackifying resins or weakly hydroxylated waxes can be used provided that the hydroxyl functions they provide are taken into account in the calculation of the total NCO / total OH molar ratio and that they are reduced in proportion the amount of alcohol (D) used for the reaction with the excess of polyisocyanate.
  • tackifying resins waxes, plasticizers are used in a known manner in hot-melt adhesives to modify the viscosity, the open time and the tackiness.
  • compositions of the invention have a determined viscosity, that is to say fluid enough, to allow rapid bonding at relatively low temperature in atmospheric medium in order to achieve bonding which can subsequently resist
  • compositions of the invention essentially do not contain a free OH function.
  • the viscosity of the compositions of the invention is advantageously less than 10,000 mPa.s and preferably between 2,000 and 6,000 15 mPa.s. These viscosities are measured at the application temperatures of the HMA of the present invention.
  • the proportions of (B) and (C) can be any, advantageously B / C by weight is between 1/100 and 100/1 and preferably from 1/10 to 2/1.
  • the proportions by weight of (C1) relative to (C) can be any preferably C1 / C is between 1/20 and 20/1.
  • the possible amount of (D) is such that by weight D / (B + C) is between 0 and 5 and preferably from 0 to 2.
  • the NCO / OH molar ratio is chosen in order to avoid gelation during the synthesis.
  • this ratio is between 2 and 30 and preferably 2 to 5.
  • the quantity of tackifying resin (E) is defined by the mass ratio (E) / (B + C) ranging from 0 to 10, preferably 0 to 1.
  • the quantity of wax (F) is defined by the mass ratio ( F) / (B + C) ranging from 0 to 10, preferably 0 to 0.5.
  • compositions of the invention can be prepared by mixing the various constituents in the molten state.
  • the present invention also relates to a process for the preparation of a composition in which first of all: a / melting and drying of the polyhydric polyol (B), of the copolymer (C) optionally tackifying resins (E ), waxes (F) and additives (G) then b / addition and reaction of the polyisocyanate (A) and any monoalcohol (D) until the desired NCO level is obtained. If (D) is not very volatile it can be introduced in step a /.
  • the hot-melt adhesives according to the invention are advantageously produced in a single step according to the following process:
  • the dry monoalcohol then the diisocyanate are then introduced in suitable proportions and the isocyanate-alcohol reaction continued at 120-125 ° C until the theoretical NCO level is obtained.
  • the ready-to-use hot-melt adhesive is recovered by casting.
  • aromatic diisocyanates the operation is generally carried out in the absence of a catalyst.
  • catalysts for the NCO / OH reaction such as tin salts (dibutyltin laurate DBLT) or amines (diazabicyclo-octane).
  • the process can be carried out in one step as described above, that is to say by adding (A) and (D) simultaneously or in two steps by adding first (A) and then (D).
  • Diisocyanates such as 2-4-toluylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) are used. Due to its lower toxicity, it is MDI which is the preferred diisocyanate of the invention.
  • the reaction between the copolymer (C) and the diisocyanate is carried out in the presence of a large molar excess of diisocyanate in order to avoid any undesired increase in viscosity.
  • the excess required depends on the OH functionality of the copolymer (C), the polydiene (B) and the isocyanate functionality and the reactivity of the diisocyanate used (a diisocyanate whose two NCO functions have the same reactivity (MDI) require a molar excess larger than a diisocyanate whose two NCO functions do not have the same reactivity (TDI)).
  • the viscosity of the adhesives of the invention at their processing temperature (110 to 140 ° C) is typically from 2000 to 6000 mPa.s. After storage at 130 ° C for 4 hours, in contact with the atmosphere, the viscosity increase of the adhesives of the invention is of the order of 15%, which allows industrial processing without problem with the existing machines (NORDSON MELTEX coating for example).
  • the present invention provides single-component hot-melt adhesives, which offer ease of application, high storage stability, ie several months at 25 ° C. and several hours at 130 ° C.
  • organometallic catalysts of the DBTL type.
  • the free isocyanate content of the adhesives according to the invention is expressed below in grams of NCO per 100 g of adhesive. It is determined according to standard AFNOR 52132.
  • melt index is measured at 190 ° C, under 2.16 kg according to standard ASTM D 1238-73 and expressed in g / 10 min.
  • ASTM D 4498 use of dimension plates: 100 mm x 25 mm x 1 mm.
  • thermopress plate Place four pads then four others joined lengthwise which will serve as wedges on the thermopress plate at 150 ° C or any other temperature of use.
  • thermometer dip a thermometer in the homogeneous holt-melt at 180 ° C. When the temperature of the thermometer reaches 150 ° C remove it from the pot with the adhesive on the lower part. Note the temperature at which the product freezes.
  • EVA-HEA ethylene-vinyl acetate-2-hydroxyethyl acrylate copolymer of MFI 450 and containing 32% by weight of vinyl acetate and 2.15% by weight of HEA produced by the company ELF ATOCHEM.
  • KRISTALEX F85 alphamethylstyrene resin supplied by the company HERCULES
  • ISONATE 125 pure MDI supplied by the company DOW (D) DODECANOL (D) RH 37 NC: tackylated hydroxylated resin supplied by the company
  • the hydroxyl number is 0.57 meq / g and the brookfield viscosity 2000 mPas at 100 ° C.
  • composition according to the invention are listed in Table 1.
  • EVA 1 supplied by the company ELF ATOCHEM with the brand EVATANE® 2805 (melt index 5 g / 10 min according to ASTMD 1238/72 and mass content of vinyl acetate 28%).
  • EVA 2 supplied by the company ELF ATOCHEM with the brand EVATANE ® 18500 (fluidity index 500 g / 10 min according to ASTMD 1238/73 and mass content of vinyl acetate 18%).
  • the viscosity of the hot melt according to Example 1 is 1350 mPa.s at 130 ° C and 4750 mPa.s at 100 ° C which allows it to be used at around 110 ° C.
  • Example 2 The hot melt according to Example 2 was carried out on the same process as Example 1 but with a greater amount of (E) and (F).
  • the hot melt according to Example 3 takes up the composition of Example 2 but in a two-step process.
  • Example 4 repeats the process of Example 2 but with a mass ratio (C) / (B) equal to 1.
  • C mass ratio
  • B mass ratio
  • the hot melt according to Example 5 uses the formulation and the process of Example 4 but with a lower ratio (D) / (B + C).
  • Brookfield viscosity is measured on 1, 1 -
  • Brookfield viscosity is measured on the first day at 130 ° C. and after aging of
  • test pieces carried out on the same day are tested regularly for 1 week.
  • Substrate a ier Kraft.
  • Temperature rise 0.4 ° C / min

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polyurethanes Or Polyureas (AREA)
EP98928371A 1997-05-29 1998-05-28 Compositions adhesives thermofusibles a base de polydiene hydroxyle Withdrawn EP0915942A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9706584 1997-05-29
FR9706584 1997-05-29
PCT/FR1998/001063 WO1998054270A1 (fr) 1997-05-29 1998-05-28 Compositions adhesives thermofusibles a base de polydiene hydroxyle

Publications (1)

Publication Number Publication Date
EP0915942A1 true EP0915942A1 (fr) 1999-05-19

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP98928371A Withdrawn EP0915942A1 (fr) 1997-05-29 1998-05-28 Compositions adhesives thermofusibles a base de polydiene hydroxyle

Country Status (9)

Country Link
US (1) US6207785B1 (ko)
EP (1) EP0915942A1 (ko)
JP (1) JP2000515583A (ko)
KR (1) KR20000029667A (ko)
CN (1) CN1236383A (ko)
AU (1) AU8023198A (ko)
BR (1) BR9806035A (ko)
CA (1) CA2262981A1 (ko)
WO (1) WO1998054270A1 (ko)

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JP4618620B2 (ja) * 2000-05-19 2011-01-26 日本発條株式会社 ハードディスクドライブケースの筺体と蓋体との間のシーリング構造
JP4862187B2 (ja) * 2000-12-18 2012-01-25 日本発條株式会社 電子部品のシーリング方法
JP2005122774A (ja) * 2003-10-14 2005-05-12 Nec Corp 記録型光ディスク装置および光ディスク媒体
US20070037955A1 (en) * 2005-08-15 2007-02-15 Richards James L Polymeric diluents for structural adhesives
US20090159206A1 (en) * 2007-12-20 2009-06-25 National Starch And Chemical Investment Holding Corporation Moisture curable hot melt adhesive
CN109439268B (zh) * 2018-10-31 2021-09-17 烟台德邦科技股份有限公司 一种光伏叠瓦组件用低Tg、低银含量的导电胶

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Publication number Priority date Publication date Assignee Title
JPS58217575A (ja) * 1982-06-11 1983-12-17 Unitika Ltd ホツトメルト接着剤
FR2698877B1 (fr) * 1992-12-04 1995-04-07 Atochem Elf Sa Composition adhésives thermofusibles réticulables à l'humidité.
EP0819711A1 (fr) * 1996-07-16 1998-01-21 Ato Findley S.A. Adhésifs monocomposants à base de polyuréthane à cohésion initiale améliorée

Non-Patent Citations (1)

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Also Published As

Publication number Publication date
KR20000029667A (ko) 2000-05-25
CA2262981A1 (fr) 1998-12-03
JP2000515583A (ja) 2000-11-21
BR9806035A (pt) 1999-08-24
US6207785B1 (en) 2001-03-27
WO1998054270A1 (fr) 1998-12-03
AU8023198A (en) 1998-12-30
CN1236383A (zh) 1999-11-24

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