WO1991018043A1 - Adhesifs thermofusibles a base de terpolymeres d'ethylene - Google Patents

Adhesifs thermofusibles a base de terpolymeres d'ethylene Download PDF

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Publication number
WO1991018043A1
WO1991018043A1 PCT/US1991/002840 US9102840W WO9118043A1 WO 1991018043 A1 WO1991018043 A1 WO 1991018043A1 US 9102840 W US9102840 W US 9102840W WO 9118043 A1 WO9118043 A1 WO 9118043A1
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WO
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Prior art keywords
composition
terpolymer
ethylene
hot melt
adhesive
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Ceased
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PCT/US1991/002840
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English (en)
Inventor
Ernest Francis Eastman
Robert Joseph Statz
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EIDP Inc
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EI Du Pont de Nemours and Co
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Publication of WO1991018043A1 publication Critical patent/WO1991018043A1/fr
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    • 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
    • C09J173/00—Adhesives based on macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C09J159/00 - C09J171/00; Adhesives based on derivatives of such polymers
    • 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
    • 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

Definitions

  • This invention relates to hot melt adhesives, and more specifically it relates to such adhesives formulated from terpolymers of ethylene, an alkyl acrylate or alkyl vinyl ether and carbon monoxide or sulfur dioxide.
  • US Pat. No. 4,434,261 to Brugel et al. discloses a hot melt adhesive sheet which is self supporting at application temperatures of 200-350°F (94-177°C) which as such can be cut and formed to configure to adherends.
  • the sheets are distinguished from 'conventional hot melt adhesives which must be applied in molten form as a premelted hot fluid'.
  • the self supporting nature of the sheet is achieved by adding 20 to 80% of a filler (most preferably 50 to 60%) in combination with 2 to 30% of a plasticizer (preferably 12 to 18%) to any of a variety of ethylene copolymers.
  • Ethylene/vinyl acetate is exemplified as the polymer component.
  • ethylene copolymers terpolymers with either vinyl acetate or alkyl acrylate and carbon monoxide or sulfur dioxide.
  • the sheets are disclosed as being capable of being laminated to fabric like structures, notably spun bonded polyester and spun bonded polypropylene.
  • US 4,600,614 to Lancaster et al. discloses multi-ply microwave film wrapping, wherein two plies of the same 'radiation sealable material' are in sealable contact with each other.
  • the radiation sealable material may be any of a large number of copolymers and terpolymers which must contain from .01 to 50 wt. % of carbon monoxide.
  • the carbon monoxide renders the polymer heatable by high frequency electromagnetic radiation (microwave energy) .
  • microwave energy electromagnetic energy
  • a termonomer may be vinyl acetate, acrylic or methacrylic acid or its esters or salts.
  • Japanese laid open patent application No 2-73828 assigned to du Pont-Mitsui discloses high performance adhesives of nylon grafted ethylene butyl acrylate carbon monoxide terpolymers. In that application, use of the terpolymers alone is shown in comparative examples to have deficient high temperature bonding performance.
  • the present invention satisfies this need by providing a thermally stable adhesive composition that may be used for adhering to a wide variety of adherends such as metals, polar and non polar plastics as well as wood and paper products, and may be applied in an economical way using common low shear hot melt adhesive application equipment. That is to say, the adhesive composition when heated for application as a hot melt adhesive takes the form of a molten fluid which is too fluid to be extrudable, or be self supporting, but ideally suited for conventional hot melt application. Accordingly, one embodiment of the present invention provides thermally stable hot melt adhesive compositions which are fluid at application temperatures, consisting essentially of ethylene 5 terpolymers containing about 40 to 87 wt.
  • % of ethylene about 10 to 50 wt.% of an alkyl acrylate or alkyl vinyl ether, and about 3 to 30 wt% of carbon monoxide or sulfur dioxide, the wt. %'s being based on the weight of the terpolymer, and about 5-80 wt% of a
  • compatible tackifier based on the weight of the terpolymer plus tackifier.
  • Plasticizers and a compatible wax may optionally be present in the compositions.
  • the terpolymer component of the adhesive compositions of the present invention provides the cohesive and adhesive strength and thermal stability to the composition.
  • Alkyl acrylate or alkyl vinyl ether can be
  • alkyl acrylate examples include those in which the alkyl group contains from 1 to 8 carbon atoms. Such examples include alkyl acrylates and methacrylates, such as methyl acrylate, ethyl acrylate, isobutyl
  • Second monomers which lower the glass transition temperature of the terpolymer will tend to make the terpolymer lower in viscosity for a given molecular weight, and ensure a tougher stronger polymer at ambient and moderately low temperatures.
  • n-Butyl acrylate is especially useful in this regard and therefore is a preferred second monomer.
  • At least about 10% by wt. of the terpolymer should consist of the alkyl acrylate monomer so that the adhesive composition can develo strong adhesive bonding.
  • the maximum amount of acrylate monomer is generally dictated by the maximum amount which is polymerizable with ethylene and the third monomer. Generally, this maximu amount is about 50% by wt.
  • the alkyl vinyl ether as the second monomer preferably contains from 1 to 8 carbon atoms in the alkyl group and can be used as an alternative to the alkyl acrylate comono er, imparting the same characteristics to the adhesive composition as the alkyl acrylate.
  • alkyl vinyl ethers include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, n-butyl vinyl ether, 2-ethylhexyl vinyl ether.
  • the alkyl acrylate and alkyl vinyl ether monomers provide greater thermal stability to the composition.
  • the adhesive compositions of the present invention, and hence the polymers used therein need foremost to have adequate thermal stability at temperatures where the polymer is fluid enough to be applied with hot melt equipment. Stability requirements are generally more stringent than those required for an extrudable or preformed adhesive, since often extended hold up times at application temperatures are involved.
  • the carbon monoxide or sulfur dioxide comonomer component can be considered the third monomer of the terpolymer.
  • This comonomer enhances the adhesive versatility of the terpolymer and thus the composition, enabling it to adhere to a wide variety of adherends. At least about 3% by wt. of the terpolymer should be carbon monoxide or sulfur dioxide to provide this versatile effect.
  • These termonomers are " polar, and this polarity imparted to the terpolymer enables the adhesive composition of the present invention to adhere to polar as well as non-polar plastic adherends. Greater than about 30% by wt. of these termonomers in the terpolymer can adversely affect the thermal stability of the terpolymer.
  • the third monomers used herein essentially destroy the thermal stability of ethylene vinyl acetate terpolymers containing CO or SO 2 , even with the presence of antioxidant.
  • the terpolymers of the present invention have far superior thermal stability, enabling them to achieve advantageous utility in hot melt adhesive compositions applied as adhesives- in the molten fluid state.
  • One aspect of thermal stability is resistance to oxidation by the composition while being held in the fluid state at application temperatures.
  • Preferred adhesive compositions of the present invention consist essentially of terpolymers containing about 45 to 80 wt. % of ethylene, about 10 to 40 wt. % akyl acrylate, and about 3 to 20 wt. % of carbon monoxide, based on the weight of the terpolymer, and about 30 to 80 wt. % of tackifier, based on the weight of terpolymer plus tackifier.
  • the polymeric components of the present invention may be prepared by the method described in U.S. Patent 3,780.140, which is hereby incorporated herein.
  • the tackifier component can be selected from a wide variety of materials, such as follows: a) Wood gum or tall oil rosin acids. They can be hydrogenated, disproportionated or mildly polymerized. b) Esters of the various classes of rosin acids referred to above. Alcohols suitable for preparing these esters include mono- and polyethylene glycol ⁇ , glycerol, pentaerythritol and related products. c) Terpene resins d) Dicyclopentadiene-aromatic hydrocarbon resins such as those described in US Pat. No. 3,023,200 covering 'Piccovar' resin manufactured by Hercules Inc. e) Low molecular weight resins based on styrene and or substituted styrenes.
  • the tackifier is selected to be compatible with the terpolymer component. This compatibility is obtained by the terpolymer and tackifier being mi ⁇ cible with one another in the molten state. Upon cooling to room temperature the composition compatibility within the composition is observable by the composition being both clear, not hazy, in appearance and flexible rather than brittle.
  • the proportion and identity of the tackifier is selected to cooperate with the terpolymer to produce the fluidity desired at the hot melt application temperature, generally falling within the range of about 250 to 400°F (121 to 204°C) .
  • Fluidity of the adhesive compositions of the present invention are described herein in terms of viscosity measured as Brookfield viscosity at 350°F (177°C) .
  • the low viscosities required for the adhesive compositions of this invention can be achieved either by starting with a relatively high viscosity terpolymer, and reducing the viscosity to the required level with a considerable amount of tackifier and optionally compatible plasticizers and/or wax or by starting with much lower viscosity terpolymer and using less tackifier.
  • the viscosity of the terpolymer can be described in terms of melt index.
  • the melt index of the terpolymer component may be from 1 to 3000 g/lOmin. measured at 190° C.
  • the viscosity of the hot melt adhesive composition of the present invention. should be at least about 1000 cp ⁇ at 177°C and generally need not.be greater than 50,000 cps at 177"C. These viscosities correspond approximately to a melt index of about 10,000 to 200g/10 min.
  • reducing molecular weight of the terpolymer component reduces its viscosity, this is accompanied by decreasing strength in the terpolymer itself.
  • less low molecular weight viscosity diluent tackifier, and optionally plasticizer and/or wax
  • the strength of the final formulation is usually a compromise between the viscosity of the terpolymer component and the amount of tackifier and plasticizer, if any, used.
  • Using an excessively high molecular weight terpolymer, and formulating to reduce the viscosity with an excessive amount of compatible tackifier, and plasticizer or wax can lead to a composition with deficient cohesive strength. At least about 20 wt % of terpolymer, is required for the composition to have adequate strength properties.
  • compositions of the present invention may also contain compatible plasticizer and/or compatible wax for the purpose of adjusting the fluidity of the composition at the application temperature and other properties of the adhesive and in the application equipment being used.
  • plasticizers tend to be more glassy and may enhance tackiness in formulations
  • plasticizers tend to be low molecular weight liquids with low glass transition temperatures.
  • plasticizers which may be used in adhesive compositions of the present invention include phthalate ⁇ , azelates, adipates, tricresyl phosphate and polyesters such as those used in flexibilizing polyvinyl choride, low molecular weight resins made from alkylated phenols, phenol modified coumaroneindene, terpenes and synethtic terpernes, and from petroleum derived processing oils.
  • becau ⁇ e waxe ⁇ may provide an inexpen ⁇ ive way to reduce viscosity, may contribute to some extent in improving resistance to temperature, reduce open time, or the time after application during which the polymer is sticky. This in turn leads to rapid application times.
  • waxe ⁇ may promote wetting and prevent blocking.
  • Paraffin wax commonly u ⁇ ed in hot melt adhesives, is generally not compatible with adhesive composition ⁇ of the pre ⁇ ent invention with the desired versatility because of the polarity imparted to the terpolymer by the CO or SO 2 co-monomer.
  • Other waxes, such as Carnauba wax can be used in adhe ⁇ ive compositions of the present invention.
  • the adhesive formulator will choose among an enormous range of possible formulation components such as tackifier, and optionally wax and/or plasticizer and well as their levels in the composition.
  • tackifier e.g., tackifier
  • wax and/or plasticizer e.g., wax and/or plasticizer
  • Antioxidant ⁇ are generally used in the formulation of ethylene copolymer hot melt adhesives, and it wa ⁇ found that they were de ⁇ irable for best performance of formulations of the present invention.
  • Suitable antioxidant ⁇ include typical hindered phenol ⁇ ⁇ uch a ⁇ butylated hydroxytoluene (BHT) , 'Ethyl'330, Ciba Geigy 'Irganox'1010 or 1098 a ⁇ well a ⁇ phosphites, butyl zi ate.
  • 'Irganox' 1010 which is a hindered phenol has been found particularly advantageou ⁇ .
  • antioxidant i ⁇ u ⁇ ed it i ⁇ u ⁇ ed in an amount which i ⁇ effective to provide the oxidative ⁇ tability de ⁇ ired above and beyond the oxidative ⁇ tability of the terpolymer.
  • Adhe ⁇ ive compo ⁇ ition ⁇ of the pre ⁇ ent invention can be made by conventional melt blending of the ingredients to produce a mi ⁇ cible melt. The melt can then be applied a ⁇ a hot melt adhesive. Used as such, the adhesive differs from ⁇ olvent-ba ⁇ ed adhe ⁇ ive ⁇ because of the ab ⁇ ence of solvent and the adhesive-aiding effect of solvents. This i ⁇ re ⁇ ponsible for the conventional hot melt adhesive ⁇ being quite ⁇ elective a ⁇ to the ⁇ ub ⁇ trate ⁇ to which they will adhere.
  • the hot melt adhesives of the present invention a ⁇ do conventional hot melt adhe ⁇ ive ⁇ which are applied in the fluid state also face stringent requirements for thermal stability, including oxidative ⁇ tability.
  • the hot melt adhe ⁇ ive component ⁇ may be melt blended in a container and maintained in the heated, melt condition until applied a ⁇ an adhe ⁇ ive.
  • well known equipment such as a ⁇ a Brabender mixer, or a Perkin ⁇ Sigma blade mixer may advantageously be employed for the melt blending step.
  • the time of maintaining the resultant composition in the molten state can depend on the size of the container and the rate the composition is applied as an adhesive. During thi ⁇ time, the composition may be exposed to the atmosphere and oxidation thereby.
  • Adhesive compo ⁇ ition ⁇ of the present invention are oxidatively stable a ⁇ well a ⁇ having stability from thermal degradation or they have sufficient thermal ⁇ tability that the u ⁇ e of antioxidant in the compo ⁇ ition can provide the addition oxidative stability de ⁇ ired.
  • the adhe ⁇ ive compositions of the present invention al ⁇ o differ from the extrudable self- ⁇ upporting sheet ⁇ di ⁇ closed in U.S. Pat. 4,434,261 in that these sheets are heated only when applied as the adhesive, and therefore are not expo ⁇ ed to the destructive effects of long-term heating, and not to heating to the* fluid or molten state at all.
  • the compo ⁇ ition ⁇ of the pre ⁇ ent invention provide a hot melt adhesive of outstanding versatility as a hot melt adhesive, in terms of application to a wide variety of adherents both polar and non-polar, and having adequate thermal stability ⁇ o a ⁇ to be useful to this purpose.
  • the adhe ⁇ ive compo ⁇ ition ⁇ of the present invention are applied in conventional manner for hot melt adhesives used in the fluid state.
  • the adhesive composition is applied in the molten fluid form to the adherend, followed by contacting the adhesive composition still in the molten fluid ⁇ tate on the fir ⁇ t adherent, with a ⁇ econd adherend, and cooling the re ⁇ ultant composite structure to create the adhesive bond.
  • the adherends will usually be at room temperature and the contacting step is usually done with the application of pre ⁇ ure ⁇ ufficient to obtain uniform di ⁇ tribution of the adhe ⁇ ive compo ⁇ ition between adherend .
  • the adherend ⁇ or ⁇ ub ⁇ trate ⁇ which can be bonded together by adhe ⁇ ive compo ⁇ ition ⁇ of the pre ⁇ ent invention can be the same or different materials, such as metal, wood, paper, and polar and non-polar pla ⁇ tic ⁇ .
  • pla ⁇ tic ⁇ include polyethylene, polye ⁇ ter ⁇ , including polycarbonate, polyacrylate ⁇ , including polymethyl methacrylate, poly ⁇ tyrene, polyvinylchloride, and ABS polymer ⁇ .
  • Example ⁇ of metal ⁇ include aluminum and ⁇ tainle ⁇ ⁇ teel.
  • the adhe ⁇ ion te ⁇ ting in the ⁇ e Example ⁇ was carried out as follows:
  • the substrates used were panels measuring about 3 x 1 x 1/4 in.
  • the adhesives were tested using the so-called 'button test', which i ⁇ carried out in the following manner.
  • Adhe ⁇ ive at about 177° C. wa ⁇ applied to one ⁇ ubstrate at room temperature, and then the ⁇ econd ⁇ ub ⁇ trate al ⁇ o at room temperature was placed on the adhe ⁇ ive, and the two ⁇ ub ⁇ trates pressed together using finger pres ⁇ ure.
  • the two sub ⁇ trate ⁇ were pre ⁇ sed together traversely so that the total bond area was about one square inch.
  • the bond wa ⁇ tested by pulling apart the substrate ⁇ in an In ⁇ tron tester at 0.5 inches/min. The force need to break the bonding wa ⁇ recorded.
  • Thermal ⁇ tability was measured u ⁇ ing a Brookfield vi ⁇ cometer, model RVT, u ⁇ ing a # 27 spindle. Viscosity was measured after various times in the viscometer. Oxidative ⁇ tability wa ⁇ mea ⁇ ured by allowing the adhe ⁇ ive compo ⁇ ition to ⁇ tand in an open ve ⁇ el 2 in. in diameter in an air oven at about 177° C. for the times indicated. The ves ⁇ el wa ⁇ filled with ⁇ ufficient material ⁇ o that the melted material wa ⁇ about 1/4 in. deep. The viscosity was then measured by transferring the cooled hot air exposed material to a Brookfield Viscometer, at 177° C.
  • Example ⁇ 1 -4 show that formulation ⁇ u ⁇ ing variou ⁇ terpolymer ⁇ of ethylene with acrylate ⁇ and carbon monoxide or sulfur dioxide are much more thermally stable than ethylene vinyl acetate carbon monoxide terpolymer which is unstable after just three hour ⁇ .
  • the comonomer added to the EVA (Cl) ju ⁇ t about de ⁇ troyed the thermal ⁇ tability of thi ⁇ terpolymer, wherea ⁇ compo ⁇ ition ⁇ of the present invention in which the terpolymer contained CO were quite thermally stable.
  • the composition of Example 1 had a relatively high vi ⁇ co ⁇ ity.
  • Thi ⁇ can be reduced by u ⁇ e of a greater proportion of tackifier, or a different tackifier which provide ⁇ greater fluidity at application temperature ⁇ and/or by incorporation of compatible pla ⁇ ticizer and/or wax into the compo ⁇ ition.
  • Example ⁇ 5 - 7 and C2 ⁇ how that ethylene n-butyl acrylate carbon monoxide terpolymer ⁇ are surprisingly just as stable a ⁇ ethylene n-butyl acrylate polymer without any carbon monoxide. The carbon monoxide doe ⁇ not hurt thermal stability at thi ⁇ level, and, a ⁇ will be ⁇ een in later example ⁇ , it improve ⁇ adhe ⁇ ive qualities.
  • Examples 8 - 10 and C3 show the oxidative ⁇ tability of compo ⁇ ition ⁇ of the present invention.
  • Stability is as good as in the comparative example C3.
  • Example ⁇ 11 - 13 and C4 illustrate the compatibility of E/nBA/CO compared with E/nBA with a range of varied tackifiers.
  • the final compo ⁇ ition must be both compatible, and flexible rather than brittle.
  • Result ⁇ of the test shown in Table 3 ⁇ how that at 25 and 26 wt% nBA for two terpolymer ⁇ and the copolymer, whether the CO level i ⁇ low (4%) or higher (9%) , the terpolymer blends show substantially greater compatibility.
  • Examples 14 - 25 and Comparative Examples C5 - CIO Examples 14 - 25 and Comparative Examples C5 - CIO.
  • Examples 14 - 25 and C5 - CIO ⁇ how that variou ⁇ terpolymer ⁇ formulated with different tackifier types, give adhesion to a whole range of varied substrate ⁇ that i ⁇ generally superior to ethylene vinyl acetate or ethylene butyl acrylate resin formulations. Despite the polar nature of the terpolymer, adhesion even to a non-polar resin like polyethylene i ⁇ still remarkably good. Ethylene vinyl acetate carbon monoxide terpolymer gives good adhe ⁇ ion, but a ⁇ ⁇ een earlier, i ⁇ thermally un ⁇ table. Re ⁇ ult ⁇ are shown in Table 4. While the visco ⁇ ity of the formulation ⁇ wa ⁇ not mea ⁇ ured in mo ⁇ t ca ⁇ e ⁇ , all formulations were fluid at the application temperature.
  • Tl Foral 105
  • T2 Kristolex 3070.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

On mélange des terpolymères d'éthylène présentant des monomères tels qu'un alkylacrylate et du monoxyde de carbone avec 5 à 80 % d'une colle compatible afin de produire des adhésifs thermofusibles thermiquement stables collant à une large variété de substrats, et lesquels sont idéalement fluides pour permettre une utilisation dans des applicateurs d'adhésifs thermofusibles à faible cisaillement communs. Les adhésifs peuvent également comprendre des plastifiants et des cires compatibles.
PCT/US1991/002840 1990-05-17 1991-05-01 Adhesifs thermofusibles a base de terpolymeres d'ethylene Ceased WO1991018043A1 (fr)

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US52537890A 1990-05-17 1990-05-17
US525,378 1990-05-17

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5209983A (en) * 1992-06-26 1993-05-11 E. I. Du Pont De Nemours And Company Adhesives for laminating vinyl to various substrates
US5234986A (en) * 1992-03-02 1993-08-10 E. I. Du Pont De Nemours And Company Hot-melt adhesives for PVC with good high temperature utility
WO1993018108A1 (fr) * 1992-03-13 1993-09-16 Allied-Signal Inc. Compositions auto-adhesives thermofusibles comprenant des copolymeres d'ethylene de faible poids moleculaire
EP0612824A1 (fr) * 1993-02-23 1994-08-31 National Starch and Chemical Investment Holding Corporation Adhésif thermofusible amélioré
EP0648801A1 (fr) * 1993-10-14 1995-04-19 Dupont Canada Inc. Collage de substrats à l'aide d'adhésifs solides
WO1997015635A1 (fr) * 1995-10-20 1997-05-01 Exxon Chemical Patents Inc. Adhesif thermofusible atomisable a base d'ethylene
US6239250B1 (en) 1999-04-16 2001-05-29 Air Products And Chemicals, Inc. Hot melt adhesives produced from linear alternating polyketones
WO2002006416A3 (fr) * 2000-07-18 2002-08-29 Exxonmobil Res & Eng Co Utilisation de polymeres a base de monoxyde de carbone comme additifs adhesifs et fluides
US7563479B2 (en) 1996-08-29 2009-07-21 H.B. Fuller Licensing & Financing, Inc Method for producing a continuous thermoplastic coating and articles constructed therefrom

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0064893A1 (fr) * 1981-04-30 1982-11-17 Société Chimique des Charbonnages Compositions applicables à la fabrication de colles thermofusibles et leur procédé de préparation
EP0101028A1 (fr) * 1982-08-06 1984-02-22 E.I. Du Pont De Nemours And Company Feuille adhésive auto-supportée, extrudable, adhérant par fusion à chaud
WO1986007010A1 (fr) * 1985-05-28 1986-12-04 The Dow Chemical Company Laminage a haute frequence de mousses polymeres
EP0300158A2 (fr) * 1987-06-19 1989-01-25 National Starch and Chemical Investment Holding Corporation Adhésifs à base de copolymère d'éthylène et d'acrylate de N-butyle

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0064893A1 (fr) * 1981-04-30 1982-11-17 Société Chimique des Charbonnages Compositions applicables à la fabrication de colles thermofusibles et leur procédé de préparation
EP0101028A1 (fr) * 1982-08-06 1984-02-22 E.I. Du Pont De Nemours And Company Feuille adhésive auto-supportée, extrudable, adhérant par fusion à chaud
WO1986007010A1 (fr) * 1985-05-28 1986-12-04 The Dow Chemical Company Laminage a haute frequence de mousses polymeres
EP0300158A2 (fr) * 1987-06-19 1989-01-25 National Starch and Chemical Investment Holding Corporation Adhésifs à base de copolymère d'éthylène et d'acrylate de N-butyle

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993018107A1 (fr) * 1992-03-02 1993-09-16 E.I. Du Pont De Nemours And Company Adhesifs thermofusibles pour pvc presentant une bonne activite a des temperatures elevees
US5234986A (en) * 1992-03-02 1993-08-10 E. I. Du Pont De Nemours And Company Hot-melt adhesives for PVC with good high temperature utility
US5391434A (en) * 1992-03-13 1995-02-21 Alliedsignal Inc. Hot melt adhesive compositions comprising low molecular weight ethylene copolymers
WO1993018108A1 (fr) * 1992-03-13 1993-09-16 Allied-Signal Inc. Compositions auto-adhesives thermofusibles comprenant des copolymeres d'ethylene de faible poids moleculaire
US5340863A (en) * 1992-03-13 1994-08-23 Alliedsignal, Inc. Hot metal adhesive compositions comprising low molecular weight ethylene copolymers
US5209983A (en) * 1992-06-26 1993-05-11 E. I. Du Pont De Nemours And Company Adhesives for laminating vinyl to various substrates
EP0612824A1 (fr) * 1993-02-23 1994-08-31 National Starch and Chemical Investment Holding Corporation Adhésif thermofusible amélioré
EP0648801A1 (fr) * 1993-10-14 1995-04-19 Dupont Canada Inc. Collage de substrats à l'aide d'adhésifs solides
US7699826B2 (en) 1995-02-23 2010-04-20 H. B. Fuller Company Article having a continuous thermoplastic coating
WO1997015635A1 (fr) * 1995-10-20 1997-05-01 Exxon Chemical Patents Inc. Adhesif thermofusible atomisable a base d'ethylene
US7563479B2 (en) 1996-08-29 2009-07-21 H.B. Fuller Licensing & Financing, Inc Method for producing a continuous thermoplastic coating and articles constructed therefrom
US6239250B1 (en) 1999-04-16 2001-05-29 Air Products And Chemicals, Inc. Hot melt adhesives produced from linear alternating polyketones
WO2002006416A3 (fr) * 2000-07-18 2002-08-29 Exxonmobil Res & Eng Co Utilisation de polymeres a base de monoxyde de carbone comme additifs adhesifs et fluides
US6573226B2 (en) 2000-07-18 2003-06-03 Exxonmobil Research And Engineering Company Use of carbon monoxide containing polymers as, adhesive additives, and fluids

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