WO1997015635A1 - Adhesif thermofusible atomisable a base d'ethylene - Google Patents

Adhesif thermofusible atomisable a base d'ethylene Download PDF

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Publication number
WO1997015635A1
WO1997015635A1 PCT/EP1996/003858 EP9603858W WO9715635A1 WO 1997015635 A1 WO1997015635 A1 WO 1997015635A1 EP 9603858 W EP9603858 W EP 9603858W WO 9715635 A1 WO9715635 A1 WO 9715635A1
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WO
WIPO (PCT)
Prior art keywords
hydrogenated
tackifier
hot melt
weight
ethylene
Prior art date
Application number
PCT/EP1996/003858
Other languages
English (en)
Inventor
Michel Louis Faissat
Herman Diederik Marie Emiel Robberechts
Original Assignee
Exxon Chemical Patents Inc.
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 Exxon Chemical Patents Inc. filed Critical Exxon Chemical Patents Inc.
Publication of WO1997015635A1 publication Critical patent/WO1997015635A1/fr

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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
    • 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 sprayable hot melt adhesives based upon ethylene copolymers and methods to apply these hot melt adhesives, particularly in disposable packaging and assembly applications and articles produced by such methods.
  • Sprayable hot melt adhesives are desirable for the economic and commercial reasons that they can be thinly, evenly and quickly coated onto a substrate, saving in both time and material, and that they allow better substrate coverage per quantitiy of adhesive.
  • Typical sprayable hot melt adhesives comprise an amorphous copolymer, generally a butene based copolymer of a styrene based block copolymer, combined with a tackifier.
  • U.S. Patent 4,959,207 discloses sprayable hot melt adhesives of butene copolymers having up to 5.5 to 10 weight % ethylene, tackifier and amorphous diluent having a softening point greater than 90 °C.
  • EP 442 045 A2 discloses sprayable hot melt adhesives of amorphous polyalphaolefins having 3 to 75 weight % C 4 to C 10 alpha-olefin, 25 to 95 weight % propylene 0 to 20 weight % ethylene.
  • amorphous polyalphaolefins having 3 to 75 weight % C 4 to C 10 alpha-olefin, 25 to 95 weight % propylene 0 to 20 weight % ethylene.
  • these blends were unsuccessful because the polymer would coagulate at the nozzle head or give uneven coating patterns of spots of unequal size rather than a regular even coating pattern.
  • JP- 4180981 A addresses the problem of coagulation at the nozzle head by disclosing a hot melt adhesives of wax, bivalent phenol stabilizer, partially aleated or fumarated rosin ester tackifier and ethylene copolymer of ethylene mono-carboxylic vinyl ester/acrylic ester and suggesting that they will not clog the nozzle head when sprayed. However, when actually sprayed these hot melt adhesives will not produce a regular even pattern.
  • WO 94 10256 discloses ethylene copolymer blends for hot melt adhesives. However these blends are not suggested for use in spraying applications.
  • this invention provides new sprayable hot melt adhesive compositions based upon ethylene copolymers.
  • This invention relates firstly to sprayable hot melt adhesive compositions comprising: a tackifier and an ethylene polymer having up to 45 weight % polar comonomer, based upon the weight of the copolymer and secondly to a process for spraying ethylene polymers comprising selecting a hot melt adhesive composition described above; provided that the tackifier should not be a rosin ester based tackifer with a softening point of 110-140 °C used in combination with a di-hydric phenol based stabilizer. atomizing, spiral spraying or melt blowing the hot melt adhesive selected onto a substrate.
  • this invention relates to sprayable hot melt adhesive compositions comprising: a tackifier, and an ethylene polymer having up to 40 weight % of a polar comonomer, based upon the weight of the copolymer; and melt index of 5 or more.
  • Preferred ethylene polymers that can be used in the practice of this invention include ethylene polymers having up to 40 weight %,from 0.5 to 33 weight %, even more preferably from 10 to 30 weight %, based upon the weight of the copolymer, of one or more polar comonomers.
  • Preferred polar comonomers may be an ester, a carboxylic acid, an acrylic, and acrylic ester, a vinyl ester or the like.
  • the polar monomer is a vinyl ester or an alkyl acrylic ester, such as vinyl acetate, acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methacrylic acid, ethacrylic acid, and derivatives thereof.
  • the ethylene polymers used in this invention have a melt index as measured by ASTM 1238, condition E, of 5 dg/min or more, preferably 15 dg/min or more, even more preferably 30 dg/min or more, even more preferably between about 100 and 10,000 dg/min.
  • the ethylene polymers of this invention are at least 50 % amorphous, preferably between 60 and 100% amorphous, even more preferably between 70 and 100% amorphous. Percent amorphous content is determined by Differential Scanning Calorimetry measurement according to ASTM E 794-85.
  • Preferred tackifiers that may be blended with the ethylene copolymers described above are those typically used in the art. Examples include, but are not limited to, aliphatic hydrocarbon resins, aromatic modified aliphatic hydrocarbon resins, hydrogenated polycyclopentadiene resins, polycyclopentadiene resins, gum rosins, gum rosin esters, wood rosins, wood rosin esters, tall oil rosins, tall oil rosin esters, polyterpenes, aromatic modified polyterpenes, terpene phenolics, aromatic modified hydrogenated polycyclopentediene resins, hydrogenated aliphatic resin, hydrogenated aliphatic aromatic resins, hydrogenated terpenes and modified terpenes, and hydrogenated rosin esters.
  • the tackifier is hydrogenated.
  • the tackifier should not be a rosin ester based tackifer with a softening point of 110-140 °C used in combination with a di-hydric phenol based stabilizer.
  • Preferred tackifiers include the tall oil rosin esters and the cyclic C5 based tackifiers.
  • the tackifier is typically present at about 15 weight % to about 75 weight %, based upon the weight of the blend, more preferably 30 weight % to 65 weight %, even more preferably 40 weight % to 60 weight %.
  • the ethylene polymer and the tackifier may be blended together by methods known in the art.
  • the ethylene copolymer and the tackifiers can be physically admixed, they can be melt blended, they can be master batched, they can be solvent blended and the like.
  • the polymer and the tackifier are melted in a Z-blade mixer of in a Brabender twin screw extruder and blended under high shear conditions.
  • Their blend components should be chosen so that a final blend viscosity of 20,000 mPaS or less is obtained, preferably 15,000 or less, even more preferably 10,000 or less, even more preferably 8,000 or less even more preferably between 500 and 8000.
  • the range of 500 to 5000 Pas at 180°C is ideal for spraying a low coating weight and wide spray pattern (spiral, net like web, or nebulized droplets) .
  • polymers include any of the polymers described above as ethylene polymers .
  • the second polymer may be present at up to 50 weight %, preferably 0.1 weight % to 30 weight %.
  • a preferred class of polymer to be added to the composition is an ethylene/propylene/butene terpolymer.
  • Ethylene/propylene/ butene terpolymers are not typically sprayable, however, when blended with the ethylene polymers described above, they can be formed into sprayable compositions.
  • Examples of preferred ethylene/propylene/butene terpolymers are VESTOPLASTTM 708, VESTOPLASTTM750, and VESTOPLASTTM408 which are commercially available from H ⁇ ls.
  • the ethylene/propylene/butene terpolymer is preferably present at up to 50 weight %, even more preferably at 0.1 weight % to 20 weight %, even more preferably at 0.1 weight % to 15 weight %.
  • plasticizers include mineral oils, polybutenes, phthalates and the like. Particularly preferred plasticizers include phthalates such as diisoundecyl phthalate (DIUP) , diisononylphthalate (DINP) , dioctylphthalates (DOP) and the like.
  • phthalates such as diisoundecyl phthalate (DIUP) , diisononylphthalate (DINP) , dioctylphthalates (DOP) and the like.
  • Another optional component of the ethylene polymer/tackifier composition is a low molecular weight product such as wax, oil or low Mn polymer, (low meaning below Mn of 5000, preferably below 4000, more preferably below 3000, even more preferably below 2500) .
  • Preferred oils include aliphatic napthenic oils.
  • Preferred low Mn polymers include polymers of lower alpha olefins such as propylene, butene, pentene, hexene and the like.
  • a particularly preferred polymer includes polybutene having an Mn of less than 1000.
  • An example of such a polymer is available under the trade name PARAPOLTM 950 from Exxon Chemical Company.
  • PARAPOLTM 950 is an liquid polybutene polymer having an Mn of 950 and a kinematic viscosity of 220cSt at 100 °C, as measured by ASTM D 445.
  • the blend may then be applied directly to a substrate as a hot melt adhesive or may be sprayed thereon.
  • Spraying is defined to include atomizing, spiral spray controlled fiberization and melt blown techniques.
  • Melt blown techniques are defined to include the methods described in U.S. patent 5,145,689 or any process where air streams are used to break up filaments of the extrudate and then used to deposit the broken filaments on a substrate.
  • melt blown techniques are processes that use air to spin hot melt adhesive fibers and convey them onto a substrate for bonding. Fibers sizes can easily be controlled from 20-200 microns by changing the melt to air ratio. Few, preferably no, stray fibers are generated due to the inherent stability of adhesive melt blown applicators. Under UV light the bonding appears as a regular, smooth, stretched dots pattern.
  • Atomization is a process that uses air to atomize hot melt adhesive into very small dots and convey them onto a substrate for bonding.
  • the blend may also be applied to a substrate using conventional techniques for applying a hot melt adhesive to a substrate.
  • hot melt jet nozzle coating hot melt multiline coating, hot melt slot die coating, hot melt wheel coating, hot melt roller coating, and solvent roller coating.
  • the blend is applied to a substrate using a spiral spray.
  • Spiral spray is a method used for producing a filamentary spiral application.
  • the hot melt adhesive and spray air are mixed inside the nozzle, eliminating external influences on the spray pattern.
  • the hot melt adhesive is drawn into a small fiber by high-velocity air jets. The fiber is then rotated by jets until it contacts the substrate, producing a helical pattern from the single strand of adhesive.
  • the sprayed hot melt adhesives of this invention can be used for disposible diaper and napkin chasis construction, elastic attachment in disposable goods converting, packaging, labelling and other assembly applications.
  • Particularly preferred applications include: baby diaper leg elastic, diaper frontal tape, diaper standing leg cuff, diaper chassis construction, diaper core stabilization, diaper liquid transfer layer, diaper outer cover lamination, diaper elastic cuff lamination, feminine napkin core stabilization, feminine napking adhesive strip, industrial filtration bonding, industrial filter material lamination, filter mask lamination, surgical gown lamination, surgical drape lamination, and perishable products packaging.
  • MI Melt Index
  • SAFT Shear Adhesion Fail Temperature
  • Melt Flow Rate was measured according to ASTM D 1238 (10 kg, 230 °C)
  • VECTORTM 4461D is a styrene-butadiene-styrene block copolymer having an melt flow rate of 23 dg/min, a styrene content of 43 weight %, and an Mw of 60,000.
  • VECTORTM 4113 is a styrene-isoprene-styrene block copolymer having an melt flow rate of 10 dg/min, a styrene content of 15 weight %, and an Mw of 143,000.
  • XW-23 is an ethylene/butyl acrylate copolymer having an MI of 320 dg/min, and a butyl acrylate content of 33 weight %.
  • PARAPOlTM 950 is a liquid polybutene having an Mn of about 950 and a Kinematic viscosity of 220 cst at 100 °c, as measured by ASTM D445.
  • ESCOREZTM 5380 is a hydrogenated polycyclopentadiene tackifier having a softening point of 85 °C.
  • ESCOREZTM 5320 is a hydrogenated polycyclopentadiene tackifier having a softening point of 125 °C.
  • ESCOREZTM 5300 is a hydrogenated polycyclopentadiene tackifier having a softening point of 105 °C.
  • ESCOREZTM 6368 (ECR 368LC) is a hydrogenated aliphatic aromatic tackifier having a softening point of 100 °C.
  • OPTEMATM XS 9304 is an ethylene/methylacryalte copolymer having and MI of 270 dg/min and density of 0.939 g/cc and an MA content of 21.5 %.
  • OPTEMATM TC 140 is an ethylene/methylacryalte copolymer having and MI of 135 dg/min and density of 0.939 g/cc and an MA content of 21.5 %.
  • ADEVATM 629 is a high modulus ethylene/vinyl actetate copolymer having an MI of 400 dg/min, and a VA content of 33%.
  • ESCORENETM UL 40028 is an ethylene/vinyl actetate copolymer having an MI of 400 dg/min, and a VA content of 28%.
  • ESCORENETM UL 15028 is an ethylene/vinyl actetate copolymer having an MI of 150 dg/min, and a VA content of 28 %.
  • ESCORENETM UL 05540 is an ethylene/vinyl actetate copolymer having an MI of 55 dg/min, and a VA content of
  • ECR 404 is a light color hydrogenated polycyclopentadiene tackifier having a softening point of 118 °C.
  • VECTORTM DPX 554 is a styrene-isoprene-styrene block copolymer having an MFR of 9 and a styrene content of 30 weight %.
  • VESTOPLASTTM750 is an ethylene/propylene/butene copolymer available from H ⁇ ls, having a density of 0.87 and an MV of 70,000.
  • VESTOPLAST TM708 is an ethylene/propylene/butene copolymer available from H ⁇ ls, having a density of 0.87 and an MV of 45,000.
  • DIUP is diisoundecyl pthalate
  • PRIMOLTM 352 is a hydrogenated white aliphatic napthenic oil available from Exxon Chemical Company.
  • Lotryl HYTM 6190 is an ethylene butyl acrylate copolymer having an MI of 400 dg/min and a butyl acrylate content of 28% available from Atochem.
  • EX 659 is a high modulus ethylene/vinyl acetate copolymer having an MI of 800 dg/min, and a VA content of 28% available from Exxon Chemical Company.
  • Meltex CT 325 is a coating machine from Nordson/Meltex.
  • EP 34-6SD spray head is a spiral spray coating head.
  • IRGANOXTM 1010 is an antioxidant available form Ciba
  • Brake roll 1 0-0.5 bar Brake roll 2: 0-0.5 bar Unwind 1: 0-0.5 bar Lamination roll 1: 4 bar Lamination roll 2: 4 bar Umwind 2 : 0-0.5 bar Cooling Unit: 15-16°c Webspeed: 125 m/min pumpspeed between 40-50 rpm on TACHO to have a coating weight of ⁇ 0.5 g/lm for a spiral diameter of 4-4.5 cm
  • 1 g/spiral spray +4cm, Adhesive spiral sprayed onto a nonwoven coverstock of thermally bonded polypropylene and then bonded to a polyethylene substrate.
  • 2 Adhesive coated onto polyethylene substrate then bonded to another polyethylene substrate.
  • 3 adhesive meltblown onto a nonwoven coverstock of thermally bonded polypropylene then bonded to polyethylene substrate.
  • Perfect blownability means that the adhesive was deposited evenly with the same coating weight left to right on the substrate.
  • Perfect spiral means that the spiral is a wide and regular spiral of about 4 cm.

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

Abstract

Cette invention porte sur des compositions d'un adhésif thermofusible atomisable comportant un polymère d'éthylène ainsi qu'un monomère polaire et un agent collant.
PCT/EP1996/003858 1995-10-20 1996-09-02 Adhesif thermofusible atomisable a base d'ethylene WO1997015635A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9521499.5 1995-10-20
GBGB9521499.5A GB9521499D0 (en) 1995-10-20 1995-10-20 Sprayable ethylene based hot melt adhesives

Publications (1)

Publication Number Publication Date
WO1997015635A1 true WO1997015635A1 (fr) 1997-05-01

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000000564A1 (fr) * 1998-06-30 2000-01-06 H.B. Fuller Licensing & Financing, Inc. Adhesifs thermofusibles ameliores contenant une resine sensiblement aliphatique donnant du collant ayant une temperature de transition vitreuse elevee
US8119747B2 (en) 2003-08-19 2012-02-21 Dow Global Technologies Llc Interpolymers suitable for use in hot melt adhesives and processes to prepare the same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6735453B1 (en) 2000-07-25 2004-05-11 Plantronics, Inc. Automatic headset hookswitch

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991018043A1 (fr) * 1990-05-17 1991-11-28 E.I. Du Pont De Nemours And Company Adhesifs thermofusibles a base de terpolymeres d'ethylene
WO1992012212A1 (fr) * 1990-12-27 1992-07-23 Exxon Chemical Patents Inc. Composition d'adhesif thermofusible
US5310803A (en) * 1988-05-04 1994-05-10 Minnesota Mining And Manufacturing Company Hot-melt composition that have good open time and form creep-resistant bonds when applied in thin layers
WO1995013332A1 (fr) * 1993-11-10 1995-05-18 Minnesota Mining And Manufacturing Company Compositions thermoplastiques pulverisables

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5310803A (en) * 1988-05-04 1994-05-10 Minnesota Mining And Manufacturing Company Hot-melt composition that have good open time and form creep-resistant bonds when applied in thin layers
WO1991018043A1 (fr) * 1990-05-17 1991-11-28 E.I. Du Pont De Nemours And Company Adhesifs thermofusibles a base de terpolymeres d'ethylene
WO1992012212A1 (fr) * 1990-12-27 1992-07-23 Exxon Chemical Patents Inc. Composition d'adhesif thermofusible
WO1995013332A1 (fr) * 1993-11-10 1995-05-18 Minnesota Mining And Manufacturing Company Compositions thermoplastiques pulverisables

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000000564A1 (fr) * 1998-06-30 2000-01-06 H.B. Fuller Licensing & Financing, Inc. Adhesifs thermofusibles ameliores contenant une resine sensiblement aliphatique donnant du collant ayant une temperature de transition vitreuse elevee
US6833404B2 (en) 1998-06-30 2004-12-21 H.B. Fuller Licensing & Financing Inc. Hot melts utilizing a high glass transition temperature substantially aliphatic tackifying resin
US8119747B2 (en) 2003-08-19 2012-02-21 Dow Global Technologies Llc Interpolymers suitable for use in hot melt adhesives and processes to prepare the same
US8420742B2 (en) 2003-08-19 2013-04-16 Dow Global Technologies Llc Interpolymers suitable for use in hot melt adhesives and processes to prepare the same

Also Published As

Publication number Publication date
GB9521499D0 (en) 1995-12-20

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