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WO2002060993A1 - Adhesifs thermofusibles - Google Patents

Adhesifs thermofusibles Download PDF

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Publication number
WO2002060993A1
WO2002060993A1 PCT/US2002/001281 US0201281W WO02060993A1 WO 2002060993 A1 WO2002060993 A1 WO 2002060993A1 US 0201281 W US0201281 W US 0201281W WO 02060993 A1 WO02060993 A1 WO 02060993A1
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WO
WIPO (PCT)
Prior art keywords
hot melt
adhesive composition
melt adhesive
copolymer
composition
Prior art date
Application number
PCT/US2002/001281
Other languages
English (en)
Inventor
Joseph D. Domine
Jean M. Tancrede
Sally Q. Pugh
Original Assignee
Exxonmobil 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 Exxonmobil Chemical Patents Inc. filed Critical Exxonmobil Chemical Patents Inc.
Priority to US10/466,454 priority Critical patent/US6946528B2/en
Priority to JP2002561555A priority patent/JP2004525214A/ja
Priority to CNB028051335A priority patent/CN1320062C/zh
Priority to EP02707504A priority patent/EP1366120A4/fr
Publication of WO2002060993A1 publication Critical patent/WO2002060993A1/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
    • C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09J123/0869—Acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0853—Ethene vinyl acetate copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes

Definitions

  • the present invention is directed to hot melt adhesive compositions.
  • the invention provides copolymers of ethylene and alkyl acrylates or alkyl methacrylates suitable for use as hot melt adhesives, or as components of hot melt adhesive formulations.
  • the invention further provides articles of manufacture using such hot melt adhesives, such as cartons, cases, trays, books, assembled products, and disposables.
  • Hot melt adhesives are widely used in industry for various applications. Typical applications include product assembly, packaging such as case, carton or tray forming, and in glue sticks. Hot melt adhesives in use today are generally based on ethylene vinyl acetate copolymers (EVA) and low molecular weight polyethylene homopolymers (LMPE). Desirable properties in a hot melt adhesive include: (a) suitability for high temperature end use; (b) low temperature flexibility; (c) low viscosity; and (d) thermal stability, to name but a few. Conventional hot melt adhesives, however, typically lack one or more such properties. LMPE-based hot melt formulations can have good elevated temperature end use characteristics, but are undesirably brittle v at low temperatures. EVA copolymers are prone to char, skin or gel when exposed to elevated temperatures in the presence of air. In addition, EVA-based adhesives generally have poor elevated temperature performance.
  • EVA ethylene vinyl acetate copolymers
  • LMPE low molecular weight polyethylene homopoly
  • Ethylene acrylate copolymers available commercially today such as ethylene methyl acrylate or ethylene n-butyl acrylate copolymers, can be formulated to give hot melt adhesives that have good thermal stability and low temperature flexibility, but these formulations still lack in elevated temperature performance.
  • High temperature performance can be improved by addition of high melting point waxes, but such waxes significantly increase the cost of the adhesive.
  • novel copolymers are also suitable for glue stick formulations where improved heat resistance is difficult to achieve with conventional polymers. Further, the novel copolymers can be formulated as adhesive compositions that can be used in bookbinding and product assembly applications, and are readily sprayable for nonwoven applications.
  • the present invention provides a hot melt adhesive composition including a tubular reactor copolymer of ethylene and 5 to 20 mol % of comonomer units derived from an alkyl acrylate or alkyl methacrylate, wherein the copolymer has a melt index of at least 300 g/10 min.
  • the alkyl group of the alkyl acrylate or alkyl methacrylate can be a linear or branched, Ci to C 12 group, particularly n-butyl.
  • the hot melt adhesive can further include tackifiers, waxes, antioxidants and other desired additives.
  • the hot melt adhesive composition shows improved heat resistance and favorable properties, such as a shear adhesion fail temperature of at least 80 °C, and adhesive melt viscosity of less than 2200 cps at 180 °C.
  • the present invention provides a low-tackifier hot melt adhesive composition
  • the composition can further include waxes, antioxidants, and other desired additives.
  • the present invention provides a hot melt adhesive composition including a copolymer of ethylene and at least 5 mol % of comonomer units derived from an alkyl acrylate or alkyl methacrylate, wherein the copolymer has a melt index of from 1 to 10,000 g/10 min, and a maximum peak melting temperature of at least 100 °C.
  • the copolymer shows increased heat resistance as characterized by a temperature required to melt 50 % of the copolymer of at least 80 °C, a temperature required to melt 80 % of the copolymer of at least 100 °C, a temperature required to melt 100 % of the copolymer of at least 110 °C.
  • the hot melt adhesive composition can further include tackifiers, waxes, antioxidants, and other additives as desired.
  • the hot melt adhesive composition has a shear adhesion fail temperature of at least 80 °C, and an adhesive melt viscosity of less than 2200 cps at 180 °C.
  • the present invention provides articles such as cartons, cases, trays, bookbindings, or disposables including the hot melt adhesive compositions described herein.
  • the present invention provides a glue stick comprising the hot melt adhesive compositions described herein.
  • Figure 1 shows the peak melting temperature obtained by differential scanning calorimetry (DSC) for commercially available ethylene vinyl acetate (EVA) and ethylene methyl acrylate (EMA) copolymers, as a function of the comonomer content.
  • Figure 2 shows the peak melting temperature obtained by differential scanning calorimetry (DSC) for commercially available ethylene vinyl acetate (EVA) copolymers, as a function of the copolymer melt index.
  • Figure 3 shows a differential scanning calorimetry (DSC) profile of a tubular reactor-produced ethylene n-butyl acrylate copolymer, Resin 5, used to prepare invention adhesives and a conventional autoclave reactor-produced ethylene n-butyl acrylate copolymer, EN 33900.
  • DSC differential scanning calorimetry
  • Figure 4 shows the differential scanning calorimetry (DSC) thermograms for a copolymer used in the present invention (Resin 1) and a comparative non- inventive copolymer (Comparative Example G).
  • Figure 5 shows the differential scanning calorimetry (DSC) thermograms for the copolymer of Resin 2 compared to the peak melting temperature of a single-point tubular copolymer of approximately the same comonomer content (Comparative Example H).
  • Figure 6 shows the differential scanning calorimetry (DSC) thermograms for a copolymer used in the invention (Resin 3), other copolymers used in the invention (Resins 7 and 8) and a conventional autoclave copolymer (Comparative Example A).
  • DSC differential scanning calorimetry
  • the copolymers of the present invention are copolymers of ethylene and at least one comonomer, wherein the comonomer is an alkyl acrylate or alkyl methacrylate ester.
  • Suitable comonomers include the acrylic acid and methacrylic acid esters of CI to C12 linear or branched alcohols, preferably acrylic acid and methacrylic acid esters of CI to C8 linear or branched alcohols.
  • alkyl acrylate or alkyl methacrylate esters suitable for use as comonomers include methyl acrylate, ethyl acrylate, n-butyl acrylate, iso-butyl acrylate, t-butyl acrylate, n-hexyl acrylate, 2-ethylbutyl acrylate, and 2-ethylhexyl acrylate, as well as the acrylic acid esters of neo-isomers of C5 to C12 alcohols.
  • N-butyl acrylate is also a suitable comonomer.
  • the copolymer can contain at least 5 mol %, preferably from 5 mol % to 20 mol %, 5 mol % to 15 mol %, 6 mol % to 14 mol %, or 7 mol % to 12 mol % comonomer derived units.
  • the copolymer contains a lower limit of at least 5 mol % or at least 6 mol % or at least 7 mol % comonomer- derived units, and an upper limit of 20 mol % or 14 mol % or 12 mol % comonomer derived units, with ranges from any lower limit to any upper limit being contemplated.
  • copolymer can contain from 5-12; 5-14; 5-15; 5-20; 6-12; 6-14;
  • the alkyl acrylate or methacrylate ester monomers can be used alone or in mixtures. Monomers other than ethylene and the alkyl acrylate or alkyl methacrylate esters can optionally be included. These additional monomers include vinyl esters, such as vinyl acetate, and monomers such as acrylic acid, methacrylic acid, or partial esters of maleic acid, and carbon monoxide. Thus, as used herein the term "copolymer" includes polymers made from two, three, or more comonomers.
  • the copolymer includes ethylene; an alkyl acrylate or alkyl methacrylate, or mixtures thereof; and a comonomer having a reactivity ratio r relative to ethylene of 2 or less, or 1.5 or less, or 1.2 or less, or about 1.
  • exemplary comonomers having such a reactivity ratio include vinyl esters, such as vinyl acetate, vinyl formate, and vinyl propionate.
  • Reactivity ratios r are well known in the art, and are described, for example, in Encyclopedia of Polymer Science and Engineering, Vol. 6, p.401-403 (1986) (John Wiley, New York); and Encyclopedia of Chemical Technology, 4th Ed., Vol. 17, p. 718-719 (1996) (John Wiley, New York).
  • the ethylene alkyl acrylate or alkyl methacrylate copolymers used in the invention can be produced in a high pressure tubular reactor.
  • High pressure tubular reactors for producing ethylene alkyl acrylate or alkyl methacrylate ester copolymers are well known; see, e.g., U.S. Patent No. 2,953,551.
  • the present invention is not limited to resins made in any specific tubular reactor design, operating pressure or temperature variables, or initiator system, provided that the tubular reactor is capable of injection of initiator into the reaction stream at least two, at least three, or at least four locations along the reaction tube.
  • tubular ethylene alkyl acrylate or alkyl methacrylate copolymer means a copolymer produced in such a multi-initiator- injection, high pressure tubular reactor.
  • the tubular reactor may be an elongated jacketed tube or pipe, usually in sections or blocks, of suitable strength and diameter.
  • a typical tubular reactor can have a length-to-diameter-ratio of from about 1000 to 1 to about 60,000 to 1.
  • the tubular reactor is typically operated at pressures from about 1000 to 3500 bar, although pressures higher than 3500 bar can be used if desired.
  • the temperature maintained in the reactor is variable, and is primarily controlled by and dependent on the specific initiator system employed. Temperatures are usually within the range of about 100 °C to 350 °C, and can vary in the different reaction zones.
  • An example of a high pressure tubular reactor suitable for use in producing the ethylene alkyl acrylate or alkyl methacrylate copolymers of the invention is shown in U.S. Patent No. 4,135,044. If the reactor shown in U.S. Patent No.
  • the polymerization reaction is carried out in the presence of free radical initiators.
  • free radical initiators include oxygen; peroxide compounds such as hydrogen peroxide, decanoyl peroxide, t-butyl peroxy neodecanoate, t-butyl peroxypivalate, 3,5,5-trimethyl hexanoyl peroxide, diethyl peroxide, t-butyl peroxy-2-ethyl hexanoate, t-butyl peroxy isobutyrate, benzoyl peroxide, t-butyl peroxy acetate, t-butyl peroxy benzoate, di-t-butyl peroxide, t-amyldecanoate, t- amylpivalate, t-amylperoctoate and 1,1,3,3-tetramethyl butyl hydroperoxide; alkali metal persulfates, perborates
  • Organic peroxides function as initiators. Mixtures of such initiators can also be used, and different initiators and/or different initiator mixtures can be used in the different initiator injections.
  • the initiator can be added to the reaction stream in any suitable manner, such as neat, dissolved in a suitable solvent, and/or mixed with the monomer or comonomer feed stream.
  • an initiator is injected into the reaction stream at least two, at least three, or least four locations.
  • monomers and comonomers are introduced into the tubular reactor at a single location, so that injection of additional initiator at second, third, fourth, and subsequent locations, is not accompanied by injection of any additional monomer or comonomer.
  • chain transfer agents include non-copolymerizable chain transfer agents: saturated aliphatic aldehydes, such as formaldehyde and acetaldehyde; saturated aliphatic ketones, such as acetone, diethyl ketone and diamyl ketone; saturated aliphatic alcohols, such as methanol, ethanol and propanol; paraffins and cycloparaffins such as pentane, hexane and cyclohexane; aromatic compounds, such as toluene, diethylbenzene and xylene; and other compounds which act as chain terminating agents such as propylene, carbon tetrachloride and chloroform.
  • Non-copolymerizable chain transfer agents such as, acetaldehyde function in this invention.
  • Alkyl acrylate or alkyl methacrylate comonomer content of from 5- 20 mol %. These mole percents represent the moles of alkyl acrylate or alkyl methacrylate comonomer-derived units in the copolymer as a percentage of the total number of moles of monomer-derived and comonomer-derived units in the copolymer. When more than one alkyl acrylate or alkyl methacrylate comonomer is used, the 5-20 mol % amount represents the total amount of all of the alkyl acrylate and alkyl methacrylate comonomer content.
  • alkyl acrylate or alkyl methacrylate comonomer-derived unit content can be at least 6%, at least 7%, at least 8%, at least 9% or at least 10% (mole percents). It is a particular feature of the copolymers of the present invention that relatively large amounts of alkyl acrylate or alkyl methacrylate comonomer can be incorporated in the copolymer while still maintaining the described properties.
  • the copolymers of the present invention preferably include at least 2 mol % or at least 3 mol % or at least 4 mol % of the alkyl acrylate or alkyl methacrylate comonomer, and at least 0.5 mol % or at least 1 mol % or at least 1.5 mol % of the comonomer having a reactivity ratio r relative to ethylene of 2 or less, with the total comonomer content being as described above.
  • melt index in g/10 min of 1 to 10,000.
  • Alternative lower limits of the melt index can be at least 100 g/10 min, at least 300 g/10 min, at least 600 g/10 min, at least 900 g/10 min, at least 1500 g/10 min, at least 2500 g/10 min, or at least 5000 g/10 min.
  • melt index, in g/10 min can fall within the following ranges: 100-10,000; 300-10,000; 600-10,000; 900-10,000; 1500-10,000; 2500-10,000; or 5,000- 10,000 g/10 min.
  • the copolymers of the present invention show a percent melted at
  • Heat resistance Temperature at % melted.
  • An alternate measure of heat resistance is the temperature required to melt a predetermined percentage of the copolymer, and this temperature can be measured by DSC.
  • the copolymers of the present invention show increased heat resistance over conventional comparable copolymers, as shown in the Examples herein; i.e., a higher temperature is required to melt a given percentage of the copolymer.
  • the temperature required to melt 50% of a sample of the copolymers of the present invention can be at least 80 °C, preferably at least 85 °C, and more preferably at least 90 °C.
  • the temperature required to melt 80%) of a sample of the copolymers of the present invention can be at least 100 °C, preferably at least 105 °C.
  • the temperature required to melt 100% of a sample of the copolymers of the present invention can be at least 110 °C, preferably at least 115 °C, and more preferably at least 120 °C.
  • the temperature required to melt 50%) of a sample of the copolymers of the present invention can be at least 40 °C or at least 50 °C or at least 60 °C; the temperature required to melt 80%) of a sample of the copolymers of the present invention can be at least 70 °C or at least 80 °C or at least 85 °C; and the temperature required to melt 100%) of a sample of the copolymers of the present invention can be at least 80 °C or at least 90 °C or at least 100 °C.
  • Vicat Softening Point Another measure of the higher heat resistance of copolymers the present invention is shown by the Vicat Softening
  • copolymers of the present invention can have a Vicat Softening Point of at least 45 °C, preferably at least 50 °C, more preferably at least 55 °C, and still more preferably at least 60 °C.
  • copolymers of the present invention can have a Vicat Softening Point of at least 30 °C or at least 35 °C or at least 40 °C.
  • copolymers the present invention show a higher peak melting point, determined by DSC, relative to conventional copolymers having the same overall composition.
  • copolymers of the present invention can have a peak melting point of at least 100 °C, at least 105 °C, or at least 1 10 °C.
  • the copolymers of the present invention can have a peak melting point at least 25 °C, at least 35 °C , or at least 50 °C greater than the peak melting temperature of a uniformly homogeneous copolymer of the same chemical composition, such as those produced in autoclave reactor products.
  • copolymers of the present invention can have a peak melting point of at least 80 °C or at least 90 °C or at least 95 °C.
  • peak melting point As used herein and in the appended claims, the term “peak melting point”, “Tm” and “maximum peak melting temperature” refer to the temperature of the peak having the highest melting temperature, such as, for example, the 111.5 °C peak of Resin 2. It should be noted in this connection that the maximum peak melting temperature can be located on a peak that appears on the DSC trace to be a higher temperature shoulder on a larger peak, such as, for example, the maximum peak melting temperature of 99.86 °C for Resin 8, shown in Figure 6.
  • tackifier and “tackifying resin” are used synonymously to include hydrocarbon resins, synthetic polyterpenes, rosin esters and natural terpenes which are semi-solid at ambient temperatures, and soften or liquefy at temperatures ranging generally from about 50 °C to about 140°C, preferably from about 85 °C to about 120 °C.
  • tackifying resins are compatible resins such as: (1) natural and modified rosins, such as gum rosin, wood rosin, tall oil rosin, distilled rosin, hydrogenated rosin, dimerized rosin, and polymerized rosin;
  • glycerol and pentaerythritol esters of natural and modified rosins such as the glycerol ester of pale, wood rosin, the glycerol ester of hydrogenated rosin, the glycerol ester of polymerized rosin, the pentaerthritol ester of hydrogenated rosin, and the phenolic modified pentaerythritol ester of rosin;
  • copolymers of natured terpenes such as styrene/te ⁇ ene and alpha methyl styrene/te ⁇ ene;
  • polyte ⁇ ene resins having a softening point, as determined by ASTM method E28-58T, of from about 50-150 °C, such resins generally resulting from the polymerization of te ⁇ ene hydrocarbons, such as the bicyclic monote ⁇ ene known as pinene, in the presence of Friedel- Crafts catalysts at moderately low temperatures; the hydrogenated polyte ⁇ ene resins are also included;
  • phenolic modified te ⁇ ene resins and their hydrogenated derivatives such as the resin product resulting from the acid medium condensation, of a bicyclic te ⁇ ene and a phenol;
  • aliphatic petroleum resins having a Ball and Ring Softening Point of from 50-135 °C, resulting from polymerization primarily olefins and diolefins; also included are the hydrogenated aliphatic petroleum hydrocarbon resins;
  • tackifying resins are those species named above that are liquid at room temperature.
  • the tackifier is present in an amount of from 5 to
  • the tackifier can be present in an amount of at least 10 percent, or at least 15 % by weight, or less than 40 %>, less than 30 %, or less than 20 % by weight. Ranges from any of the lower limits to any of the upper limits are also within the scope of the invention. That is, tackifier can be present at 5-20%; 5-30%; 5-40%; 5-60%;
  • the tackifier is present at less than 15% by weight.
  • the tackifier can be present in amounts of 1% or 5% to 10%) or 15%, with ranges from any of the lower limits to any of the upper limits also being within the scope of the invention: 1-10; 1-15; 5-10; or 5-15% by weight.
  • the present invention provides adhesive compositions without the need for tackifiers.
  • Some embodiments of the invention include waxes.
  • the optional waxes can be included to further reduce viscosity and to alter adhesive open and set times.
  • Suitable waxes include paraffin waxes, microcrystalline waxes, high density low molecular weight polyethylene waxes, by-product polyethylene waxes, Fischer-Tropsch waxes, oxidized Fischer-Tropsch waxes, and hydroxy stearamide waxes.
  • synthetic high melting point wax is commonly used to refer to high density low molecular weight polyethylene waxes, by-product polyethylene waxes, and Fischer-Tropsch waxes, and these synthetic high melting point waxes are suitable.
  • the present invention provides adhesive compositions that can have the desired viscosity and other properties without the need for expensive, high melting point waxes.
  • the amount of wax used will depend upon the properties desired, and the particular wax chosen, but is generally 0-20%) or 5- 20; 0-15; or 5-15%> by weight, based on the total weight of the composition.
  • Hot melt adhesive compositions of the invention can also use a variety of other additives commonly used in the art, such as plasticizers, stabilizers, antioxidants, pigments, and the like.
  • Liquid plasticizers such as oils, and solid plasticizers such as benzoate esters available from Velsicol Chemical Co ⁇ . in Rosemont, 111 under the trade name Benzoflex, can be used to obtain longer open times, lower viscosity, improved adhesion and improved cold temperature flexibility.
  • Plasticizing oils that have been found useful include olefin oligomers and low molecular weight polymers, as well as vegetable and animal oils and their derivatives.
  • Suitable petroleum-derived oils are relatively high boiling point materials containing only a minor proportion of aromatic hydrocarbons, preferably less than 30%, and more preferably less than 15%> by weight of the oil. Alternatively, the oil may be essentially free of aromatics.
  • a stabilizer or antioxidant is also preferably used in hot melt adhesives.
  • antioxidants are commercially available from Ciba Geigy located in Hawthorne, N.Y., and include Irganox 565, Irganox 1010, and Irganox 1076, which are hindered phenolic antioxidants. These primary antioxidants act as free radical scavengers and may be used alone or in combination with other antioxidants such as phosphite antioxidants. Phosphite antioxidants are considered secondary antioxidants, and are not generally used alone; these secondary antioxidants are primarily used as peroxide decomposers. Many other antioxidants are available for use by themselves, or in combination with other antioxidants, and are well- known in the art. These antioxidants are typically used in amounts of 0 to 2%> by weight.
  • the hot melt adhesive compositions described herein can be prepared using conventional methods well known in the art.
  • the polymer, tackifier, and desired optional ingredients such as plasticizer oil, wax, liquid resin tackifiers, etc.
  • Mixing temperatures depend upon the particular adhesive formulation, and are generally in the range of 130 °C - 200 °C, with about 150 °C to about 160 °C being a typical suitable range.
  • Other embodiments use mixing temperatures selected from the following ranges; 130- 160; 130-200; 150-160; and 150-200 °C.
  • tubular reactor ethylene alkyl acrylate or alkyl methacrylate copolymers themselves are suitable for use as hot melt adhesives, without the need to inco ⁇ orate additional components. It should be understood that for these "neat" copolymer adhesives, the term "adhesive composition" is still used, although the composition may contain only a single component, and optionally conventional additives.
  • Hot melt adhesives of the invention are particularly well-suited to various applications, such as, but not limited to:
  • packaging applications such as forming cases, cartons, trays and the like, and/or sealing such cases, cartons or trays;
  • the present invention is directed to an article having a first surface and a second surface at least a portion of which is adhered to the first surface by any of the hot melt adhesives described herein.
  • the article can be, for example, a case, a carton or a tray, wherein the hot melt adhesive is used to adhere one or more surfaces to form the case, carton or tray, or to close the case carton or tray; a book, wherein the hot melt adhesive is used as a bookbinding adhesive; or a product in which the hot melt adhesive is used as a product assembly adhesive.
  • Such products can include, for example, disposables.
  • the hot melt adhesives of the present invention can be used in glue stick formulations where the improved heat resistance of such hot melt adhesives is advantageous.
  • the present invention provides a glue stick, the glue stick including a hot melt adhesive composition as described above.
  • the hot melt adhesives described herein may be applied using conventional technology, such as piston or gear pump extrusion equipment, or wheel applicators. Examples of such equipment are those manufactured by Nordson, ITW Dynatec, and Slauterback.
  • the hot melt adhesives can also be applied using air assisted extrusion applicators such as spiral, random or melt blown spray patterns. Such equipment is available from Nordson, J and M, and ITW Dynatec.
  • the particular method of application will depend upon various factors well understood in the art, such as the article to which the adhesive is applied, and the conditions under which the adhesive or article needs to function. Application of hot melt adhesives by any such conventional techniques is well within the understanding of one skilled in the art.
  • the adhesive compositions of the present invention are suitable for other process applications.
  • the present invention provides adhesive compositions that have a low application temperature.
  • the present invention provides adhesive compositions that can have a melt viscosity of less than 3300 cps at 140 °C while still possessing good adhesion properties and good heat resistance as shown, for example, by Example 3 below.
  • the present invention provides sprayable adhesive compositions.
  • the present invention provides adhesive compositions that do not require a tackifier (e.g., the copolymer itself, or formulated with other, non-tackifier additives), or use only a relatively small amount of tackifier, such as adhesive compositions with less than 20% tackifier by weight.
  • a tackifier e.g., the copolymer itself, or formulated with other, non-tackifier additives
  • the example hot melt adhesive compositions were prepared by blending all of the components under low or high shear mixing at elevated temperatures to form a fluid melt. Mixing temperatures can vary from about 130 °C to about 200 °C, generally from about 150 °C to about 160 °C.
  • Bond specimens were peeled back in a tensile tester at a constant crosshead speed of 2 in/min (51 mm/min). The average force required to peel the bond (5 specimens) apart was recorded.
  • SAFT Shear Adhesion Fail Temperature
  • (g) Melt Index determined according to ASTM D-1238, with the following exceptions and clarifications. For samples with Mis of less than about 100 g/10 min, condition 190/2.16 of the ASTM method is used. For samples with Mis greater than about 100 g/10 min, the reported MI is based on a mathematical equation used to correlate data from condition 125/0.325 to condition 190/2.16. For those samples, the time needed for the piston to travel 25.4 mm at a melt temperature of 125 °C and 0.325 kg load is determined and used in the equation below to calculate the logarithm of a melt flow rate at 190 °C and 2.16 kg; the antilog of this value is reported as the Melt Index:
  • DSC Differential Scanning Calorimetry
  • the adhesive examples are made using several are ethylene n-butyl acrylate (EnBA) copolymers produced in a tubular reactor by ExxonMobil Chemical Company located in Houston, TX.
  • Ethylene n-butyl acrylate copolymers of the present invention were produced in a high pressure tubular reactor similar in design to the tubular reactor disclosed in U.S. Patent No. 4,135,044, but without side-streams feeding the reactor.
  • the monomers were of conventional, commercial purity and there were no efforts to increase purity or modify them in any way.
  • the n-butyl acrylate monomer was not stripped of oxygen or storage stabilizer.
  • the polymerization was initiated using the following mixture of initiators at the indicated amounts by weight: t-amylperoxyneodecanoate, 39.5%>, t-amyl peroxypivalate, 23.7%>, and t-amyl peroxy-2-ethylhexanoate, 36.8%. These were dissolved in a hydrocarbon solvent at 34.3 wt % initiator mixture to 65.7 wt %> solvent.
  • Reactor throughput was held constant at 18.5 metric tons/hour. Reactor conditions and production results are shown in Table 1 below. Throughout the campaign, no significant reactor or pre-heater fouling was apparent. In Table 1 , “LPS” and “HPS” indicate the low pressure separator and the high pressure separator, respectively. The tubular reactor was configured for either 3-point initiator injection or 4-point initiator injection. The dashed lines “— " in Table 1 indicate runs in which only 3-point initiation injection was used. The total initiator feed to the downstream injection points is given in Table 1 below. Initiator feed to each of the individual downstream injection points was apportioned between all of them to get the indicated peak temperatures.
  • Acetaldehyde was used as the chain transfer agent for all these samples.
  • the concentration of n-butyl acrylate in the Example copolymers was checked during the run for the pu ⁇ ose of process control by the plant Quality Control Laboratory using an FTIR method they had developed and use routinely for autoclave polymerized ethylene n-butyl acrylate copolymer made at the same plant. This method requires appropriate calibration standards to yield correct values.
  • the comonomer contents of the Example copolymers were also subsequently determined by proton NMR as described above, and lower values were obtained. Proton NMR is an absolute analytical method that does not require any calibration standards to determine correct values. The difference in values determined by the two methods indicates that the more crystalline tubular reactor copolymers of the present invention have infrared absorbance characteristics which are different than those characteristics of conventional autoclave-produced ethylene n-butyl acrylate copolymers.
  • Initiator Feed Rate Sum of 19.4 19.4 19.4 23.4 25.2
  • Resins contain relatively high levels of n-butyl acrylate comonomer, from about 7 mol % to over 10 mol %.
  • Melt index ranged from a low of about 364 g/10 min to over an estimated 2500; melt viscosity at 190°C was used in place of melt index for the grades with greater than 330 MI. Melt viscosity ranged from as high as about 48,000 mPa-s to as low as about 2400 mPa-s.
  • the composition, melt viscosity (or melt index I 2. ⁇ 6 ) and density of the copolymers, labeled as Resins 1-5, are shown in Table 2.
  • the Resins 1-5 were used to prepare a series of hot melt adhesives in accordance with the present invention.
  • ESCOREZ 2596 is an aromatic-modified aliphatic resin available from ExxonMobil Chemical Company.
  • ESCOREZ 5600 is a hydrogenated aromatic-modified cycloaliphatic tackifier also available from ExxonMobil Chemical Company.
  • SYLVALITE RE 100 is a tall oil rosin ester available from Arizona Chemical located in Panama City, FL.
  • PARAFLINT HI is a Fischer-
  • IRGANOX 1010 is a hindered phenolic antioxidant available from Ciba-Geigy Co ⁇ oration located in Hawthorne, NY.
  • KAYDOL is a white mineral oil available from Witco Co ⁇ oration located in Greenwich, CT.
  • ENABLE EN 33330 (33 wt. % nBA; 330 MI) and EN 33900 (33 wt nBA; 8,300 cps @ 190°C) are EnBA copolymers produced in an autoclave reactor by ExxonMobil Chemical Company.
  • the MI value for ENABLE EN 33900 is estimated to about 900.
  • ESCORENE 7710 (28 wt % VA; 420 MI), ESCORENE MV 02528 (28 wt % VA; 3,100 cps @ 190°C) and MV 02520 (20 wt % VA; 3,200 cps @ 190°C) are ethylene vinylacetate copolymers available from ExxonMobil Chemical Company. MI values of EVA copolymers like
  • ESCORENE MV 02520 and MV 02528 are generally not measured but have been estimated to be approximately 2500 based on their melt viscosity at 190°C.
  • EPOLENE CIO is a low molecular weight polyethylene homopolymer (2250 MI) available from Eastman Chemical Co. located in Kingsport, TN. Formulations used to make comparative Examples A through G are shown in Table 7.
  • composition A B C D Composition A B C D
  • Figure 7 shows a differential scanning calorimetry (DSC) profile of the tubular reactor-produced ethylene n-butyl acrylate copolymer RESIN 4 (as in Table 1) and the conventional autoclave reactor-produced ethylene n-butyl acrylate copolymer EN 33900.
  • DSC differential scanning calorimetry
  • the novel copolymer of the present invention shows a peak melting temperature more than 50 degrees higher than the conventional copolymer, even though the two polymers have approximately the same n-butyl acrylate comonomer content (32 wt % and 33 wt %, respectively) and similar viscosities (about 11,000 and 8,000 cps at 190 °C, respectively).
  • Comparative Example A represents a conventional EVA-based hot melt adhesive used for case and carton sealing and for tray forming.
  • the comparative Example B and C hot melt adhesives are based on EnBA copolymers produced in an autoclave.
  • Examples 2 and 3 which contain EnBA copolymers of the invention produced in a tubular reactor, have superior elevated temperature performance (SAFT) than comparative Examples A-C while maintaining the good low temperature properties of the autoclave-produced EnBA counte ⁇ arts.
  • SAFT elevated temperature performance
  • the adhesion performance of Examples 2 and 3 is comparable to comparative Example A.
  • Examples 1 and 10-13 also provide comparable elevated temperature performance as compared to Examples 4-9, as well as good low temperature adhesion to Kraft paper.
  • Examples 4-9 are based on the low viscosity, high MI EnBA copolymers made in a tubular reactor. These tubular EnBA copolymers differ primarily in n- butyl acrylate comonomer content.
  • Examples 7, 8, and 9 are blended with different types of tackifiers, namely aliphatic, hydrogenated aromatic-modified cycloaliphatic, and tall oil rosin ester, respectively. Comparative Examples D and
  • Comparative Example F represents a hot melt packaging formulation based on a low molecular weight polyethylene homopolymer. Note the superior elevated temperature performance of the tubular
  • Example F Comparative Example F also has poor low-temperature performance versus the Examples of this invention.
  • tubular EnBA copolymers retain the advantageous attributes of EnBA copolymers made in an autoclave (adhesion, stability, low temperature adhesion) while su ⁇ risingly improving the elevated temperature performance. These high MI tubular EnBA copolymers can be formulated for low application temperatures by one skilled in the art.
  • Example 13A
  • a further sample 13A was made with 50% by weight RESIN 3, 30% ESCOREZ 5600 and 20%> Kaydol oil.
  • Resins 6-11 the monomer mixture included ethylene, n-butyl acrylate and vinyl acetate.
  • the process conditions are shown in Table 9.
  • the reactor throughput was 21.3-23.0 metric tons per hour.
  • IRGANOX 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 1010
  • Table 12 many other tackifier compositions can be used to formulated EnBAVA copolymer adhesive systems.
  • Tall Oil Rosen Esters give good adhesion properties but the adhesive itself remains cloudy over a broad temperature range.
  • Cloud Point 95 140 160 95 102 115 200+ (°C)

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

Abstract

L'invention concerne une composition d'adhésif thermofusible comprenant un copolymère de réacteur tubulaire d'éthylène et entre 5 et 20 % d'unités comonomères dérivées d'un acrylate d'alkyle ou d'un méthacrylate d'alkyle, ce copolymère présentant un indice de fusion d'au moins 300g/10 min. Le groupe alkyle de l'acrylate d'alkyle ou du méthacrylate d'alkyle peut être un groupe C1 à C12 linéaire ou ramifié, et notamment un groupe n-butyle. Si nécessaire, cet adhésif thermofusible peut également comprendre des agents poisseux, des cires, des antioxydants et d'autres additifs souhaités. Ladite composition d'adhésif thermofusible présente une résistance à la chaleur accrue et des propriétés améliorées, et notamment une température de défaut d'adhérence par cisaillement d'au moins 80 °C, sans qu'il soit nécessaire d'utiliser des cires à point de fusion élevé. L'invention concerne également des produits tels que des cartons, des boîtes, des plateaux, des reliures ou des articles jetables comprenant ces compositions d'adhésif thermofusible.
PCT/US2002/001281 2001-01-19 2002-01-18 Adhesifs thermofusibles WO2002060993A1 (fr)

Priority Applications (4)

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US10/466,454 US6946528B2 (en) 2001-01-19 2002-01-18 Hot melt adhesives
JP2002561555A JP2004525214A (ja) 2001-01-19 2002-01-18 ホットメルト接着剤
CNB028051335A CN1320062C (zh) 2001-01-19 2002-01-18 热熔粘合剂
EP02707504A EP1366120A4 (fr) 2001-01-19 2002-01-18 Adhesifs thermofusibles

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US60/263,002 2001-01-19
US60/263,000 2001-01-19

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Cited By (7)

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Publication number Priority date Publication date Assignee Title
JP2005036067A (ja) * 2003-07-17 2005-02-10 Tosoh Corp ホットメルト接着剤
WO2005037539A1 (fr) * 2003-10-17 2005-04-28 E.I. Dupont De Nemours And Company Adhesion d'une feuille de metal a des polymeres thermoplastiques
EP1675927B1 (fr) * 2003-09-03 2010-02-17 H.B. Fuller Licensing & Financing, Inc. Composition et procede associes a un adhesif thermofusible
WO2011129926A1 (fr) * 2010-04-13 2011-10-20 Exxonmobil Chemical Patents Inc. Compositions adhésives et procédés
EP1811114B2 (fr) † 2006-01-19 2016-06-01 Thiele Glas GmbH Coin entièrement en verre isolant
WO2018115789A1 (fr) * 2016-12-22 2018-06-28 Arkema France Utilisation d'un copolymère éthylène-acrylate de butyle particulier dans une composition adhésive thermofusible transparente à l'état fondu
US10669423B2 (en) 2015-08-07 2020-06-02 Performance Materials Na, Inc. Modified asphalt using phosphorous acid

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US5500472A (en) * 1995-02-17 1996-03-19 National Starch And Chemical Investment Holding Corporation Low application temperature hot melt adhesive
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005036067A (ja) * 2003-07-17 2005-02-10 Tosoh Corp ホットメルト接着剤
JP4655186B2 (ja) * 2003-07-17 2011-03-23 東ソー株式会社 ホットメルト接着剤
EP1675927B1 (fr) * 2003-09-03 2010-02-17 H.B. Fuller Licensing & Financing, Inc. Composition et procede associes a un adhesif thermofusible
WO2005037539A1 (fr) * 2003-10-17 2005-04-28 E.I. Dupont De Nemours And Company Adhesion d'une feuille de metal a des polymeres thermoplastiques
AU2004281270B2 (en) * 2003-10-17 2010-05-06 E.I. Dupont De Nemours And Company Adhesion of foil to thermoplastic polymers
US8137776B2 (en) 2003-10-17 2012-03-20 E.I. Du Pont De Nemours And Company Lamination adhesion of foil to thermoplastic polymers
EP1811114B2 (fr) † 2006-01-19 2016-06-01 Thiele Glas GmbH Coin entièrement en verre isolant
WO2011129926A1 (fr) * 2010-04-13 2011-10-20 Exxonmobil Chemical Patents Inc. Compositions adhésives et procédés
US9260636B2 (en) 2010-04-13 2016-02-16 Exxonmobil Chemical Patents Inc. Adhesive compositions and methods
US10669423B2 (en) 2015-08-07 2020-06-02 Performance Materials Na, Inc. Modified asphalt using phosphorous acid
WO2018115789A1 (fr) * 2016-12-22 2018-06-28 Arkema France Utilisation d'un copolymère éthylène-acrylate de butyle particulier dans une composition adhésive thermofusible transparente à l'état fondu
FR3061192A1 (fr) * 2016-12-22 2018-06-29 Arkema France Utilisation d'un copolymere ethylene-acrylate de butyle particulier dans une composition adhesive thermofusible transparente a l'etat fondu

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