WO2022181765A1 - Composition adhésive thermoplastique - Google Patents

Composition adhésive thermoplastique Download PDF

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Publication number
WO2022181765A1
WO2022181765A1 PCT/JP2022/007882 JP2022007882W WO2022181765A1 WO 2022181765 A1 WO2022181765 A1 WO 2022181765A1 JP 2022007882 W JP2022007882 W JP 2022007882W WO 2022181765 A1 WO2022181765 A1 WO 2022181765A1
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Prior art keywords
component
adhesive composition
thermoplastic adhesive
weight
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PCT/JP2022/007882
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English (en)
Japanese (ja)
Inventor
孝介 森谷
麻希 佐見津
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株式会社Moresco
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Publication of WO2022181765A1 publication Critical patent/WO2022181765A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation
    • 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
    • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms

Definitions

  • Metallocene-based polyolefin is a hard material. Therefore, a thermoplastic adhesive containing a metallocene-based polyolefin has a problem of poor adhesiveness to polyethylene, which is a soft material. Even in the prior art described above, there is still room for improvement in the adhesiveness to polyethylene.
  • An object of one aspect of the present invention is to improve adhesion to polyethylene in a thermoplastic adhesive composition containing a metallocene-based polyolefin.
  • thermoplastic adhesive composition comprising the following component A, component B1 and component C, and optionally containing 1 part by weight or less of component B2 below (provided that the total weight of the thermoplastic adhesive composition is 100 parts by weight),
  • Component A metallocene-based polyolefin;
  • Component B1 one or more resins selected from polybutene and its hydrides, polybutadiene, polyisobutylene and its hydrides, and polyisoprene;
  • Component B2 oil;
  • Component C tackifying resin;
  • the component A contains a polypropylene resin,
  • the thermoplastic adhesive composition, wherein the polypropylene-based resin has a crystal melting endotherm of 80 g/J or less.
  • thermoplastic adhesive composition according to ⁇ 1> containing 3 to 50 parts by weight of component A.
  • component B1 contains one or more resins selected from polybutene and hydrides thereof.
  • thermoplastic adhesive composition according to any one of ⁇ 1> to ⁇ 6>, containing 20 parts by weight or more of Component C.
  • ⁇ 8> An article in which a first adherend and a second adherend are bonded via an adhesive layer, An article, wherein the adhesive layer comprises the thermoplastic adhesive composition according to any one of ⁇ 1> to ⁇ 7>.
  • ⁇ 9> The article according to ⁇ 8>, wherein at least one of the first adherend and the second adherend contains a polyethylene-based resin.
  • ⁇ 11> forming an adhesive layer adjacent to the first adhesive surface; a step of bringing a second adhesive surface into contact with the adhesive layer so as to face the first adhesive surface through the adhesive layer;
  • An adhesion method comprising A method, wherein the adhesive layer comprises the thermoplastic adhesive composition according to any one of ⁇ 1> to ⁇ 7>.
  • ⁇ 12> The method according to ⁇ 11>, wherein at least one of the first adhesive surface and the second adhesive surface contains a polyethylene-based resin.
  • thermoplastic adhesive composition containing a metallocene-based polyolefin has improved adhesion to polyethylene.
  • thermoplastic adhesive composition is expressed in parts by weight (the total weight of the thermoplastic adhesive composition is 100 parts by weight).
  • the thermoplastic adhesive composition according to one aspect of the present invention comprises component A: metallocene-based polyolefin, and component B1: one selected from polybutene and its hydrides, polybutadiene, polyisobutylene and its hydrides, and polyisoprene. It contains the above resins and Component C: a tackifying resin.
  • Component A contains a polypropylene-based resin, and the crystalline melting endotherm of this polypropylene-based resin is 80 J/g or less.
  • This thermoplastic adhesive composition may optionally contain component B2: oil in an amount of 1 part by weight or less.
  • the thermoplastic adhesive composition may contain component D1: amorphous polyolefin and/or component D2: rubber.
  • thermoplastic adhesive composition has a base polymer, a softening agent and a tackifying resin as main components.
  • Component A corresponds to the base polymer
  • Components B1 and B2 correspond to the softeners
  • Component C corresponds to the tackifying resin.
  • One aspect of the present invention has the effect of improving adhesion to polyethylene by using a softening agent that satisfies specific conditions in a thermoplastic adhesive composition that uses a metallocene-based polyolefin as a base polymer.
  • the component A contains a polypropylene-based resin having a crystal melting endotherm of 80 J/g or less, stable coating of the thermoplastic adhesive composition becomes possible.
  • Component A is a metallocene-based polyolefin.
  • a metallocene-based polyolefin represents a polymer obtained by polymerizing an olefin in the presence of a metallocene catalyst.
  • Component A contains a polypropylene resin.
  • the polypropylene-based resin may be in the form of wax.
  • Component A may contain a polypropylene wax.
  • Component A may contain metallocene-based polyolefins other than polypropylene-based resins.
  • polyolefins other than polypropylene resins include polyethylene resins, polybutene resins, and poly ⁇ olefin resins.
  • a polypropylene-based resin is a resin having units derived from propylene. Propylene-derived units may account for 50% or more, 70% or more or 90% or more of the total units. Specific examples of polypropylene-based resins include polypropylene homopolymers and propylene/ ⁇ -olefin copolymers (propylene/ethylene copolymers, propylene/butene copolymers, etc.).
  • component A may contain a metallocene polypropylene wax.
  • Wax refers to a low-molecular-weight resin that is solid at room temperature and becomes liquid when heated.
  • the wax has a weight average molecular weight of less than 40,000 and a weight average molecular weight of 300 or more, or 500 or more. Weight average molecular weight can be measured by high temperature gel permeation chromatography (high temperature GPC).
  • the metallocene-based polyolefin may be an acid-modified polyolefin.
  • the acid-modified polyolefin resin is a resin obtained by subjecting a polyolefin to a graft reaction and/or an addition reaction with an unsaturated carboxylic acid or a derivative thereof.
  • an acid-modified polyolefin can be synthesized by heating and mixing an unsaturated carboxylic acid or a derivative thereof and a polyolefin in the presence of a radical generator.
  • unsaturated carboxylic acids or derivatives thereof include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, derivatives thereof, and mixtures thereof.
  • unsaturated monocarboxylic acids include acrylic acid and methacrylic acid.
  • unsaturated dicarboxylic acids include maleic acid and fumaric acid.
  • derivatives of unsaturated carboxylic acids include anhydrides, esters and metal salts (sodium, potassium, calcium salts, etc.). Among these, unsaturated dicarboxylic acids are preferred, and one or more selected from the group consisting of maleic acid, maleic anhydride, maleic acid esters and maleic acid metal salts is more preferred.
  • Component A contains a maleic acid-modified propylene-based resin.
  • a maleic acid-modified propylene-based resin is a resin obtained by modifying a propylene-based resin with maleic acid or maleic anhydride.
  • a conventionally known method can be employed for this modification treatment. For example, a method of kneading a propylene-based resin, maleic acid or maleic anhydride, and a peroxide using a kneading extruder to cause a graft reaction can be mentioned.
  • the maleic acid modification rate of the maleic acid-modified propylene resin is preferably 0.1 to 10% by weight in terms of maleic acid groups.
  • component A contains a polypropylene resin (including acid-modified polypropylene).
  • the proportion of polypropylene resin in component A is, for example, 50% by weight or more, 70% by weight or more, or 90% by weight or more.
  • component A consists entirely of polypropylene-based resin.
  • the upper limit of the crystal melting endothermic amount of the polypropylene resin contained in component A is preferably 80 J/g or less, more preferably 75 J/g or less, and even more preferably 70 J/g or less.
  • the lower limit of the crystal melting endotherm is not particularly limited, it may be 0 J/g or more or 5 J/g or more. If the crystal melting endotherm is within the above range, the thermoplastic adhesive composition can be stably applied.
  • the crystal melting endotherm is measured by scanning calorimetry (DSC) in accordance with JIS K7122.
  • amorphous polypropylene resins do not show a clear peak in scanning calorimetry (DSC) in accordance with JIS K7122, and the crystalline melting endotherm cannot be measured.
  • the amount of heat absorbed should be 70 J/g or less.
  • Component A contains a metallocene.
  • metallocenes include compounds represented by the following formulae. where M is a metal (Ti, Zr, Hf, V, Cr, Mn, Ni, Fe, Co, Pd, etc.). A halogen atom or the like may be bonded to M. Two dicyclopentazinide groups may form a condensed ring with a benzene ring. These rings may be substituted by a substituent (alkyl group, nitro group, amino group, sulfo group, halogen group, etc.) or may be linked by a linking group (alkylene group, etc.).
  • half-metallocenes and post-metallocenes are also included in metallocenes.
  • a half-metallocene is a compound of the above chemical formula in which only one dicyclopentazinide group is coordinated.
  • a post-metallocene is a compound of the above chemical formula in which a ligand other than a dicyclopentazinide group is coordinated.
  • the upper limit of the metallocene content in the thermoplastic adhesive composition is 20 ppm or less or 15 ppm or less in terms of metal atoms. In one embodiment, the lower limit of the metallocene content in the thermoplastic adhesive composition is 3 ppm or more or 5 ppm or more in terms of metal atoms.
  • the metal atom content can be quantified by, for example, ICP-OES/ICP-AES (inductively coupled plasma emission spectroscopy).
  • the lower limit of the melting point of component A is preferably 40°C or higher, more preferably 45°C or higher, and even more preferably 50°C or higher.
  • the upper limit of the melting point of Component A is preferably 170°C or lower, more preferably 155°C or lower, and even more preferably 140°C or lower. If the melting point is within the above range, the melting point and thermal stability of the resulting thermoplastic adhesive composition will be within appropriate ranges.
  • the melting point is measured by differential scanning calorimetry (DSC) in accordance with JIS K7122.
  • the lower limit of the number average molecular weight (Mn) of component A is preferably 2,000 or more, more preferably 6,000 or more, and even more preferably 10,000 or more.
  • the upper limit of the number average molecular weight (Mn) of Component A is preferably 300,000 or less, more preferably 250,000 or less, and even more preferably 200,000 or less.
  • the lower limit of the weight average molecular weight (Mw) of component A is preferably 6,000 or more, more preferably 20,000 or more, and even more preferably 40,000 or more.
  • the upper limit of the weight average molecular weight (Mw) of component A is preferably 600,000 or less, more preferably 500,000 or less, and even more preferably 450,000 or less.
  • the lower limit of the molecular weight distribution (Mw/Mn) of component A is preferably 1.0 or more, more preferably 1.3 or more, and even more preferably 1.6 or more.
  • the upper limit of the weight average molecular weight (Mw/Mn) of component A is preferably 8.0 or less, more preferably 6.0 or less, and even more preferably 4.0 or less. Number average molecular weight and weight average molecular weight can be measured by high temperature gel permeation chromatography (high temperature GPC).
  • thermoplastic adhesive composition according to one embodiment of the present invention, only one type of component A may be used, or two or more types may be used in combination.
  • the content of component A is not particularly limited.
  • the lower limit of the content of component A is preferably 3 parts by weight or more, more preferably 5 parts by weight or more, and even more preferably 10 parts by weight or more.
  • the upper limit of the content of component A is preferably 50 parts by weight or less, more preferably 30 parts by weight or less. If the content of component A is within the above range, the resulting thermoplastic adhesive composition will have sufficient thermal stability.
  • Component B1 is one or more resins selected from polybutene and its hydrides, polybutadiene, polyisobutylene and its hydrides, and polyisoprene.
  • the incorporation of component B1 improves the adhesion of the thermoplastic adhesive composition to polyethylene.
  • These resins are hydrocarbons that are more viscous than oils. Therefore, it is presumed that the thermoplastic adhesive composition can be made flexible and the adhesiveness to the polyethylene resin, which is a soft material, can be improved.
  • Component B1 can be synthesized by a known method. Alternatively, a commercially available product may be used as component B1. A commercially available product may be used without hydrogenation, or may be used after hydrogenation.
  • component B1 contains one or more resins selected from polybutene and its hydrides.
  • the total proportion of polybutene and its hydrides in the total weight of component B1 can be 50% by weight or more, 70% by weight or more or 90% by weight or more.
  • component B1 is one or more resins selected from polybutene and its hydrides.
  • component B1 is one or more resins selected from polybutene and its hydrides and one or more resins selected from polyisobutylene and its hydrides.
  • the lower limit of the number average molecular weight (Mn) of component B is preferably 800 or more, more preferably 900 or more, and even more preferably 1,000 or more.
  • the upper limit of the number average molecular weight (Mn) of component B is preferably 150,000 or less, more preferably 130,000 or less, even more preferably 110,000 or less.
  • the lower limit of the weight average molecular weight (Mw) of component B is preferably 1,400 or more, more preferably 1,700 or more, and even more preferably 2,000 or more.
  • the upper limit of the weight average molecular weight (Mw) of component B is preferably 400,000 or less, more preferably 300,000 or less, and even more preferably 200,000 or less.
  • the lower limit of the molecular weight distribution (Mw/Mn) of component B is preferably 1.0 or more, more preferably 1.3 or more, and even more preferably 1.6 or more.
  • the upper limit of the weight average molecular weight (Mw/Mn) of component B is preferably 7.0 or less, more preferably 5.0 or less, and even more preferably 3.0 or less. Number average molecular weight and weight average molecular weight can be measured by gel permeation chromatography (GPC).
  • thermoplastic adhesive composition according to one embodiment of the present invention, only one type of component B1 may be used, or two or more types may be used in combination.
  • the content of component B1 is not particularly limited.
  • the lower limit of the content of component B1 is preferably 1 part by weight or more, more preferably 5 parts by weight or more.
  • the upper limit of the content of component B1 is preferably 65 parts by weight or less, more preferably 60 parts by weight or less. If the content of component B1 is within the above range, the adhesiveness of the resulting thermoplastic adhesive composition to polyethylene can be improved.
  • Component B2 is an oil.
  • Examples of component B2 include mineral oils, synthetic oils and vegetable oils.
  • mineral oils include process oils (paraffinic process oils, naphthenic process oils, aromatic process oils, etc.) and liquid paraffin.
  • paraffinic process oils include n-paraffins (butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, heneicosane, docosane, tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane, triacontane, hentriacontane, dotriacontane, pentatriacontane, etc.
  • the naphthenic ring compound contained in the naphthenic process oil includes cyclic compounds having 3 or more carbon atoms. More specific examples of naphthene ring compounds include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane and cyclooctane.
  • synthetic oils include ether oils, ester oils, phosphate esters, and chlorinated paraffins.
  • thermoplastic adhesive composition according to one embodiment of the present invention, only one type of component B2 may be used, or two or more types may be used in combination.
  • Component B2 is an optional component, and its content is 1 part by weight or less (component B2 may not be included).
  • component B2 may not be included.
  • the content of component B2 is preferably 0.7 parts by weight or less, more preferably 0.5 parts by weight or less, even more preferably 0.3 parts by weight or less, and particularly preferably 0 parts by weight.
  • Component C is a tackifying resin.
  • Component C is not particularly limited as long as it is commonly used in thermoplastic adhesive compositions.
  • Examples of Component C include rosin-based resins, terpene-based resins, petroleum-based resins, and styrene-based resins.
  • rosin-based resins examples include natural rosin (gum rosin, tall rosin, wood rosin, etc.), disproportionated rosin, polymerized rosin, glycerol esters of these rosins, and pentaerythritol esters of these rosins.
  • a hydrogenated rosin-based resin such as the above-described rosin-based resin hydride is used.
  • terpene-based resins examples include terpene resins, hydrocarbon-modified terpene resins, aromatic modified terpene resins, and phenol-based modified terpene resins.
  • Hydrogenated terpene-based resins are preferably used.
  • aromatic modified terpene resin hydrides are particularly preferred.
  • Examples of petroleum resins include aliphatic petroleum resins, alicyclic petroleum resins, and aromatic petroleum resins. Hydrogenated petroleum-based resins (such as the hydrides of petroleum-based resins described above) are preferably used. Examples of alicyclic petroleum resin hydrides include hydrogenated C9 petroleum resin and hydrogenated dicyclopentadiene petroleum resin.
  • styrene resins include pure polymers such as styrene, methylstyrene, vinyltoluene, methoxystyrene, tertiary butylstyrene, and chlorostyrene. More specific examples include styrene homopolymer and ⁇ -methylstyrene homopolymer.
  • a hydrogenated styrene-based resin such as the hydride of the above-mentioned styrene-based resin is used.
  • the hydrogenation rate is preferably 50% or more, more preferably 70% or more, even more preferably 80% or more, and particularly preferably 90% or more.
  • thermoplastic adhesive composition according to one embodiment of the present invention, only one type of component C may be used, or two or more types may be used in combination.
  • the content of component C is not particularly limited.
  • the lower limit of the content of component C is preferably 20 parts by weight or more, more preferably 25 parts by weight or more.
  • the upper limit of the content of component C is preferably 50 parts by weight or less, more preferably 47 parts by weight or less. If the content of component C is within the above range, sufficient adhesive strength can be imparted even in a low-temperature environment.
  • thermoplastic adhesive composition according to one embodiment of the present invention, only one type of component D1 may be used, or two or more types may be used in combination.
  • the content of component D1 is not particularly limited.
  • the lower limit of the content of component D1 is preferably 1 part by weight or more, more preferably 3 parts by weight or more.
  • the upper limit of the content of component D1 is preferably 35 parts by weight or less, more preferably 30 parts by weight or less, and even more preferably 25 parts by weight or less.
  • Amorphous polyolefins are characterized by poor heat resistance compared to metallocene polyolefins. Therefore, from the viewpoint of heat resistance, the amorphous polyolefin content is preferably 35 parts by weight or less.
  • Component D2 is a rubber.
  • Component D2 is an optional component.
  • Component D2 is not particularly limited as long as it is a rubber commonly used in thermoplastic adhesive compositions.
  • Specific examples of component D2 include butyl rubber (IIR); halogenated butyl rubber (chlorinated butyl rubber, brominated butyl rubber, etc.); natural rubber (NR); diene rubber (polyisoprene rubber (IR), styrene-butadiene rubbers ( SBR), styrene-ethylene/butadiene-styrene rubber (SEBS), polybutadiene rubbers (BR), acrylonitrile-butadiene rubbers (NBR), uncrosslinked ethylene-propylene-diene rubber (EPDM), etc.); non-diene rubbers ( chlorosulfonated polyethylene, etc.).
  • IIR butyl rubber
  • NR natural rubber
  • NR diene rubber
  • IR polyisoprene rubber
  • thermoplastic adhesive composition according to one embodiment of the present invention, only one type of component D2 may be used, or two or more types may be used in combination.
  • the lower limit of the content of component D2 is preferably 1 part by weight or more, more preferably 3 parts by weight or more.
  • the content of component D2 is not particularly limited.
  • the upper limit of the content of component D2 is preferably 30 parts by weight or less, more preferably 20 parts by weight or less. When the content of component D2 is within the above range, pattern coatability and adhesive strength immediately after coating are improved.
  • a thermoplastic adhesive composition according to one embodiment of the present invention may contain components other than components A, B1, B2, C, D1 and D2 described above.
  • examples of such components include antioxidants, heat stabilizers, light stabilizers, UV absorbers, fillers, surfactants, coupling agents, colorants, antistatic agents, flame retardants, metallocene-based polyolefin waxes. Waxes, plasticizers, antibacterial agents, fragrances other than
  • antioxidants examples include phenolic antioxidants and organic sulfur antioxidants.
  • phenolic antioxidants include 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2 -tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacrylate, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxy phenyl)propionate]methane.
  • organic sulfur antioxidants examples include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, and pentaeryth. lytyl tetrakis (3-laurylthiopropionate). These antioxidants may be used alone or in combination of two or more.
  • waxes other than metallocene-based polyolefin waxes include synthetic waxes, petroleum waxes, and vegetable waxes.
  • synthetic waxes include polyolefin waxes (Fischer-Tropsch wax, polyethylene wax, etc.) and waxes that are solid at room temperature (higher fatty acid esters, fatty acid amides, ketones/amines, hydrogenated oils, etc.).
  • petroleum waxes include paraffin wax, microcrystalline wax and petrolatum.
  • vegetable waxes include beeswax, montan wax, carnauba wax, palm wax, rice wax, candelilla wax. These waxes may be used alone or in combination of two or more. Also, these waxes and a metallocene-based polyolefin wax (metallocene-based polypropylene wax, etc.) may be used in combination.
  • thermoplastic adhesive compositions The crystalline melting endotherm of waxes commonly used in thermoplastic adhesive compositions is 5 to 290 J/g.
  • the upper limit of the 160° C. melt viscosity of the thermoplastic adhesive composition is preferably 50,000 mPa ⁇ s or less, more preferably 35,000 mPa ⁇ s or less.
  • the lower limit of the viscosity is preferably 1,000 mPa ⁇ s or more, more preferably 2,000 mPa ⁇ s or more. If the viscosity of the thermoplastic adhesive composition is within the above range, the thermoplastic adhesive composition can be applied in a stable coating shape. Melt viscosity is measured by a viscometer according to JIS K 6862.
  • thermoplastic adhesive composition [2. Manufacturing method, use and bonding method of thermoplastic adhesive composition] [2.1. Production method]
  • a method for producing a thermoplastic adhesive composition according to one embodiment of the present invention is not particularly limited.
  • One example is a method of heating and melting each component contained in the thermoplastic adhesive composition and stirring and kneading.
  • a thermoplastic adhesive composition in which each component is sufficiently dispersed can be obtained.
  • Such a production method can be carried out, for example, by a device in which a heating device is combined with a stirring kneader, rolls, Banbury mixer, kneader, extruder, or the like.
  • An article according to an aspect of the present invention has a first adherend and a second adherend bonded together via an adhesive layer.
  • the adhesive layer comprises a thermoplastic adhesive composition according to one embodiment of the invention.
  • the adhesive layer consists solely of a thermoplastic adhesive composition.
  • the adhesive layer contains other ingredients (fillers, antioxidants, heat stabilizers, light stabilizers, UV absorbers, surfactants, coupling agents, colorants, antistatic agents, flame retardants , waxes, plasticizers, antibacterial agents, fragrances, etc.).
  • thermoplastic adhesive composition according to one embodiment of the present invention has improved adhesion to polyethylene. Therefore, in the article described above, at least one of the first adherend and the second adherend preferably contains a polyethylene-based resin.
  • the first adherend (or the second adherend) contains a polyethylene-based resin means that of the total volume of the first adherend (or the second adherend), 30% or more, 50% or more, 70% or more, 90% or more, or 100% is polyethylene resin.
  • the first adherend (or the second adherend) contains a polyethylene-based resin
  • the adhesive layer of the first adherend (or the second adherend) is in contact with It means that 30% or more, 50% or more, 70% or more, 90% or more, or 100% of the area of the portion is polyethylene resin.
  • the polyethylene-based resin has 50% or more, 70% or more, or 90% or more of all units derived from ethylene.
  • polyethylene resins include low-density polyethylene, high-density polyethylene, ethylene- ⁇ -olefin copolymer (ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-propylene-butene copolymer, ethylene-octene copolymers, ethylene-styrene copolymers, ethylene-cyclic olefin copolymers, etc.), and ultra-high molecular weight polyethylene.
  • thermoplastic adhesive composition according to one embodiment of the present invention may be contained in an adhesive layer that adheres the tape and/or gathers to the substrate.
  • a bonding method includes the following steps. Step 1: Forming an adhesive layer adjacent to the first adhesive surface. Step 2: A step of bringing the second adhesive surface into contact with the adhesive layer so as to face the first adhesive surface through the adhesive layer.
  • the adhesive layer contains a thermoplastic adhesive composition according to one embodiment of the present invention.
  • the adhesive layer consists solely of a thermoplastic adhesive composition.
  • the adhesive layer contains other ingredients (fillers, antioxidants, heat stabilizers, light stabilizers, UV absorbers, surfactants, coupling agents, colorants, antistatic agents, flame retardants , waxes, plasticizers, antibacterial agents, fragrances, etc.).
  • a step of heating and melting the thermoplastic adhesive composition may be provided prior to step 1, a step of heating and melting the thermoplastic adhesive composition may be provided.
  • step 2 a laminated structure of the first adhesive surface-adhesive layer-second adhesive surface is formed.
  • the thermoplastic adhesive composition cools and solidifies.
  • the first adhesive surface and the second adhesive surface are bonded via the solidified adhesive layer.
  • the thermoplastic adhesive composition according to one embodiment of the present invention has improved adhesion to polyethylene. Therefore, in the bonding method described above, at least one of the first bonding surface and the second bonding surface preferably contains a polyethylene resin.
  • the first adhesive surface (or the second adhesive surface) contains a polyethylene-based resin means that 30% or more of the total area of the first adhesive surface (or the second adhesive surface), It represents that 50% or more, 70% or more, 90% or more, or 100% is a polyethylene resin.
  • the first adhesive surface (or second adhesive surface) is the portion of the first adherend (or second adherend) that is in contact with the adhesive layer.
  • the polyethylene resin see [2.2. ] section.
  • the method of forming the adhesive layer on the adhesive surface is not particularly limited.
  • One example is the contact coating method.
  • the contact coating method refers to a coating method in which a coating device (coating machine, etc.) is in contact with the adhesive surface when the adhesive layer is formed on the adhesive surface.
  • Specific examples of the contact coating method include slot coating (a slot coat gun manufactured by Nordson Co., Ltd. can be used) and a roll coater (manufactured by Ebino Kosan Co., Ltd.).
  • thermoplastic adhesive composition heated and melted at 180° C. by a heater was filled in an applicator equipped with a spiral nozzle.
  • the coating weight of the applicator at the start of the test was set to 20 g/m 2 and was not changed during the test period. From this state, the cycle of "discharging the thermoplastic adhesive composition at 180° C. for 12 hours ⁇ at room temperature and allowing to cool for 12 hours" was repeated five times.
  • thermoplastic adhesive composition was heated to 180° C. and the basis weight of the applicator was measured. Evaluation criteria are as follows. +: Reduced by less than 10% from the basis weight set at the start of the test. -: Reduced by 10% or more from the basis weight set at the start of the test.
  • ⁇ Nozzle diameter about 0.3 mm ⁇
  • Air temperature 180°C ⁇ Distance from heater to nozzle: about 100mm
  • Peeling test A and B are tests assuming situations where thin members are adhered (such as when sanitary products are manufactured).
  • the peeling test C is a test assuming a situation where relatively thick members are adhered (for example, when manufacturing automobile parts).
  • thermoplastic adhesive composition was melted by heating to 180°C.
  • the thermoplastic adhesive composition in its molten state was applied by spiral spray onto one side of the spunbond nonwoven fabric.
  • the basis weight at this time was 20 gsm (g/m 2 ).
  • the spunbond nonwoven fabric and the polyethylene film were laminated together and pressed at 23° C. and 50 gf/cm 2 for 5 seconds.
  • the resulting laminate was cut in a width of 25 mm in the direction (CD) perpendicular to the advance of the base material to obtain strip-shaped test pieces.
  • This test piece was allowed to stand at 23° C. and 65% RH for 30 minutes.
  • this test piece was subjected to a T-type peel test in accordance with JIS K6845. Specifically, the strength (N/25 mm) when the test piece was peeled at a tensile speed of 300 mm/min was measured. The peel test was performed under conditions of 23° C. and 65% RH.
  • Peel test B Peel strength after 1 day (polyethylene film)
  • the test piece prepared in the peel test A was allowed to stand at 23° C. and 65% RH for 1 day. Next, the peel strength was measured under the same conditions as in the peel test A. The evaluation criteria for the results are the same as for peel test A.
  • thermoplastic adhesive composition was melted by heating to 180°C.
  • the thermoplastic adhesive composition in its molten state was applied by spiral spray onto one side of the spunbond nonwoven fabric.
  • the basis weight at this time was 20 gsm (g/m 2 ).
  • the spunbond nonwoven fabric and the polyethylene plate were bonded together and pressed at 23° C. and 50 gf/cm 2 for 5 seconds. This test piece was allowed to stand at 23° C. and 65% RH for 1 day.
  • the obtained laminate was cut at a width of 25 mm in the direction (CD) perpendicular to the advance of the base material to obtain strip-shaped test pieces.
  • this test piece was subjected to a 180° peel test in accordance with JIS K6854. Specifically, the strength (N/25 mm) when the test piece was peeled at a tensile speed of 300 mm/min was measured. The peel test was performed under conditions of 23° C. and 65% RH. The evaluation criteria for the results are the same as for peel test A.
  • thermoplastic adhesive composition [Materials used in Examples] In this example, the following materials were used as components constituting the thermoplastic adhesive composition.
  • PP polypropylene
  • PE polyethylene
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • ⁇ GPC measurement device ⁇ Apparatus: HLC-8321GPC/HT (manufactured by Tosoh Corporation) ⁇ Column: TSK-gel GMH HR -H (S) HT2 (manufactured by Tosoh Corporation) ⁇ Measurement conditions> ⁇ Solvent: ortho-dichlorobenzene (manufactured by Wako Pure Chemical Industries, Ltd., for GPC analysis) ⁇ Sample concentration: 1.0 mg/mL ⁇ Flow rate: 1.0 mL/min ⁇ Measurement temperature: 145°C
  • the melting point and crystalline melting endotherm were measured by differential scanning calorimetry (DSC) in accordance with JIS K7122.
  • the measurement conditions are as follows. ⁇ DSC measuring device> ⁇ Device: Differential scanning calorimeter DSC-3100SR (manufactured by Bruker AXS) ⁇ Measurement conditions> ⁇ Temperature rising cooling rate: 10°C/min ⁇ Sample amount: 15 mg
  • the unpublished comonomer composition was estimated by pyrolysis GC-MS.
  • Metallocene-based PP1 L-MODU S600 (manufactured by Idemitsu Kosan Co., Ltd., propylene homopolymer, melting point: 80 ° C., crystal melting endotherm: 34 J / g, Mn: 35,000, Mw: 75,000, Mw / Mn: 2.1)
  • Metallocene-based PP/PE Vistamaxx6202 (manufactured by ExxonMobil Chemical, propylene/ethylene copolymer, melting point: 105°C, crystal melting endotherm: 9 J/g, Mn: 100,000, Mw: 230,000, Mw/Mn: 2.3)
  • Metallocene-based PP/ ⁇ -olefin Tafmer (registered trademark) PN-2070 (manufactured by Mitsui Chemicals, Inc., propylene/ ⁇ -olefin copolymer, melting point: 140°C, crystal melting endotherm: 18 J/g, Mn: 1
  • thermoplastic adhesive composition [Examples 1 to 13, Comparative Examples 1 to 6] Each of the above materials was kneaded in the composition (unit: parts by weight) shown in Table 1 below to prepare a thermoplastic adhesive composition. Specific procedures are as follows. 1. Waxes, softeners (Components B1 and B2), tackifying resin (Component C), amorphous polyolefin (Component D1), rubber (Component D2) and additives were charged into a stirring kneader. These were stirred in a heated state of 150 to 190° C. and melted sufficiently. 2. The base polymer (component A) was introduced into the resulting melt. By kneading in a heated state of 150 to 190° C., component A was also sufficiently melted and uniformly dispersed in the melt. Thus, a thermoplastic adhesive composition was obtained.
  • thermoplastic adhesive composition The peel strength of the resulting thermoplastic adhesive composition was measured by the method described above. Table 1 shows the results.
  • thermoplastic adhesive compositions according to Examples 1-12 contained component A, component B1 and component C, and the content of component B2 was 1 part by weight or less. Further, component A contained a polypropylene resin having a crystal melting endotherm of 80 J/g or less, and did not contain a polypropylene resin having a crystal melting endotherm exceeding 80 J/g. As a result, these thermoplastic adhesive compositions exhibited good to excellent adhesion and coating stability to polyethylene.
  • thermoplastic adhesive composition according to Comparative Example 1 contained more than 1 part by weight of component B2.
  • the thermoplastic adhesive composition according to Comparative Example 2 contained no component B1 and contained more than 1 part by weight of component B2.
  • the thermoplastic adhesive composition according to Comparative Example 3 contained 1 part by weight or less of component B2, but did not contain component B1. As a result, these thermoplastic adhesive compositions exhibited poor adhesion to polyethylene. These results suggest that the adhesiveness can be improved by blending component B1 as a softening agent and limiting the blending amount of component B2 to 1 part by weight or less.
  • thermoplastic adhesive compositions according to Comparative Examples 4 to 6 do not contain a metallocene polypropylene resin having a crystalline melting endotherm of 80 J/g or less, but contain a polypropylene wax having a crystalline melting endotherm of more than 80 J/g. Was. As a result, after continuous use for 5 days, the coating weight decreased by 10% or more and the coating stability was poor.
  • thermoplastic adhesives containing polyethylene wax having a crystal melting endotherm of 80 J/g or more without containing a metallocene polypropylene resin having a crystal melting endotherm of 80 J/g or less No decrease in basis weight was observed with the agent composition. This is probably because the crystalline melting temperature of polyethylene wax is lower than that of polypropylene, making it easier to melt. However, the heat resistance was poor because no polypropylene-based resin was blended.
  • Comparing Example 4 and Example 12 it was found that the adhesiveness was improved when component B2 was not contained. Comparing Example 5 and Example 11, when the content of component B1 was 5 parts by weight, the adhesion was improved more than when the content of component B1 was 1 part by weight. Comparing Examples 9 and 10, when the content of component B1 was 60 parts by weight, the adhesion was improved more than when the content of component B1 was 65 parts by weight. Comparing Examples 9 and 10, when the content of component C was 25 parts by weight, the adhesion was improved more than when the content of component C was 20 parts by weight.
  • the present invention can be used for thermoplastic adhesive compositions and the like.

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

Abstract

La présente invention améliore l'adhérence au polyéthylène dans une composition adhésive thermoplastique contenant une polyoléfine métallocène. Une composition adhésive thermoplastique selon un mode de réalisation de la présente invention comprend : un constituant A qui est une polyoléfine métallocène ; un constituant B1 qui est une ou plusieurs résines choisies parmi le polybutène et l'hydrure de celui-ci, le polybutadiène, le polyisobutylène et l'hydrure de celui-ci, et le polyisoprène ; et un constituant C qui est une résine donnant du collant. La composition adhésive thermoplastique comprend, en tant que constituant optionnel, une partie en poids ou moins d'un constituant B2 qui est une huile (le poids total de la composition adhésive thermoplastique étant de 100 parties en poids). Le constituant A comprend une résine de polypropylène ayant un taux d'absorption de la chaleur de fusion de la phase cristalline inférieure ou égale à 80 g/J.
PCT/JP2022/007882 2021-02-25 2022-02-25 Composition adhésive thermoplastique WO2022181765A1 (fr)

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JP2012512924A (ja) * 2008-12-19 2012-06-07 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン メタロセン触媒オレフィン−ｃ３−ｃ２０−オレフィンコポリマーに基づく接触接着剤
JP2014514390A (ja) * 2011-03-24 2014-06-19 ヘンケル コーポレイション 伸縮性フィルム積層接着剤
JP2017538806A (ja) * 2014-11-07 2017-12-28 エイチ．ビー．フラー カンパニー 半結晶性プロピレンポリマー及びワックスを含むホットメルト接着剤組成物並びにこれを含む物品
JP2018514613A (ja) * 2015-04-17 2018-06-07 ヘンケル アイピー アンド ホールディング ゲゼルシャフト ミット ベシュレンクテル ハフツング ホットメルト接着剤およびその使用
JP2019011422A (ja) * 2017-06-30 2019-01-24 ヘンケルジャパン株式会社 ホットメルト接着剤
WO2020050225A1 (fr) * 2018-09-04 2020-03-12 出光興産株式会社 Composition de résine thermoplastique et adhésif thermofusible
JP2020512414A (ja) * 2016-11-28 2020-04-23 ボスティック，インコーポレイテッド エラストマー部品、不織材料および熱可塑性フィルムを結合するためのホットメルト接着剤

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012512924A (ja) * 2008-12-19 2012-06-07 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン メタロセン触媒オレフィン−ｃ３−ｃ２０−オレフィンコポリマーに基づく接触接着剤
JP2014514390A (ja) * 2011-03-24 2014-06-19 ヘンケル コーポレイション 伸縮性フィルム積層接着剤
JP2017538806A (ja) * 2014-11-07 2017-12-28 エイチ．ビー．フラー カンパニー 半結晶性プロピレンポリマー及びワックスを含むホットメルト接着剤組成物並びにこれを含む物品
JP2018514613A (ja) * 2015-04-17 2018-06-07 ヘンケル アイピー アンド ホールディング ゲゼルシャフト ミット ベシュレンクテル ハフツング ホットメルト接着剤およびその使用
JP2020512414A (ja) * 2016-11-28 2020-04-23 ボスティック，インコーポレイテッド エラストマー部品、不織材料および熱可塑性フィルムを結合するためのホットメルト接着剤
JP2019011422A (ja) * 2017-06-30 2019-01-24 ヘンケルジャパン株式会社 ホットメルト接着剤
WO2020050225A1 (fr) * 2018-09-04 2020-03-12 出光興産株式会社 Composition de résine thermoplastique et adhésif thermofusible

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