WO2023112688A1 - 接着剤、積層体、包装材 - Google Patents

接着剤、積層体、包装材 Download PDF

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Publication number
WO2023112688A1
WO2023112688A1 PCT/JP2022/044321 JP2022044321W WO2023112688A1 WO 2023112688 A1 WO2023112688 A1 WO 2023112688A1 JP 2022044321 W JP2022044321 W JP 2022044321W WO 2023112688 A1 WO2023112688 A1 WO 2023112688A1
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WIPO (PCT)
Prior art keywords
film
adhesive
polyisocyanate
acid
polyol
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Application number
PCT/JP2022/044321
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
丈史 黒井
克佳 手塚
豊 濱砂
康生 山下
Original Assignee
Dic株式会社
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
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Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to CN202280075861.9A priority Critical patent/CN118234825A/zh
Priority to JP2023567674A priority patent/JPWO2023112688A1/ja
Publication of WO2023112688A1 publication Critical patent/WO2023112688A1/ja

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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
    • 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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters

Definitions

  • the present invention relates to an adhesive, a laminate obtained using the adhesive, and a packaging material.
  • multi-layer laminates of metal foils such as aluminum foil or metallized films and plastic films such as polyethylene, polypropylene, vinyl chloride, polyester, and nylon are used. It is These laminates are obtained by appropriately combining various types of plastic films, metal vapor-deposited films, or metal foils according to the properties required for each application, and bonding them together with an adhesive.
  • the adhesive a two-liquid curable adhesive composed of a polyol composition and a polyisocyanate composition is generally used (for example, Patent Document 1).
  • the level of demand for these properties for adhesives is increasing day by day.
  • there is a growing movement to improve food sterilization efficiency in line with the trend of improving eating habits, and there is an opportunity to replace the conventional hot water storage type retort processing with hot water spray type retort processing. is increasing.
  • high-temperature and high-pressure hot water spray may directly hit the laminate, so the adhesive is required to have a higher level of retort resistance than conventional ones.
  • the present invention has been made in view of such circumstances, and an object of the present invention is to provide a laminating adhesive having excellent retort resistance (heat resistance and deformation relaxation property).
  • the present invention comprises a polyisocyanate composition (X) and a polyol composition (Y), wherein the polyisocyanate composition (X) is a bifunctional polyisocyanate compound (A1) and a trifunctional or higher polyisocyanate compound ( A2), the polyol composition (Y) contains the polyester polyol (B), and the amount of the polyisocyanate compound (A1) in the total amount of the polyisocyanate compound (A1) and the polyisocyanate compound (A2) is 5 to It relates to a two-component curing adhesive that is 50% by mass.
  • the polyisocyanate composition (X) is a bifunctional polyisocyanate compound (A1) and a trifunctional or higher polyisocyanate compound ( A2)
  • the polyol composition (Y) contains the polyester polyol (B)
  • the amount of the polyisocyanate compound (A1) in the total amount of the polyisocyanate compound (A1) and the polyisocyanate compound (A2) is 5 to It
  • the adhesive of the present invention it is possible to provide adhesives, laminates, and packaging materials with excellent retort resistance.
  • the adhesive of the present invention comprises a polyisocyanate composition (X) and a polyol composition (Y), wherein the polyisocyanate composition (X) is a difunctional polyisocyanate compound (A1) and a trifunctional or higher poly and the isocyanate compound (A2), the polyol composition (Y) contains the polyester polyol (B), and the amount of the polyisocyanate compound (A1) in the total amount of the polyisocyanate compound (A1) and the polyisocyanate compound (A2) is a two-component curing adhesive with a content of 5 to 50% by mass.
  • the adhesive of the present invention will be described in detail below.
  • the polyisocyanate composition (X) contains a bifunctional polyisocyanate compound (A1) and a trifunctional or higher polyisocyanate compound (A2).
  • Known polyisocyanate compounds can be used without any particular limitation.
  • bifunctional polyisocyanate compound (A1) examples include butane-1,4-diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, Aliphatic diisocyanates such as xylylene diisocyanate, m-tetramethylxylylene diisocyanate, lysine diisocyanate;
  • 1,5-naphthylene diisocyanate 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate , dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, aromatic diisocyanate such as tolylene diisocyanate,
  • Examples include adducts which are reaction products of these diisocyanates and low-molecular-weight diols, allophanates and uretdiones of these diisocyanates, and modified products obtained by modifying some of the isocyanate groups of these polyisocyanates with carbodiimide.
  • Examples of the tri- or more functional polyisocyanate compound (A2) include adducts which are reaction products of the above diisocyanate and tri- or more functional polyols, allophanate forms, biuret forms, nurate forms, and oligomers (e.g., polymeric MDI) of the above diisocyanates. etc.
  • the average number of functional groups of the polyisocyanate compound (A2) is preferably 5 or less, more preferably 4 or less.
  • Trimethylolethane, trimethylolpropane, glycerin, hexanetriol, pentaerythritol and the like are examples of tri- or higher functional polyols used for synthesis of adducts, but are not limited thereto. Moreover, you may use individually by 1 type, and may use 2 or more types together.
  • the amount of the polyisocyanate compound (A1) in the total amount of the polyisocyanate compound (A1) and the polyisocyanate compound (A2) is 5 to 50% by mass.
  • the adhesive can be excellent in retort resistance (heat resistance, deformation relaxation property).
  • the content of the polyisocyanate compound (A1) is more preferably 10% by mass or more, more preferably 15% by mass or more. Moreover, it is more preferably 40% by mass or less, and more preferably 30% by mass or less.
  • the adhesive of the present invention is excellent in retort resistance is presumed as follows.
  • a laminate obtained by laminating a plurality of substrates using a laminating adhesive is subjected to a retort treatment, separation is likely to occur at the interface between the adhesive and the laminate. This is presumably because the adhesive layer cannot mitigate the deformation of the base material due to retorting.
  • the adhesive layer is too soft, the heat applied during the retort treatment will reduce the adhesive strength, resulting in peeling of the laminate.
  • a bifunctional polyisocyanate compound (A1) and a trifunctional or higher polyisocyanate compound (A2) are used in combination as a polyisocyanate composition, and the compounding ratio is within the above range, so that the adhesive layer can be formed by retort treatment.
  • At least one of the polyisocyanate compounds (A1) and (A2) preferably contains an aliphatic polyisocyanate, and hexamethylene diisocyanate and its derivatives (adduct, allophanate, nurate, biuret, carbodiimide modified) preferably included.
  • the flexibility of the coating film can be further increased, and the adhesive can be excellent in deformation relaxation.
  • At least one of the polyisocyanate compounds (A1) and (A2) preferably contains an aromatic polyisocyanate.
  • the adhesive can have excellent normal state adhesive strength and heat resistance.
  • polyester composition (B1) is a reaction product of a monomer composition containing polyhydric carboxylic acid and polyhydric alcohol.
  • Polyvalent carboxylic acids used in the synthesis of the polyester polyol (B1) include malonic acid, ethylmalonic acid, dimethylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, succinic anhydride, alkenylsuccinic anhydride, and glutaric acid. , adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, dimer acid, trimer acid, tetramer acid and other aliphatic polycarboxylic acids;
  • Aliphatic polycarboxylic acids such as dimethyl malonate, diethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, diethyl pimelate, diethyl sebacate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, and diethyl maleate alkyl esters of acids;
  • methyl esters of aromatic polyvalent carboxylic acids such as dimethyl terephthalic acid and dimethyl 2,6-naphthalenedicarboxylate;
  • the polyhydric alcohol used for synthesizing the polyester polyol (B1) may be a diol or a trifunctional or higher polyol.
  • the diol include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1, 2,2-trimethyl-1,3-propanediol, 2,2-dimethyl-3-isopropyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1, 3-butanediol, 1,5-pentanediol, 3-methyl 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-bis(hydroxymethyl)cyclohexane, 2,2,4- Aliphatic diols such as trimethyl-1,3-pentanediol and dimer diol;
  • Ether glycols such as polyoxyethylene glycol and polyoxypropylene glycol
  • a lactone-based polyester polyol obtained by a polycondensation reaction between the aliphatic diol and various lactones such as lactanoids and ⁇ -caprolactone;
  • Bisphenols such as bisphenol A and bisphenol F;
  • Examples include alkylene oxide adducts of bisphenols obtained by adding ethylene oxide, propylene oxide, etc. to bisphenols such as bisphenol A and bisphenol F.
  • the tri- or more functional polyols are aliphatic polyols such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, and pentaerythritol;
  • Modification obtained by ring-opening polymerization of the aliphatic polyol with various cyclic ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether polyether polyols;
  • Examples include lactone-based polyester polyols obtained by a polycondensation reaction between the above-mentioned aliphatic polyol and various lactones such as ⁇ -caprolactone.
  • the polyester polyol (B1) is a polyester polyurethane polyol obtained by chain-extending a polyester polyol which is a reaction product of a polyhydric carboxylic acid and a polyhydric alcohol with a polyisocyanate compound, or a polyhydric alcohol, a polyhydric carboxylic acid and a polyisocyanate compound. Also preferred is a polyester polyurethane polyol that is the reaction product of a composition comprising: As the polyisocyanate compound used for synthesizing the polyester polyurethane polyol, the same compounds as exemplified as the polyisocyanate compounds (A1) and (A2) can be used.
  • the polyester polyol (B1) used in the present invention preferably contains a tetramer acid as the polyvalent carboxylic acid.
  • Tetramer acid is a product of the Diels-Alder reaction of unsaturated fatty acids such as oleic acid and linoleic acid. and tetrafunctional carboxylic acids obtained by reacting unsaturated fatty acids contained in recovered oils including natural oils of these fatty acids. It may be acyclic, monocyclic, polycyclic, or aromatic, or may be a combination of any two or more.
  • the carboxyl group of the tetramer acid is directly bonded to the saturated alkyl group, and the distance from the branch point to the reaction point (carboxyl group) is long, so it is less susceptible to steric hindrance. Combined with the fact that it becomes liquid at a relatively low temperature, the carboxyl group of the tetramer acid is highly reactive and is preferentially consumed at the beginning of the esterification reaction. Therefore, the polyester polyol (B1) using a tetramer acid as a starting material contains the polyester polyol (b1) having a star-shaped branched structure centered on the tetramer acid.
  • the branch points derived from the polyester polyol (b1) are less likely to undergo decomposition reactions even in a high-temperature environment or in the presence of moisture. Therefore, the branched structure can be maintained even in a high-temperature environment, and a decrease in adhesive strength can be suppressed. That is, the adhesive can be excellent in heat resistance and hot water resistance.
  • polyester polyol (b1) does not have localized ester bonds near the branch point derived from the tetramer acid. For this reason, flexibility can be maintained even if the branching point concentration of the cured coating film is high, and it can be used not only for adhesion between films, but also for relatively hard layers such as aluminum foil, aluminum vapor deposition layers, and inorganic oxide vapor deposition layers. , the adhesion to a relatively soft layer such as a resin film is also excellent.
  • the adhesive layer can also be expected to act as a buffer to prevent cracking and peeling of the deposited aluminum layer and deposited inorganic oxide layer. Even when water penetrates into the effect coating film, the molecular chains are not cut at once near the branch point, so the adhesive can have good hot water resistance.
  • the polycarboxylic acid used for synthesizing the polyester polyol (B1) contains a tetramer acid
  • the amount thereof is not particularly limited. When it is 0.1% by mass or more, the heat resistance tends to be improved, which is preferable. There is no particular upper limit, but if it is too large, gelation tends to occur during the production of the polyester polyol (B1), making production more difficult. More preferably, it is 0.1% by mass or more and 2.0% by mass or less.
  • the polyester polyol (B1) is a polyester polyurethane polyol
  • the monomer composition contains polyhydric carboxylic acid, polyhydric alcohol, and polyisocyanate compound used for its synthesis.
  • the polyester polyol (B1) used in the present invention preferably contains an aromatic polycarboxylic acid as the polycarboxylic acid. Thereby, it can be set as the adhesive agent excellent in heat resistance.
  • the polyhydric carboxylic acid contains an aromatic polyhydric carboxylic acid
  • the blending amount thereof can be appropriately adjusted, but is, for example, 5% by mass or more, 30% by mass or more, or 50% by mass or more.
  • the upper limit is also adjusted appropriately, and as an example, it is 95% by mass or less, and 90% by mass or less.
  • the number average molecular weight (Mn) of the polyester polyol (B1) is not particularly limited, it is, for example, 500 to 100,000, more preferably 1,000 to 50,000.
  • the weight average molecular weight (Mw) is, for example, 1,000 to 300,000, more preferably 2,000 to 200,000.
  • the number average molecular weight (Mn) and weight average molecular weight (Mw) are values measured by gel permeation chromatography (GPC) under certain conditions.
  • HLC-8320GPC manufactured by Tosoh Corporation Column
  • TSKgel 4000HXL TSKgel 3000HXL
  • TSKgel 2000HXL TSKgel 1000HXL manufactured by Tosoh Corporation Detector
  • RI differential refractometer
  • Multi-station GPC-8020modelII manufactured by Tosoh Corporation Measurement conditions
  • Monodisperse polystyrene Sample 0.2 mass% tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 ⁇ l)
  • the hydroxyl value of the polyester polyol (B1) is preferably in the range of 1 to 150 mgKOH/g, more preferably 3 mgKOH/g or more and 100 mgKOH/g or less.
  • the acid value of the polyester polyol (B) is not particularly limited, it is preferably 10.0 mgKOH/g or less. Although there is no particular lower limit, an example is 0.5 mgKOH/g or more. It may be 0 mg KOH/g.
  • a hydroxyl value and an acid value can be measured by the method described in JIS-K0070.
  • the polyol composition (Y) may contain a polyol (B2) other than the polyester polyol (B1).
  • the polyol (B2) include those exemplified as polyhydric alcohols used for preparing the polyester polyol (B1).
  • the blending amount of the polyester polyol (B1) is 70 parts by mass or more with respect to the total 100 parts by mass of the blending amount of the polyester polyol (B1) and the polyol (B2). It is preferably 80 parts by mass or more, more preferably 90 parts by mass or more.
  • the adhesive of the present invention may contain components other than those mentioned above. These components may be contained in either or both of the polyisocyanate composition (X) and the polyol composition (Y), or they may be prepared separately from the polyisocyanate composition (X) and the polyol composition (Y) immediately before coating the adhesive. It may be used by mixing with the composition (X) and the polyol composition (Y). Each component will be described below.
  • the adhesive of the present invention may be either solvent-based or non-solvent-based.
  • the "solvent type" adhesive referred to in the present invention is a method of applying the adhesive to a base material, heating it in an oven or the like to volatilize the organic solvent in the coating film, and then bonding it to another base material. , refers to a form used in a so-called dry lamination method.
  • Either one or both of the polyisocyanate composition (X) and the polyol composition (Y) can dissolve (dilute) the polyisocyanate composition (X) and the polyol composition (Y) used in the present invention. Contains organic solvents.
  • organic solvents examples include esters such as ethyl acetate, butyl acetate and cellosolve acetate; ketones such as acetone, methyl ethyl ketone, isobutyl ketone and cyclohexanone; ethers such as tetrahydrofuran and dioxane; and aromatic hydrocarbons such as toluene and xylene. , methylene chloride, halogenated hydrocarbons such as ethylene chloride, dimethylsulfoxide, dimethylsulfamide and the like.
  • the organic solvent used as a reaction medium during the production of the constituents of the polyisocyanate composition (X) or the polyol composition (Y) may also be used as a diluent during coating.
  • solvent-free adhesive means that the polyisocyanate composition (X) and the polyol composition (Y) are substantially The form of the adhesive used in the so-called non-solvent lamination method, which is a method in which the adhesive is applied to the base material and then laminated to another base material without the process of heating in an oven or the like to volatilize the solvent.
  • non-solvent lamination method is a method in which the adhesive is applied to the base material and then laminated to another base material without the process of heating in an oven or the like to volatilize the solvent.
  • the constituent components of the polyisocyanate composition (X) or the polyol composition (Y) and the organic solvent used as the reaction medium during the production of the raw materials cannot be completely removed, resulting in the polyisocyanate composition (X) or the polyol composition ( If a small amount of organic solvent remains in Y), it is understood that the organic solvent is not substantially contained.
  • the polyol composition (Y) contains a low-molecular-weight alcohol
  • the low-molecular-weight alcohol reacts with the polyisocyanate composition (X) and becomes part of the coating film, so it is not necessary to volatilize after coating.
  • Such forms are therefore also treated as solventless adhesives and low molecular weight alcohols are not considered organic solvents.
  • the polyester polyol (B) has a large number average molecular weight.
  • the adhesives of the present invention are solvent-based, as they can be easily adjusted.
  • the polyisocyanate composition (X) and the polyol composition (Y) are divided into isocyanate groups contained in the polyisocyanate composition (X) and polyol compositions (Y). It is preferable to adjust the molar ratio ([NCO]/[OH]) with the hydroxyl group to be 1.0 to 4.0.
  • the adhesive of the present invention can accelerate the curing reaction by using a catalyst as necessary.
  • the catalyst is not particularly limited as long as it promotes the urethanization reaction between the polyisocyanate composition (X) and the polyol composition (Y), and includes metal-based catalysts, amine-based catalysts, aliphatic cyclic amide compounds, titanium Chelate complexes and the like are exemplified.
  • Metal-based catalysts include metal complex-based, inorganic metal-based, and organic metal-based catalysts.
  • the metal complex catalyst a group consisting of Fe (iron), Mn (manganese), Cu (copper), Zr (zirconium), Th (thorium), Ti (titanium), Al (aluminum), Co (cobalt) Examples include acetylacetonate salts of metals selected from the above, such as iron acetylacetonate, manganese acetylacetonate, copper acetylacetonate, zirconia acetylacetonate and the like. From the point of view of toxicity and catalytic activity, iron acetylacetonate (Fe(acac) 3 ) or manganese acetylacetonate (Mn(acac) 2 ) are preferred.
  • inorganic metal-based catalysts examples include those selected from Sn, Fe, Mn, Cu, Zr, Th, Ti, Al, Co, and the like.
  • Organometallic catalysts include organozinc compounds such as zinc octylate, zinc neodecanoate, and zinc naphthenate; , dioctyltin dilaurate, dibutyltin oxide, dibutyltin dichloride and other organic tin compounds, nickel octylate, nickel naphthenate and other organic nickel compounds, cobalt octylate, cobalt naphthenate and other organic cobalt compounds, bismuth octylate, neodecanoic acid
  • organozinc compounds such as zinc octylate, zinc neodecanoate, and zinc naphthenate
  • dioctyltin dilaurate dibutyltin oxide, dibutyltin dichloride and other organic tin compounds
  • nickel octylate, nickel naphthenate and other organic nickel compounds cobalt octylate, cobalt nap
  • Amine catalysts include triethylenediamine, 2-methyltriethylenediamine, quinuclidine, 2-methylquinuclidine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyl Propylenediamine, N,N,N',N',N''-pentamethyldiethylenetriamine, N,N,N',N'',N'-pentamethyl-(3-aminopropyl)ethylenediamine, N,N,N', N′′,N′′-pentamethyldipropylenetriamine, N,N,N′,N′-tetramethylhexamethylenediamine, bis(2-dimethylaminoethyl)ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol , N,N-dimethyl-N'-(2-hydroxyethyl)ethylenediamine, N,N-dimethyl
  • Aliphatic cyclic amide compounds include, for example, ⁇ -valerolactam, ⁇ -caprolactam, ⁇ -enanthollactam, ⁇ -capryllactam, ⁇ -propiolactam and the like.
  • ⁇ -caprolactam is more effective in accelerating hardening.
  • the titanium chelate complex is a compound whose catalytic activity is enhanced by ultraviolet irradiation, and a titanium chelate complex having an aliphatic or aromatic diketone as a ligand is preferable from the viewpoint of excellent curing acceleration effect. Further, in the present invention, in addition to aromatic or aliphatic diketones, those having alcohols having 2 to 10 carbon atoms as ligands are preferred from the viewpoint that the effects of the present invention are more pronounced.
  • the amount of the catalyst compounded is preferably 0.001 to 3 parts by mass, more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the total solid content of the polyisocyanate composition (X) and the polyol composition (Y). is more preferable.
  • the adhesive of the present invention may contain a pigment if necessary.
  • the pigments used are not particularly limited, and extender pigments, white pigments, black pigments, gray pigments, red pigments, brown pigments, green pigments, and blue pigments described in the 1970 edition of the Handbook of Paint Materials (edited by the Japan Paint Manufacturers Association).
  • Organic and inorganic pigments such as pigments, metal powder pigments, luminescent pigments, and pearlescent pigments, and plastic pigments can be used.
  • Extender pigments include, for example, precipitated barium sulfate, rice flour, precipitated calcium carbonate, calcium bicarbonate, Kansui stone, alumina white, silica, hydrous fine silica (white carbon), ultrafine anhydrous silica (Aerosil), silica sand (silica sand), talc, precipitated magnesium carbonate, bentonite, clay, kaolin, loess, and the like.
  • organic pigments include various insoluble azo pigments such as Benzidine Yellow, Hansa Yellow and Laked 4R; soluble azo pigments such as Laked C, Carmine 6B and Bordeaux 10; various (copper) pigments such as phthalocyanine blue and phthalocyanine green.
  • insoluble azo pigments such as Benzidine Yellow, Hansa Yellow and Laked 4R
  • soluble azo pigments such as Laked C, Carmine 6B and Bordeaux 10
  • various (copper) pigments such as phthalocyanine blue and phthalocyanine green.
  • Phthalocyanine pigments various chlorine dyeing lakes such as rhodamine lake and methyl violet lake; various mordant pigments such as quinoline lake and fast sky blue; various pigments such as anthraquinone pigments, thioindigo pigments and perinone pigments vat dye-based pigments; various quinacridone-based pigments such as Cincasia Red B; various dioxazine-based pigments such as dioxazine violet; various condensed azo pigments such as chromophtal;
  • inorganic pigments include various chromates such as yellow lead, zinc chromate, molybdate orange; various ferrocyanic compounds such as Prussian blue; Various metal oxides such as zirconium oxide; various sulfides and selenides such as cadmium yellow, cadmium red, and mercury sulfide; various sulfates such as barium sulfate and lead sulfate; various types of silicon such as calcium silicate and ultramarine blue.
  • chromates such as yellow lead, zinc chromate, molybdate orange
  • ferrocyanic compounds such as Prussian blue
  • metal oxides such as zirconium oxide
  • various sulfides and selenides such as cadmium yellow, cadmium red, and mercury sulfide
  • various sulfates such as barium sulfate and lead sulfate
  • silicon such as calcium silicate and ultramarine blue.
  • various acid salts such as calcium carbonate and magnesium carbonate; various phosphates such as cobalt violet and manganese purple; various metal powder pigments such as aluminum powder, gold powder, silver powder, copper powder, bronze powder and brass powder; These metal flake pigments and mica flake pigments; metallic pigments and pearl pigments such as mica-like iron oxide pigments and mica-like iron oxide pigments coated with metal oxides; graphite, carbon black and the like.
  • plastic pigments examples include "Grandol PP-1000" and “PP-2000S” manufactured by DIC Corporation.
  • the pigment to be used may be appropriately selected according to the purpose.
  • inorganic oxides such as titanium oxide and zinc oxide are preferably used as white pigments because they are excellent in durability, weather resistance, and design.
  • Carbon black is preferably used as the pigment.
  • the amount of the pigment compounded is, for example, 1 to 400 parts by mass with respect to 100 parts by mass of the total solid content of the polyisocyanate composition (X) and the polyol composition (Y). 10 to 300 parts by mass is more preferable.
  • the adhesive of the present invention may contain an adhesion promoter.
  • adhesion promoters include coupling agents such as silane coupling agents, titanate coupling agents and aluminum coupling agents, and epoxy resins.
  • Silane coupling agents include ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl)- ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl)- ⁇ -amino Aminosilanes such as propyltrimethyldimethoxysilane and N-phenyl- ⁇ -aminopropyltrimethoxysilane; ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxy epoxysilanes such as propyltriethoxysilane; vinylsilanes such as vinyltris( ⁇ -methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, ⁇ -methacryloxypropyl
  • Titanate-based coupling agents include, for example, tetraisopropoxytitanium, tetra-n-butoxytitanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate, titanium lactate, tetrastearoxy Titanium etc. are mentioned.
  • aluminum-based coupling agents examples include acetoalkoxyaluminum diisopropylate.
  • epoxy resin generally commercially available epibis type, novolak type, ⁇ -methyl epichloro type, cyclic oxirane type, glycidyl ether type, glycidyl ester type, polyglycol ether type, glycol ether type, epoxidized fatty acid ester type, poly Various epoxy resins such as carboxylic acid ester type, aminoglycidyl type, resorcinol type, triglycidyl tris(2-hydroxyethyl) isocyanurate, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, acryl glycidyl compounds such as ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, phenol glycidyl ether, pt-butylphenyl glycidyl ether, diglycidyl
  • the adhesive of the present invention includes a leveling agent, inorganic fine particles such as colloidal silica and alumina sol, polymethyl methacrylate organic fine particles, an antifoaming agent, an anti-sagging agent, a wetting and dispersing agent, and a viscosity modifier.
  • a leveling agent such as colloidal silica and alumina sol, polymethyl methacrylate organic fine particles, an antifoaming agent, an anti-sagging agent, a wetting and dispersing agent, and a viscosity modifier.
  • UV absorber metal deactivator, peroxide decomposer, flame retardant, reinforcing agent, plasticizer, lubricant, rust inhibitor, fluorescent whitening agent, inorganic heat ray absorber, flame retardant, electrification Inhibitors, dehydrating agents, known and commonly used thermoplastic elastomers, tackifiers, phosphoric compounds, melamine resins, reactive elastomers and the like may also be included.
  • dehydrating agents known and commonly used thermoplastic elastomers, tackifiers, phosphoric compounds, melamine resins, reactive elastomers and the like may also be included.
  • the blending amount of these additives is appropriately adjusted within a range that does not impair the desired properties of the adhesive of the present invention.
  • the laminate of the present invention is obtained by laminating a plurality of films or papers using the adhesive of the present invention by a dry lamination method or a non-solvent lamination method.
  • the film to be used is not particularly limited, and a suitable film can be selected according to the application.
  • polyethylene terephthalate (PET) film polystyrene film, polyamide film, polyacrylonitrile film
  • polyethylene film LLDPE: low density polyethylene film
  • HDPE high density polyethylene film
  • MDOPE uniaxially oriented polyethylene film
  • OPE Biaxially stretched polyethylene film
  • polypropylene film CPP: non-stretched polypropylene film
  • OPP biaxially stretched polypropylene film
  • ethylene vinyl alcohol copolymer polyvinyl alcohol
  • polyvinyl alcohol or other gas-barrier resins with olefin on one or both sides
  • Polyolefin films such as gas-barrier heat-sealable films provided with a heat-sealable resin layer, polyvinyl alcohol films, ethylene-vinyl alcohol copolymer films, and the like.
  • Biomass films are sold by various companies, and for example, sheets listed in the list of certified biomass products described by the Japan Organic Resources Association can be used.
  • biomass films include those made from biomass-derived ethylene glycol.
  • Biomass-derived ethylene glycol is produced from biomass-derived ethanol (biomass ethanol).
  • biomass-derived ethylene glycol can be obtained by a method in which biomass ethanol is converted into ethylene glycol via ethylene oxide by a conventionally known method.
  • commercially available biomass ethylene glycol may be used, and for example, biomass ethylene glycol commercially available from India Glycol can be preferably used.
  • films containing biomass polyester, biomass polyethylene terephthalate, etc. having biomass-derived ethylene glycol as a diol unit and fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit. It has been known.
  • the dicarboxylic acid unit of biomass polyester uses the dicarboxylic acid derived from a fossil fuel.
  • dicarboxylic acids aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and derivatives thereof can be used without limitation.
  • a difunctional oxycarboxylic acid, a trifunctional or higher polyhydric alcohol for forming a crosslinked structure, a trifunctional or higher polycarboxylic acid and/or its anhydride in addition to the above diol component and dicarboxylic acid component, a difunctional oxycarboxylic acid, a trifunctional or higher polyhydric alcohol for forming a crosslinked structure, a trifunctional or higher polycarboxylic acid and/or its anhydride.
  • a copolymerization component such as at least one polyfunctional compound selected from the group consisting of polycarboxylic acids and tri- or more functional oxycarboxylic acids.
  • biomass polyolefin films such as biomass polyethylene films containing polyethylene resins made from biomass-derived ethylene glycol, biomass polyethylene-polypropylene films, etc. Films are also known.
  • the polyethylene-based resin is not particularly limited except that the biomass-derived ethylene glycol is used as a part of the raw material.
  • the ⁇ -olefin constituting the copolymer of ethylene and ⁇ -olefin is not particularly limited, and may be 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, or the like having 4 to 10 carbon atoms. 8 ⁇ -olefins.
  • Known polyethylene resins such as low density polyethylene resins, medium density polyethylene resins and linear low density polyethylene resins can be used.
  • linear low-density polyethylene resin (LLDPE) (a copolymer of ethylene and 1-hexene, or ethylene and 1 - octene) are preferred, and linear low density polyethylene resins with densities between 0.910 and 0.925 g/cm 3 are more preferred.
  • Radiocarbon 14C exists in the atmosphere at a rate of 1 in 1012, and this rate does not change even with carbon dioxide in the atmosphere. Therefore, the carbon of the plant-derived resin contains radioactive carbon 14C. In contrast, the carbon of the fossil fuel-derived resin contains almost no radioactive carbon 14C. Therefore, by measuring the concentration of radioactive carbon 14C in the resin with an accelerator mass spectrometer, the content ratio of the plant-derived resin in the resin, that is, the degree of biomass plasticity can be obtained.
  • plant-derived low-density polyethylene which is a biomass plastic having a biomass plastic degree of 80% or more, preferably 90% or more, as defined by ISO 16620 or ASTM D6866
  • plant-derived low-density polyethylene which is a biomass plastic having a biomass plastic degree of 80% or more, preferably 90% or more, as defined by ISO 16620 or ASTM D6866
  • Examples of plant-derived low-density polyethylene, which is a biomass plastic having a biomass plastic degree of 80% or more, preferably 90% or more, as defined by ISO 16620 or ASTM D6866 include, for example, Braskem's product names "SBC818" and "SPB608". "SBF0323HC”, “STN7006”, “SEB853", “SPB681” and the like can be mentioned, and films using these as raw materials can be preferably used.
  • Films and sheets containing starch which is a biomass raw material, and polylactic acid are also known. These can be appropriately selected and used depending on the application.
  • the biomass film may be a laminate obtained by laminating a plurality of biomass films, or may be a laminate of a conventional petroleum-based film and a biomass film. Moreover, these biomass films may be either unstretched films or stretched films, and the manufacturing method thereof is not limited.
  • the film may be stretched.
  • a stretching treatment method it is common to melt-extrude a resin into a sheet by an extrusion film-forming method or the like, and then subject the sheet to simultaneous biaxial stretching or sequential biaxial stretching.
  • sequential biaxial stretching it is common to first perform longitudinal stretching and then laterally stretching. Specifically, a method of combining longitudinal stretching using a speed difference between rolls and lateral stretching using a tenter is often used.
  • Various surface treatments such as flame treatment and corona discharge treatment may be applied to the film surface as necessary so that an adhesive layer without defects such as film breakage and repellency is formed.
  • a barrier film containing a vapor-deposited layer of a metal such as aluminum, a metal oxide such as silica or alumina, or a gas barrier layer such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, or vinylidene chloride may be used in combination. good too.
  • a known paper base material can be used without any particular limitation. Specifically, it is produced by a known paper machine using natural fibers for papermaking such as wood pulp, but the papermaking conditions are not particularly specified.
  • natural fibers for papermaking include wood pulp such as softwood pulp and hardwood pulp, non-wood pulp such as Manila hemp pulp, sisal pulp and flax pulp, and pulp obtained by chemically modifying these pulps.
  • the types of pulp that can be used include chemical pulp, ground pulp, chemi-grand pulp, thermomechanical pulp, and the like prepared by sulfate cooking, acidic/neutral/alkaline sulfite cooking, soda salt cooking, and the like.
  • a printed layer may be provided on the outer surface or the inner surface of the paper layer, if necessary.
  • Base film 1/Adhesive layer 1/Sealant film (2) Base film 1/Adhesive layer 1/Metal-deposited unstretched film (3) Base film 1/Adhesive layer 1/Metal-deposited stretched film (4) Transparent vapor deposited stretched film/adhesive layer 1/sealant film (5) Base film 1/adhesive layer 1/base film 2/adhesive layer 2/sealant film (6) Base film 1/adhesive layer 1/metal vapor deposited stretched film /adhesive layer 2/sealant film (7) base film 1/adhesive layer 1/transparent deposited stretched film/adhesive layer 2/sealant film (8) base film 1/adhesive layer 1/metal layer/adhesive layer 2/sealant Film (9) Base film 1/Adhesive layer 1/Base film 2/Adhesive layer 2/Metal
  • Examples of the base material 1 used in configuration (1) include MDOPE film, OPE film, OPP film, PET film, nylon film, paper, and the like. Further, as the base material 1, a material coated for the purpose of improving gas barrier properties and ink receptivity when providing a printing layer, which will be described later, may be used. Commercially available products of the coated base film 1 include K-OPP film and K-PET film.
  • the adhesive layer 1 is a cured coating film of the adhesive of the present invention. Sealant films include CPP films, LLDPE films, gas barrier heat seal films, and the like.
  • a printing layer may be provided on the surface of the substrate 1 on the side of the adhesive layer 1 (the surface of the coating layer on the side of the adhesive layer 1 when a coated substrate film 1 is used) or the surface opposite to the adhesive layer 1, A printing layer may be provided.
  • the printing layer is formed by general printing methods conventionally used for printing on polymer films and paper using various printing inks such as gravure ink, flexographic ink, offset ink, stencil ink, and inkjet ink.
  • the base material 1 used in configurations (2) and (3) examples include MDOPE film, OPE film, OPP film, PET film, paper, and the like.
  • the adhesive layer 1 is a cured coating film of the adhesive of the present invention.
  • unstretched metal-deposited films include CPP films, LLDPE films, and VM-CPP films and VM-LLDPE films obtained by subjecting a gas-barrier heat seal film to metal deposition such as aluminum.
  • An OPE film, a VM-MDOPE film obtained by subjecting an OPP film to vapor deposition of metal such as aluminum, a VM-OPE film, and a VM-OPP film can be used.
  • a printed layer may be provided on either side of the substrate 1 in the same manner as in configuration (1).
  • Examples of transparent vapor-deposited stretched films used in configuration (4) include films obtained by vapor-depositing silica or alumina on MDOPE films, OPE films, OPP films, PET films, nylon films, and the like.
  • a film obtained by coating the deposition layer may be used.
  • the adhesive layer 1 is a cured coating film of the adhesive of the present invention.
  • Examples of the sealant film include those similar to those of the configuration (1).
  • a printed layer may be provided on the adhesive layer 1 side of the transparent vapor deposited stretched film (when using a film having a coated inorganic vapor deposited layer, the surface of the coating layer on the adhesive layer 1 side). The method of forming the printed layer is the same as that of configuration (1).
  • Examples of the base material 1 used in configuration (5) include PET film, paper, and the like.
  • Examples of the base material 2 include a nylon film and the like.
  • At least one of adhesive layer 1 and adhesive layer 2 is a cured coating film of the adhesive of the present invention.
  • Examples of the sealant film include those similar to those of the configuration (1).
  • a printed layer may be provided on either side of the substrate 1 in the same manner as in configuration (1).
  • the base material 1 of configuration (6) As the base material 1 of configuration (6), the same ones as those of configurations (2) and (3) can be mentioned.
  • the metallized stretched film include MDOPE film, OPE film, OPP film, VM-MDOPE film obtained by vapor-depositing metal such as aluminum on PET film, VM-OPE film, VM-OPP film and VM-PET film.
  • At least one of adhesive layer 1 and adhesive layer 2 is a cured coating film of the adhesive of the present invention.
  • the sealant film include those similar to those of the configuration (1).
  • a printed layer may be provided on either side of the substrate 1 in the same manner as in configuration (1).
  • Examples of the base material 1 of configuration (7) include PET film, paper, and the like. Examples of the transparent vapor-deposited stretched film include those similar to those of the configuration (4). At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those of the configuration (1). A printed layer may be provided on either side of the substrate 1 in the same manner as in configuration (1).
  • Examples of the base material 1 of configuration (8) include PET film, paper, and the like. Aluminum foil etc. are mentioned as a metal layer. At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include those similar to those of the configuration (1). A printed layer may be provided on either side of the substrate 1 in the same manner as in configuration (1).
  • Examples of the base material 1 of configurations (9) and (10) include PET film, paper, and the like.
  • Examples of the base material 2 include a nylon film and the like. Aluminum foil etc. are mentioned as a metal layer.
  • At least one of the adhesive layers 1, 2 and 3 is a cured coating film of the adhesive of the present invention.
  • Examples of the sealant film include those similar to those of the configuration (1).
  • a printed layer may be provided on either side of the substrate 1 in the same manner as in configuration (1).
  • the adhesive of the present invention is a solvent type
  • the adhesive of the present invention is applied to the film material that will be the substrate using a roll such as a gravure roll, and the organic solvent is volatilized by heating in an oven or the like.
  • the laminate of the present invention is obtained by laminating the other base material. It is preferable to perform an aging treatment after lamination.
  • the aging temperature is preferably room temperature to 80° C.
  • the aging time is preferably 12 to 240 hours.
  • the adhesive of the present invention is solvent-free, after applying the adhesive of the present invention that has been preheated to about 40° C. to 100° C. to the base film material using a roll such as a gravure roll. , the other substrate is immediately laminated to obtain the laminate of the present invention. It is preferable to perform an aging treatment after lamination.
  • the aging temperature is preferably room temperature to 70° C., and the aging time is preferably 6 to 240 hours.
  • the amount of adhesive to be applied is appropriately adjusted.
  • the solid content is adjusted to 1 g/m 2 or more and 10 g/m 2 or less, preferably 2 g/m 2 or more and 5 g/m 2 or less.
  • the coating amount of the adhesive is, for example, 1 g/m 2 or more and 5 g/m 2 or less, preferably 1 g/m 2 or more and 3 g/m 2 or less.
  • the laminate of the present invention may further contain other films and substrates in addition to the above-described configurations (1) to (10).
  • other substrates in addition to the stretched film, unstretched film, and transparent vapor-deposited film described above, porous substrates such as paper, wood, and leather, which will be described later, can also be used.
  • the adhesive used when bonding other substrates may or may not be the adhesive of the present invention.
  • “Other layers” may contain known additives and stabilizers, such as antistatic agents, easy-adhesion coating agents, plasticizers, lubricants, and antioxidants.
  • the "other layers” are pre-treated with corona treatment, plasma treatment, ozone treatment, chemical treatment, solvent treatment, etc. in order to improve adhesion when laminated with other materials. may
  • the laminate of the present invention can be used in various applications, such as packaging materials for foods, pharmaceuticals, and daily necessities, lids, paper straws, paper napkins, paper spoons, paper plates, paper cups and other paper tableware, barrier materials, and roofs. materials, solar cell panel materials, battery packaging materials, window materials, outdoor flooring materials, lighting protection materials, automotive parts, signboards, outdoor industrial applications such as stickers, decorative sheets used for injection molding simultaneous decoration methods, etc. It can be suitably used as packaging materials for liquid laundry detergents, liquid kitchen detergents, liquid bath detergents, liquid bath soaps, liquid shampoos, liquid conditioners, and the like.
  • the laminate of the present invention is excellent in heat resistance and deformation relaxation, it can be particularly suitably used for applications requiring these properties.
  • Applications in which a laminate having an adhesive layer having heat resistance and deformation relaxation properties are suitably used include packaging materials for boiling and retorting.
  • Applications in which the laminate having an adhesive layer with heat resistance is preferably used include automotive interior materials and heat-dissipating sheet members.
  • PTP packaging and the like are examples of applications in which a laminate having an adhesive layer having deformation relaxation properties is preferably used.
  • PET film/Ny film/aluminum foil/CPP film PET film/aluminum foil/Ny film/CPP film, Ny film/aluminum foil/Ny film/CPP film, and the like.
  • a film and an aluminum foil are laminated using the adhesive of the present invention.
  • Other films may be laminated using a general-purpose adhesive, or may be laminated using the adhesive of the present invention. It goes without saying that a printing layer may be provided at an appropriate position of the laminate.
  • the laminate of the present invention can be used as a multilayer packaging material for the purpose of protecting foods, medicines, and the like.
  • the layer structure may vary depending on the contents, usage environment, and usage pattern.
  • the package of the present invention may be appropriately provided with an easy-opening treatment or a resealing means.
  • the packaging material of the present invention is obtained by using the laminate of the present invention, superimposing the sealant film surfaces of the laminate on each other, and then heat-sealing the peripheral edges to form a bag.
  • the laminate of the present invention is folded or overlapped so that the inner layer surface (sealant film surface) faces each other, and the peripheral edge is sealed, for example, by a side seal type, a two-sided seal type, There are three-sided seal type, four-sided seal type, envelope pasted seal type, palm pasted seal type, pleated seal type, flat bottom seal type, square bottom seal type, gusset type, and other heat seal methods. be done.
  • the packaging material of the present invention can take various forms depending on the contents, environment of use, and form of use. A self-supporting packaging material (standing pouch) or the like is also possible.
  • As a heat sealing method known methods such as bar sealing, rotary roll sealing, belt sealing, impulse sealing, high frequency sealing and ultrasonic sealing can be used.
  • the opening is heat-sealed to manufacture a product using the packaging material of the present invention.
  • filling contents include foods such as rice confectionery, bean confectionery, nuts, biscuits and cookies, wafer confectionery, marshmallows, pies, half-baked cakes, candy, snacks, bread, snack noodles, and instant noodles.
  • Non-food items include cigarettes, disposable body warmers, medicines such as infusion packs, liquid laundry detergents, liquid kitchen detergents, liquid bath detergents, liquid bath soaps, liquid shampoos, liquid conditioners, cosmetics such as lotions and milky lotions, and vacuum cleaners. It can also be used as various packaging materials such as heat insulators, batteries and the like.
  • Polyester polyol (B1-1) Ethylene glycol: 6.4 parts, neopentyl glycol: 22.3 parts, 1,6-hexanediol: 9.9 parts, isophthalate were added to a polyester reaction vessel equipped with a stirrer, a nitrogen gas inlet tube, a Snyder tube, and a condenser.
  • Acid 17.3 parts, terephthalic acid: 21.3 parts, adipic acid: 11.9 parts, monomer acid: 0.2 parts, dimer acid: 6.4 parts, trimer acid: 1.3 parts, tetramer acid: 0.2 parts of titanium tetraisopropoxide and 10 ppm of titanium tetraisopropoxide were charged, and the inside temperature was maintained at 260°C by gradually heating so that the temperature at the top of the rectifying tube did not exceed 100°C. After the acid value fell below the specified value, the reaction was continued for an additional hour. The pressure was reduced to 30 mmHg and held for 3 hours to obtain an intermediate polyester polyol having a solid content acid value of 0.6 mgKOH/g and a hydroxyl value of 20 mgKOH/g. Yield was 85%.
  • Isophorone diisocyanate 2.4 parts by mass was added to 100 parts by mass of the obtained intermediate polyester polyol, and the mixture was heated to 50 to 90 ° C. to perform a urethanization reaction until free NCO groups were substantially eliminated, and the hydroxyl value was A polyester polyurethane polyol of 8 mg KOH/g was obtained. This was diluted with ethyl acetate and 200 ppm of dibutyltin dilaurate was added to the polyester polyurethane polyol (solid content) to obtain a polyester polyol (B1-1) having a polyester polyurethane polyol solid content of 60%.
  • Polyester polyol (B1-2) Ethylene glycol: 8.2 parts, diethylene glycol: 7.3 parts, neopentyl glycol: 4.5 parts, 1,6-hexanediol were added to a polyester reaction vessel equipped with an agitator, a nitrogen gas inlet tube, a Snyder tube, and a condenser.
  • Example 1 Carbodiimide-modified diphenylmethane diisocyanate (Lupranate MM-103B, manufactured by BASF INOAC Polyurethane), trimethylolpropane adduct of toluene diisocyanate (Desmodur L75, manufactured by Covestro), biuret of hexamethylene diisocyanate (Desmodur N3210A, manufactured by Covestro) , and polyester polyol (B1-1) in the formulation shown in Table 1 to prepare the adhesive of Example 1.
  • Adhesives of Examples 2 to 6 were prepared in the same manner as in Example 1 except that the polyisocyanate compounds (A1), (A2) and polyester polyol (B1) used and their formulations were changed to those shown in Tables 1 and 2. was prepared.
  • the allophanate form of hexamethylene diisocyanate in the table is Duranate D101 manufactured by Asahi Kasei Corporation.
  • Comparative Example 1 Adhesives of Comparative Examples 1 and 2 were prepared in the same manner as in Example 1 except that the polyisocyanate compounds (A1), (A2) and polyester polyol (B1) used and their formulations were changed to those shown in Table 2.
  • the compounding amount in the table is the solid content amount, and (A1) / ((A1) + (A2)) is the ratio of the polyisocyanate compound (A1) to the total amount of the polyisocyanate compounds (A1) and (A2) ( % by mass), and [NCO]/[OH] is the molar ratio between the isocyanate groups contained in the polyisocyanate composition (X) and the hydroxyl groups contained in the polyol composition (Y).
  • the adhesive of Examples or Comparative Examples was applied to the aluminum foil surface of the laminate so that the coating amount was 3.5 g/m 2 (solid content), and dried by volatilizing ethyl acetate with a dryer set at a temperature of 70 degrees. bottom. An adhesive and a CPP film with a thickness of 70 ⁇ m were laminated together. Aging was performed at 40° C. for 3 days to obtain a laminate.
  • test piece was cut out from the laminate, folded with the CPP film facing inward, and heat-sealed on three sides with a width of 10 mm other than the fold. Next, a cut (notch) of 1.5 mm was provided at an arbitrary portion of the heat-sealed end to prepare a test piece. Twenty test pieces prepared in the same manner were placed near the hot water shower nozzle of a shower retort sterilizer (Flavor Ace, manufactured by Hisaka Seisakusho) so that the notch of each test piece was positioned, and the temperature was maintained at 135 ° C. for 30 minutes.
  • a shower retort sterilizer Fluvor Ace, manufactured by Hisaka Seisakusho
  • the retort treatment was performed under the conditions of The state of the test piece after retorting was evaluated as follows and summarized in Tables 1 and 2. 5: Less than 3 peels with a major diameter of 1 mm or less 4: 3 or more and less than 5 peels with a major diameter of 1 mm or less 3: 5 or more and less than 10 peels with a major diameter of 1 mm or less 2: Peeling with a major diameter of 1 mm or less 10 or more, or less than 5 peels exceeding 1 mm 1: 5 or more peels with a major diameter exceeding 1 mm
  • the adhesive of the present invention was excellent in normal state adhesive strength, hot adhesive strength, and retort resistance.
  • the adhesives of Comparative Examples were inferior in retort resistance to the adhesives of Examples.

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001107016A (ja) * 1999-08-02 2001-04-17 Takeda Chem Ind Ltd ラミネート用接着剤
JP2012201731A (ja) * 2011-03-24 2012-10-22 Dic Corp 接着剤及びそれを使用した酸素バリア性フィルム
JP2013129105A (ja) * 2011-12-21 2013-07-04 Dic Corp バリア性易開封ラミネートフィルム及びこれを用いる包装材
WO2017221661A1 (ja) * 2016-06-23 2017-12-28 Dic株式会社 ウレタン系接着剤、ウレタン系接着剤用ポリオール組成物、ウレタン系接着剤用ポリイソシアネート組成物、前記ウレタン系接着剤の硬化物、及び積層フィルム
JP2020094154A (ja) * 2018-12-14 2020-06-18 Dic株式会社 反応性接着剤、積層フィルム、及び包装体

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001107016A (ja) * 1999-08-02 2001-04-17 Takeda Chem Ind Ltd ラミネート用接着剤
JP2012201731A (ja) * 2011-03-24 2012-10-22 Dic Corp 接着剤及びそれを使用した酸素バリア性フィルム
JP2013129105A (ja) * 2011-12-21 2013-07-04 Dic Corp バリア性易開封ラミネートフィルム及びこれを用いる包装材
WO2017221661A1 (ja) * 2016-06-23 2017-12-28 Dic株式会社 ウレタン系接着剤、ウレタン系接着剤用ポリオール組成物、ウレタン系接着剤用ポリイソシアネート組成物、前記ウレタン系接着剤の硬化物、及び積層フィルム
JP2020094154A (ja) * 2018-12-14 2020-06-18 Dic株式会社 反応性接着剤、積層フィルム、及び包装体

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