WO2021039338A1 - Adhésif de type à deux composants, corps multicouche, corps moulé et matériau d'emballage - Google Patents

Adhésif de type à deux composants, corps multicouche, corps moulé et matériau d'emballage Download PDF

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Publication number
WO2021039338A1
WO2021039338A1 PCT/JP2020/030110 JP2020030110W WO2021039338A1 WO 2021039338 A1 WO2021039338 A1 WO 2021039338A1 JP 2020030110 W JP2020030110 W JP 2020030110W WO 2021039338 A1 WO2021039338 A1 WO 2021039338A1
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resin
polyhydric alcohol
acid
polyester polyol
layer
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PCT/JP2020/030110
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English (en)
Japanese (ja)
Inventor
裕季 小林
勉 菅野
倫康 村上
崇 三原
伊東　孝之
英美 中村
神山　達哉
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Dic株式会社
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Priority to JP2021509231A priority Critical patent/JP6892036B1/ja
Priority to CN202080042194.5A priority patent/CN113993966A/zh
Publication of WO2021039338A1 publication Critical patent/WO2021039338A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • 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
    • C08G18/28—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
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • 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
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a two-component adhesive, a laminate obtained by using the two-component adhesive, a molded body, and a packaging material.
  • Packaging materials used for packaging various stored items such as foods, daily necessities, and electronic elements are resistant to strength and cracking in order to protect the contents from impacts received during distribution and deterioration due to oxygen and moisture.
  • Gas barrier properties, etc. are required.
  • retort resistance, heat resistance, etc. are required, and transparency may be required so that the contents can be confirmed.
  • the non-stretched polyolefin film used when sealing by heat sealing is excellent in heat processability, but has insufficient oxygen barrier property.
  • Nylon film on the other hand, has excellent gas barrier properties, but is inferior in heat seal properties.
  • a laminate in which one or more storage portions are formed by molding the laminate may be used as a packaging material (Patent Document 1-3).
  • a laminate in which one or more storage portions are formed is joined to a laminate in which storage portions having the same shape are formed or a laminate in which no storage portion is formed (not molded). Seal the compartment. Heat fusion (heat sealing) is used as the joining method.
  • the present invention is a packaging material suitable for such applications, that is, it has excellent moldability, and even after heat fusion between the sealant layers performed for sealing the stored material, the adhesive strength between the layers does not decrease, and the layers do not deteriorate. It is an object of the present invention to provide a packaging material having no appearance defects such as floating. Another object of the present invention is to provide a two-component adhesive having excellent moldability and heat resistance, which is suitable for producing such a packaging material, and a laminate or a molded product using the same.
  • the present invention comprises a polyol composition (A) containing a polyester polyol (A1) and a polyisocyanate composition (B) containing an isocyanate compound (B1), wherein the polyester polyol (A1) is a polybasic acid or a derivative thereof.
  • a polyhydric alcohol (a2) which is a reaction product of (a1) and a polyhydric alcohol (a2) and in which the polyhydric alcohol (a2) has 5 or more and 19 or less carbon atoms in the methylene chain between two hydroxyl groups and is an odd number.
  • the present invention relates to a two-component adhesive comprising -1).
  • the two-component adhesive of the present invention has excellent moldability, and even after heat fusion between the sealant layers performed to seal the stored material, the adhesive strength between the layers does not decrease, and the layers do not deteriorate. It is possible to obtain a packaging material that does not have an appearance defect such as floating.
  • the adhesive of the present invention contains a polyol composition (A) containing a polyester polyol (A1) and a polyisocyanate composition (B) containing an isocyanate compound (B1) as essential components, and the polyester polyol (A1) is a polybase. It is a reaction product of an acid or its derivative (a1) and a polyhydric alcohol (a2), and the polyhydric alcohol (a2) has an odd number of carbon atoms in the methylene chain between two hydroxyl groups of 5 or more and 19 or less. It is a two-component adhesive containing a valent alcohol (a2-1).
  • polyester polyol (A1) is a reaction product of a polybasic acid or a derivative thereof (a1) and a polyhydric alcohol (a2).
  • Examples of the polybasic acid or its derivative (a1) used as a raw material of the polyester polyol (A1) include malonic acid, ethylmalonic acid, dimethylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, succinic acid anhydride, and alkenyl anhydride.
  • An aliphatic polybasic acid such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, malonic acid, malonic acid anhydride, and itaconic acid;
  • An aliphatic polybasic acid such as dimethyl malonate, diethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, diethyl pimelic acid, diethyl sebacate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate, etc.
  • Alkyl esterified product such as dimethyl malonate, diethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, diethyl pimelic acid, diethyl sebacate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate, etc.
  • 1,1-Cyclopentanedicarboxylic acid 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid , Tetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydrous, hymic anhydride, hetic anhydride, etc.
  • Group polybasic acid
  • Methyl esterified products of aromatic polybasic acids such as dimethyl terephthalic acid and dimethyl 2,6-naphthalenedicarboxylic acid; and the like; one type or a combination of two or more types can be used.
  • adipic acid, azelaic acid, sebacic acid, dimer acid, orthophthalic acid, isophthalic acid, terephthalic acid, trimellitic acid and their anhydrides and methyl ester compounds thereof are preferably used.
  • the polybasic acid or its derivative (a1) preferably contains a polybasic acid having an aromatic ring or its derivative (a1-1).
  • Orthophthalic acid, terephthalic acid, terephthalic acid, trimellitic acid and its anhydride and its methyl ester compound are preferable, and isophthalic acid, terephthalic acid, trimellitic acid and its acid anhydride and its methyl ester compound are more preferable.
  • the polyhydric alcohol (a2) may be a diol or a trifunctional or higher functional polyol, and the diol may be, for example, ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,2,2-trimethyl-1.
  • 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 lactanoid and ⁇ -caprolactone;
  • Bisphenols such as bisphenol A and bisphenol F;
  • Examples thereof include an alkylene oxide adduct of bisphenol obtained by adding ethylene oxide, proprene oxide, etc. to bisphenol such as bisphenol A and bisphenol F.
  • the trifunctional or higher functional polyol is an aliphatic polyol such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, or pentaerythritol;
  • Examples thereof include a lactone-based polyester polyol obtained by a polycondensation reaction between the aliphatic polyol and various lactones such as ⁇ -caprolactone.
  • the polyhydric alcohol (a2) contains, as an essential component, the polyhydric alcohol (a2-1) in which the number of carbon atoms of the methylene chain between the two hydroxyl groups is 5 or more and 19 or less and an odd number.
  • the methylene chain may be linear or branched with side chains. When the methylene chain contains a side chain, the number of carbon atoms in the side chain is not included in the number of carbon atoms in the methylene chain.
  • such a diol is also simply referred to as a polyhydric alcohol (a2-1).
  • Polyhydric alcohols (a2-1) having a linear methylene chain include 1,5-pentanediol, 1,7-heptandiol, 1,9-nonanediol, 1,11-undecanediol, and 1,13. Examples thereof include -tridecanediol, 1,15-pentadecanediol, 1,17-heptadecanediol, and 1,19-nonadecandiol.
  • Polyhydric alcohols (a2-1) having branched methylene chains include 1-methyl-1,5-pentanediol, 2-methyl-1,5-pentanediol, and 3-methyl-1,5-pentanediol.
  • the adhesive of the present invention can be made excellent in adhesiveness, moldability and heat resistance.
  • the reason for this is presumed as follows.
  • ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, and isosorbide are used in the main skeleton of the polyester polyol.
  • Succinic acid, 1,4-cyclohexanedicarboxylic acid, orthophthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, and other components that enhance the cohesiveness of polyester polyols are preferably incorporated.
  • the glass transition temperature of the polyester polyol rises, and the moldability and wettability of the adhesive decrease. The decrease in wettability causes a decrease in adhesiveness.
  • the polyester polyol (A1) using the polyhydric alcohol (a2-1) (a two-component adhesive using the polyhydric alcohol (a2-1)).
  • the blending amount of the component that enhances the cohesive force of the polyester polyol is appropriately set in consideration of the balance with other components. As an example, it is 30 mol% or more and 90 mol% or less of the total amount of the polybasic acid or its derivative (a1) and the polyhydric alcohol (a2).
  • the blending amount of the polyhydric alcohol (a2-1) may be appropriately adjusted in consideration of the degree of required moldability (molding temperature, molding depth, etc.).
  • the content of the polyhydric alcohol (a2) is preferably 10 mol% or more, more preferably 30 mol% or more, and 40 mol% or more. More preferably.
  • the upper limit is not particularly limited, but is preferably 90 mol% or less, more preferably 85 mol% or less, and even more preferably 80 mol% or less.
  • the number of carbon atoms in the methylene chain of the polyhydric alcohol (a2-1) is 5 or more and 11 or less, it is preferably 20 mol% or more, preferably 90 mol% or less of the polyhydric alcohol (a2). It is preferably 40 mol% or more and 80 mol% or less, more preferably.
  • the number of carbon atoms in the methylene chain of the polyhydric alcohol (a2-1) is 13 or more and 19 or less, it is preferably 10 mol% or more and 60 mol% or less, and 15 mol% or more and 40 mol% or less. More preferred.
  • the methylene chain of the polyhydric alcohol (a2-1) is preferably linear because it is excellent in both moldability and heat resistance.
  • the number of carbon atoms in the methylene chain is more preferably 7 or more and 15 or less, and more preferably 9 or more and 13 or less.
  • the polyhydric alcohol (a2) preferably further contains at least one selected from the group consisting of a polyhydric alcohol having a branched alkylene structure (a2-2) and a polyhydric alcohol having a cyclic structure (a2-3).
  • a polyhydric alcohol having a branched alkylene structure a2-2
  • a polyhydric alcohol having a cyclic structure a2-3
  • the polyhydric alcohol (a2-3) having a cyclic structure is also referred to as a polyhydric alcohol (a2-3). ..
  • the polyhydric alcohol (a2-2) is a polyhydric alcohol having a tertiary or quaternary carbon atom in the molecular structure, for example, 1,2-propanediol, 2-methyl-1,3-propanediol, neopentyl.
  • the polyhydric alcohol (a2-3) is a polyhydric alcohol having a cyclic structure in its molecular structure.
  • the cyclic structure may be monocyclic or polycyclic, and may be an aromatic ring type or an alicyclic type. It may be a heterocycle.
  • Examples of such polyhydric alcohol (a2-3) include 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, and 4- (hydroxymethyl) cyclo.
  • the solubility of the polyester polyol (A1) in an organic solvent decreases, and the cured coating film (adhesive layer) with the polyisocyanate composition (B) described later ) May decrease in elastic modulus.
  • the solubility in an organic solvent is lowered, the storage stability is lowered when the two-component adhesive of the present invention is made into a solvent type, and when the elastic modulus of the cured coating film is lowered, the adhesive layer is destroyed during the molding process.
  • the polyhydric alcohol (a2) contains at least one selected from the group consisting of the polyhydric alcohol (a2-2) and the polyhydric alcohol (a2-3), that is, the polyester polyol (A1) is the polyhydric alcohol.
  • the polyhydric alcohols (a2-2) and (a2-3) can be expected to have an effect of improving the hydrolysis resistance of the cured coating film.
  • the total amount of the polyhydric alcohol (a2-2) and the polyhydric alcohol (a2-3) is appropriately adjusted depending on the balance with other components, but as an example, it may be 10 mol% or more and 90 mol% or less. preferable. More preferably, it is 15 mol% or more and 70 mol% or less, and 20 mol% or more and 60 mol% or less.
  • the polyhydric alcohol (a2) may contain a polyhydric alcohol (a-4) other than the polyhydric alcohols (a2-1) to (a2-3) as long as the effects of the present invention are not impaired.
  • the polyester polyol (A1) may be a polyester polyurethane polyol containing a polybasic acid or a derivative thereof (a1), a polyhydric alcohol (a2), and a polyisocyanate as essential raw materials.
  • the polyisocyanate used in that case include a diisocyanate compound and a trifunctional or higher functional polyisocyanate compound.
  • Each of these polyisocyanates may be used alone, or two or more of them may be used in combination.
  • diisocyanate compound examples include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, and m-tetramethylxylylene diisocyanate.
  • Aliphatic diisocyanates such as isocyanate and lysine diisocyanate;
  • Cyclohexane-1,4-diisocyanate isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexanediisocyanate, isopropyridene dicyclohexyl-4,4'-diisocyanate, norbornane diisocyanate, etc.
  • Alicyclic diisocyanate isophorone diisocyanate
  • dicyclohexylmethane-4,4'-diisocyanate 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexanediisocyanate, isopropyridene dicyclohexyl-4,4'-diisocyanate, norbornane diisocyanate, etc.
  • Alicyclic diisocyanate isophorone diisocyanate,
  • 1,5-naphthylene diisocyanis 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyldiisocyanate , Dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylenediisocyanate, 1,4-phenylenediisocyanate, tolylene diisocyanate and other aromatic diisocyanates.
  • Examples of the trifunctional or higher functional polyisocyanate compound include a diisocyanate oligomer, an adduct-type polyisocyanate compound having a urethane bond site in the molecule, and a nurate-type polyisocyanate compound having an isocyanurate ring structure in the molecule.
  • the adduct-type polyisocyanate compound having a urethane bond site in the molecule is obtained, for example, by reacting a diisocyanate compound with a polyhydric alcohol.
  • the diisocyanate compound used in the reaction include various diisocyanate compounds exemplified as the diisocyanate compound, and these may be used alone or in combination of two or more.
  • the polyol compound used in the reaction include various polyol compounds exemplified as the polyhydric alcohol (a2), polyester polyol obtained by reacting the polyhydric alcohol with a polybasic acid, and the like, respectively. It may be used alone or in combination of two or more.
  • a nurate-type polyisocyanate compound having an isocyanurate ring structure in the molecule is obtained, for example, by reacting a diisocyanate compound with a monoalcohol and / or a diol.
  • the diisocyanate compound used in the reaction include various diisocyanate compounds exemplified as the diisocyanate compound, and these may be used alone or in combination of two or more.
  • the monoalcohols used in the reaction include hexanol, 2-ethylhexanol, octanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, n-pentadecanol, and n-.
  • the polyester polyol (A1) used in the present invention is a reaction product of a polybasic acid or a derivative thereof (a1) and a polyvalent alcohol (a2), and forms an aromatic ring in the polybasic acid or a derivative thereof (a1).
  • the proportion of the polybasic acid or its derivative (a1-1) is preferably 30 mol% or more. This makes it possible to obtain an adhesive having excellent storage stability. Further, since moldability and heat resistance are improved, the ratio of the polybasic acid having an aromatic ring or its derivative (a1-1) in the polybasic acid or its derivative (a1) is 50 mol% or more. It is preferably 70 mol% or more, more preferably 96 mol% or more. All of the polybasic acid or its derivative (a1) may be a polybasic acid having an aromatic ring or a derivative thereof (a1-1).
  • the polyester polyol (A1) used in the present invention may be a reaction product of a polybasic acid or a derivative thereof (a1), a polyvalent alcohol (a2), and a polyisocyanate, and the polybasic acid or a derivative thereof.
  • the ratio of the polybasic acid having an aromatic ring or its derivative (a1-1) in (a1) is preferably 30 mol% or more. This makes it possible to obtain an adhesive having excellent storage stability. Further, since moldability and heat resistance are improved, the ratio of the polybasic acid having an aromatic ring or its derivative (a1-1) in the polybasic acid or its derivative (a1) is 50 mol% or more. It is preferably 70 mol% or more, more preferably 96 mol% or more. All of the polybasic acid or its derivative (a1) may be a polybasic acid having an aromatic ring or a derivative thereof (a1-1).
  • the hydroxyl value of the polyester polyol (A1) used in the present invention is preferably in the range of 1 to 40 mgKOH / g, more preferably 3 mgKOH / g or more, and 30 mgKOH / g or less because it is superior in adhesive strength. is there.
  • the number average molecular weight (Mn) of the polyester polyol (A1) used in the present invention is preferably in the range of 2,000 to 100,000 because it is superior in adhesive strength when used for adhesive applications. 000 to 50,000 is still preferred. When the number average molecular weight is less than 2,000, the crosslink density in the cured coating film becomes too high, and the appearance and moldability of the laminated body may be deteriorated. On the other hand, the weight average molecular weight (Mw) is preferably in the range of 5,000 to 300,000, and more preferably in the range of 10,000 to 200,000.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC) under the following conditions.
  • HLC-8320GPC manufactured by Tosoh Corporation Column; Tosoh Corporation TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL Detector; RI (Differential Refractometer) Data processing; Multi-station GPC-8020modelII manufactured by Tosoh Corporation Measurement conditions; column temperature 40 ° C Solvent tetrahydrofuran Tetrahydrofuran flow velocity 0.35 ml / min Standard; Monodisperse polystyrene sample; 0.2 mass% tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 ⁇ l)
  • the solid acid value of the polyester polyol (A1) used in the present invention is not particularly limited, but is preferably 10.0 mgKOH / g or less. It is preferable that the amount is 5.0 mgKOH / g or less because of its excellent moisture and heat resistance.
  • the lower limit of the solid acid value is not particularly limited, but is 0.5 mgKOH / g or more as an example. It may be 0 mgKOH / g.
  • the glass transition temperature of the polyester polyol (A1) used in the present invention is preferably ⁇ 30 ° C. or higher and 20 ° C. or lower. When the glass transition temperature of the polyester polyol (A1) is in this range, an adhesive having excellent adhesive strength, moldability, heat resistance, and moisture heat resistance can be obtained when used in combination with the resin (A2) described later.
  • the glass transition temperature of the polyester polyol (A1) is more preferably ⁇ 20 ° C. or higher, and more preferably 15 ° C. or lower.
  • the glass transition temperature in the present invention refers to a value measured as follows. Using a differential scanning calorimetry device (DSC-7000 manufactured by SII Nanotechnology Co., Ltd., hereinafter referred to as DSC), 5 mg of the sample was heated from room temperature to 200 ° C. at 10 ° C./min under a nitrogen stream of 30 mL / min. After that, it is cooled to ⁇ 80 ° C. at 10 ° C./min. The DSC curve was measured by raising the temperature to 150 ° C at 10 ° C / min again, and the straight line extending the baseline on the low temperature side to the high temperature side in the measurement results observed in the second temperature rise step and the glass transition staircase.
  • DSC-7000 differential scanning calorimetry device manufactured by SII Nanotechnology Co., Ltd.
  • the intersection with the tangent line drawn at the point where the slope of the curve of the shaped portion is maximized is defined as the glass transition point, and the temperature at this time is defined as the glass transition temperature.
  • the temperature is raised to 200 ° C. at the first temperature rise, but this may be a temperature at which the polyester polyol (A1) is sufficiently melted, and if 200 ° C. is insufficient, the temperature is appropriately adjusted.
  • the cooling temperature of ⁇ 80 ° C. is insufficient (for example, when the glass transition temperature is lower), the cooling temperature is adjusted as appropriate.
  • the reaction of the polybasic acid or its derivative with the polyhydric alcohol, or the reaction of the polybasic acid or its derivative with the polyhydric alcohol and the polyisocyanate may be carried out by a known method.
  • the reaction of a polybasic acid or a derivative thereof with the polyhydric alcohol can be carried out by a polycondensation reaction.
  • the reaction of the polybasic acid or its derivative with the polyhydric alcohol and the polyisocyanate requires a polyester polyol obtained by reacting the polybasic acid or its derivative with the polyhydric alcohol by the method and the polyisocyanate.
  • the polyester polyol (A1) of the present invention can be obtained by reacting in the presence of a known and commonly used urethanization catalyst.
  • the polybasic acid or a derivative thereof, the polyhydric alcohol, and a polymerization catalyst are charged into a reaction vessel equipped with a stirrer and a rectification facility, and the mixture is stirred.
  • the temperature is raised to about 130 ° C. at normal pressure.
  • the generated water is distilled off while raising the temperature at a reaction temperature in the range of 130 to 260 ° C. at a rate of 5 to 10 ° C. per hour.
  • the polyester polyol (A1) is produced by distilling off excess polyhydric alcohol and accelerating the reaction while gradually increasing the degree of depressurization from normal pressure to the range of 1 to 300 trr. Can be manufactured.
  • the polymerization catalyst used in the esterification reaction is composed of at least one metal selected from the group consisting of groups 2, 4, 12, 13, 14, and 15 of the periodic table, or a compound of the metal.
  • a polymerization catalyst is preferred.
  • the polymerization catalyst composed of such a metal or a metal compound thereof include metals such as Ti, Sn, Zn, Al, Zr, Mg, Hf, and Ge, compounds of these metals, and more specifically, titanium tetraisopropoxide and titanium.
  • Tetrabutoxide titaniumoxyacetylacetonate, tin octanoate, 2-ethylhexanetin, acetylacetonate zinc, zirconium tetrachloride, zirconium tetrachloride tetrahydrofuran complex, hafnium tetrachloride, hafnium tetrachloride tetrahydrofuran complex, germanium oxide, tetraethoxygermanium And so on.
  • Preferred examples include catalysts and inorganic tin compounds.
  • the amount of these polymerization catalysts used is not particularly limited as long as the esterification reaction can be controlled and a polyester polyol (A1) of good quality can be obtained, but as an example, a polybasic acid or a derivative thereof and a polyhydric alcohol are used. It is 10 to 1000 ppm, preferably 20 to 800 ppm with respect to the total amount of. In order to suppress the coloring of the polyester polyol (A1), it is more preferably 30 to 500 ppm.
  • the polyester polyurethane polyol used in the present invention is obtained by chain-extending the polyester polyol obtained by the above method with polyisocyanate.
  • a polyester polyol, a polyisocyanate, a chain extension catalyst, and a good solvent of the polyester polyol and the polyisocyanate used as needed are charged in a reaction vessel, and the reaction temperature is 60 to 90 ° C. Stir with. The reaction is carried out until the isocyanate group derived from the polyisocyanate used is substantially eliminated to obtain the polyester polyurethane polyol used in the present invention.
  • the chain extension catalyst a known and public catalyst used as a normal urethanization catalyst can be used. Specific examples thereof include organic tin compounds, organic carboxylic acid tin salts, lead carboxylates, bismuth carboxylates, titanium compounds, zirconium compounds and the like, which can be used alone or in combination.
  • the amount of the chain extension catalyst used may be an amount that sufficiently promotes the reaction between the polyester polyol and the polyisocyanate, and specifically, 5.0 mass by mass with respect to the total amount of the polyester polyol and the polyisocyanate. % Or less is preferable. In order to suppress hydrolysis and coloring of the resin by the catalyst, 1.0% by mass or less is more preferable. Further, these chain extension catalysts may be used in consideration of the action of the polyol composition (A) and the isocyanate composition (B) described later as a curing catalyst.
  • Examples of a good solvent used for producing a polyester polyurethane polyol include ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, toluene, xylene and the like. It may be used alone or in combination of two or more.
  • the polyol composition (A) of the present invention preferably contains a resin (A2) having a glass transition temperature of 50 ° C. or higher and 110 ° C. or lower because the adhesiveness, moldability, and heat resistance can be improved. ..
  • a resin (A2) is difficult to be compatible with the polyester polyol (A1) and forms a sea-island structure in a cured coating film, so that the polyester polyol (A1) has excellent wettability, adhesiveness, and moldability to a base material.
  • the portion derived from the polyester polyol (A1) of the cured coating film decreases under high temperature and high humidity, the portion derived from the resin (A2) is pseudo-like a filler. It is considered that the adhesive layer is hard to soften to play a role and exhibits good adhesiveness and heat resistance.
  • the resin (A2) can be used without particular limitation as long as the glass transition temperature is 50 ° C. or higher and 110 ° C. or lower.
  • polyester resin, polyurethane resin, polyurea resin, acrylic resin, polyamide resin, polyimide resin, epoxy resin, rosin Examples include modified epoxy resins.
  • the resin (A2) is not completely compatible with the polyester polyol (A1), and 50 parts by mass of the polyester polyol (A1) and the resin (A2).
  • the peak derived from the polyester polyol (A1) and the resin (A2) were added to the loss tangent (tan ⁇ ) when the dynamic viscoelasticity of the composition obtained by adding 30 parts by mass of the trimethylolpropane adduct of toluene diisocyanate to the mass part was measured. ) Derived peak can be confirmed.
  • the resin (A2) may or may not have a functional group such as a hydroxyl group, a carboxyl group, an amino group, an amide group, a thiol group, and a glycidyl group.
  • the resin (A2) When the resin (A2) has a hydroxyl group, it is preferably a secondary or tertiary hydroxyl group.
  • the hydroxyl value of the resin (A2) is preferably in the range of 1 to 40 mgKOH / g, more preferably 3 mgKOH / g or more, and 30 mgKOH / g or less because it is more excellent in adhesive strength. Further, the hydroxyl value of the resin (A2) is preferably equal to or lower than the hydroxyl value of the polyester polyol (A1).
  • the solid acid value of the resin (A2) is not particularly limited, but is preferably 10.0 mgKOH / g or less. It is preferable that the amount is 5.0 mgKOH / g or less because of its excellent moisture and heat resistance.
  • the lower limit of the solid acid value is not particularly limited, but is 0.5 mgKOH / g or more as an example.
  • the glass transition temperature of the resin (A2) is 50 ° C. or higher and 110 ° C. or lower. When the glass transition temperature of the resin (A2) is in this range, it is possible to obtain an adhesive having excellent adhesive strength, moldability, heat resistance, and moisture heat resistance when used in combination with the polyester polyol (A1).
  • the glass transition temperature of the resin (A2) is more preferably 60 ° C. or higher, and more preferably 65 ° C. or higher. Further, the glass transition temperature of the resin (A2) is more preferably 100 ° C. or lower, and more preferably 90 ° C. or lower.
  • the blending amount of the resin (A2) is not particularly limited because it is appropriately adjusted depending on the degree of heat resistance required, but it may be 90 parts by mass or less with respect to 100 parts by mass in total of the polyester polyol (A1) and the resin (A2). preferable. It is more preferably 3 parts by mass or more and 65 parts by mass or less, and further preferably 5 parts by mass or more and 50 parts by mass or less. As a result, the adhesiveness, moldability, heat resistance, and moisture heat resistance can be improved more reliably.
  • the polyisocyanate composition (B) used in the present invention contains an isocyanate compound (B).
  • the isocyanate compound (B) is not particularly limited as long as it is a compound having two or more isocyanate groups in one molecule, and various compounds can be used.
  • the above-mentioned polyester polyol (A1), various diisocyanate compounds described as raw materials for the polyester polyol (A2), oligomers of diisocyanate compounds, and adduct-modified diisocyanates obtained by reacting various diisocyanate compounds with diol compounds.
  • Compounds, modified biuret compounds, modified allophanates, and various trifunctional or higher polyisocyanate compounds can be used.
  • Each of these isocyanate compounds (B) may be used alone, or two or more of them may be used in combination.
  • the polyol composition (A) may contain a polyester polyol (A1) and a polyester polyol (A3) that does not correspond to the resin (A2).
  • the polyester polyol (A3) is a polyester polyol which is a reaction product of a polybasic acid or a derivative thereof and a polyhydric alcohol, or a polyester which is a reaction product of a polybasic acid or a derivative thereof, a polyhydric alcohol and a polyisocyanate.
  • Polyurethane polyol can be used.
  • polyhydric alcohol and polyisocyanate used for the synthesis of the polyester polyol (A3) the same ones as those of the polyester polyol (A1) can be used.
  • the polyester polyol (A3) is preferably a polyester polyol or a polyester polyurethane polyol in which the proportion of the polybasic acid having an aromatic ring or its derivative in the polybasic acid or its derivative is 30 mol% or more. This makes it possible to obtain an adhesive having excellent storage stability. Further, since moldability and heat resistance are improved, the proportion of the polybasic acid having an aromatic ring or its derivative in the polybasic acid or its derivative is more preferably 50 mol% or more, and more preferably 70 mol% or more. Is more preferable, and 96 mol% or more is more preferable. All of the polybasic acid or its derivative may be a polybasic acid having an aromatic ring or a derivative thereof.
  • the hydroxyl value of the polyester polyol (A3) is preferably in the range of 1 to 40 mgKOH / g, more preferably 3 mgKOH / g or more, and 30 mgKOH / g or less because it is superior in adhesive strength.
  • the number average molecular weight (Mn) of the polyester polyol (A3) is preferably in the range of 2,000 to 100,000, preferably in the range of 2,000 to 50, because it is superior in adhesive strength when used in adhesive applications. 000 is still preferable. When the number average molecular weight is less than 2,000, the crosslink density in the cured coating film becomes too high, and the appearance and moldability of the laminated body may be deteriorated. On the other hand, the weight average molecular weight (Mw) is preferably in the range of 5,000 to 300,000, and more preferably in the range of 10,000 to 200,000.
  • the solid acid value of the polyester polyol (A3) is not particularly limited, but is preferably 10.0 mgKOH / g or less. It is preferable that the amount is 5.0 mgKOH / g or less because of its excellent moisture and heat resistance.
  • the lower limit of the solid acid value is not particularly limited, but is 0.5 mgKOH / g or more as an example. It may be 0 mgKOH / g.
  • the glass transition temperature of the polyester polyol (A3) is preferably ⁇ 30 ° C. or higher and 20 ° C. or lower, more preferably ⁇ 20 ° C. or higher, and even more preferably 15 ° C. or lower.
  • the blending amount of the polyester polyol (A3) is not particularly limited, but it is preferably 90 parts by mass or less with respect to a total of 100 parts by mass of the polyester polyol (A1) and the polyester polyol (A3). It is more preferably 3 parts by mass or more and 65 parts by mass or less, and further preferably 3 parts by mass or more and 50 parts by mass or less.
  • the polyol composition contains a polyester polyol (A1), a resin (A2), and a polyester polyol (A3)
  • the blending amount of the resin (A2) is 3 parts by mass or more and 65 parts by mass with respect to 100 parts by mass in total. It is preferably less than a part.
  • the polyol composition (A) preferably contains a polycarbonate polyol compound.
  • the total amount of the polyester polyol (A1) and the resin (A2) and the blending ratio of the polycarbonate polyol compound are high in adhesiveness to various base materials and excellent in moisture and heat resistance.
  • the total mass of the polyester polyol (A1) and the resin (A2) is preferably in the range of 30 to 99.5% by mass, and preferably in the range of 60 to 99% by mass with respect to the mass.
  • the number average molecular weight (Mn) of the polycarbonate polyol compound is preferably in the range of 300 to 2,000 because it is an adhesive having high adhesiveness to various substrates and excellent moisture and heat resistance.
  • the hydroxyl value is preferably in the range of 30 to 250 mgKOH / g, and more preferably in the range of 40 to 200 mgKOH / g.
  • the polycarbonate polyol compound is preferably a polycarbonate diol compound.
  • the polyol composition (A) preferably contains a polyoxyalkylene-modified polyol compound.
  • the total amount of the polyester polyol (A1) and the resin (A2) and the blending ratio of the polyoxyalkylene-modified polyol compound are high in adhesiveness to various substrates and excellent in moisture and heat resistance.
  • the total mass of the polyester polyol (A1) and the resin (A2) is preferably in the range of 30 to 99.5% by mass, and preferably in the range of 60 to 99% by mass with respect to the total mass of both.
  • the number average molecular weight (Mn) of the polyoxyalkylene-modified polyol compound is preferably in the range of 300 to 2,000 because it is an adhesive having high adhesiveness to various substrates and excellent moisture and heat resistance.
  • the hydroxyl value is preferably in the range of 40 to 250 mgKOH / g, and more preferably in the range of 50 to 200 mgKOH / g.
  • the polyoxyalkylene-modified polyol compound is preferably a polyoxyalkylene-modified diol compound.
  • the polyol composition (A) may contain other resin components in addition to the polyester polyol (A1) and the resin (A2). When other resin components are used, it is preferably used in an amount of 50% by mass or less, preferably 30% by mass or less, based on the total mass of the main agent. Specific examples of other resin components include epoxy resins.
  • the epoxy resin is, for example, a bisphenol type epoxy resin such as a bisphenol A type epoxy resin or a bisphenol F type epoxy resin; a biphenyl type epoxy resin such as a biphenyl type epoxy resin or a tetramethyl biphenyl type epoxy resin; a dicyclopentadiene-phenol addition reaction type. Epoxy resin and the like can be mentioned. Each of these may be used alone, or two or more types may be used in combination. Among these, it is preferable to use a bisphenol type epoxy resin because it is an adhesive having high adhesiveness to various substrates and excellent moisture and heat resistance.
  • the number average molecular weight (Mn) of the epoxy resin is preferably in the range of 300 to 2,000 because it is an adhesive having high adhesiveness to various substrates and excellent moisture and heat resistance.
  • the epoxy equivalent is preferably in the range of 150 to 1000 g / equivalent.
  • the total amount of the polyester polyol (A1) and the resin (A2) and the compounding ratio of the epoxy resin are high in adhesiveness to various base materials and excellent in moisture and heat resistance.
  • the total mass of the polyester polyol (A1) and the resin (A2) is preferably in the range of 30 to 99.5 mass%, and preferably in the range of 60 to 99 mass% with respect to the total mass of.
  • the polyol composition (A) used in the present invention may contain a tackifier.
  • the tackifier include a rosin-based or rosin ester-based tackifier, a terpene-based or terpene-phenol-based tackifier, a saturated hydrocarbon resin, a kumaron-based tackifier, a kumaron-inden-based tackifier, and a styrene resin-based tackifier.
  • examples thereof include a tackifier, a xylene resin-based tackifier, a phenol resin-based tackifier, a petroleum resin-based tackifier, and a ketone resin-based tackifier.
  • Ketone resin-based tackifiers are preferable, and ketone resin-based tackifiers are more preferable. Each of these may be used alone, or two or more types may be used in combination.
  • the total mass of the polyester polyol (A1) and the resin (A2) is 80 to 99.99% by mass with respect to the total mass of the polyester polyol (A1), the resin (A2) and the tackifier. It is preferably 85 to 99.9% by mass, and more preferably 85 to 99.9% by mass.
  • rosin-based or rosin ester-based rosins examples include polymerized rosins, disproportionated rosins, hydrogenated rosins, maleated rosins, fumarized rosins, and their glycerin esters, pentaerythritol esters, methyl esters, ethyl esters, butyl esters, and ethylene glycols. Examples thereof include esters, diethylene glycol esters and triethylene glycol esters.
  • terpene type or terpene phenol type examples include low-polymerization terpene type, ⁇ -pinene polymer, ⁇ -pinene polymer, terpene phenol type, aromatic-modified terpene type, and hydrogenated terpene type.
  • Petroleum resin systems include petroleum resins obtained by polymerizing petroleum distillates having 5 carbon atoms obtained from penten, pentadiene, isoprene, etc., inden, methylinden, vinyltoluene, styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, etc.
  • phenol resin system a condensate of phenols and formaldehyde can be used.
  • the phenols include phenol, m-cresol, 3,5-xylenol, p-alkylphenol, resorcin, etc., and these phenols and formaldehyde are subjected to an addition reaction with an alkali catalyst, or a condensation reaction is carried out with an acid catalyst. Examples thereof include Novolac obtained in the above. Further, a rosin phenol resin obtained by adding phenol to rosin with an acid catalyst and thermally polymerizing it can also be exemplified.
  • ketone resin examples include known and commonly used ones, but formaldehyde resin, cyclohexanone / formaldehyde resin, ketone aldehyde condensed resin and the like can be preferably used.
  • a tackifier having various softening points can be obtained, but the softening point is 70 to 70 or more in terms of compatibility, color tone, thermal stability, etc. when mixed with other resins constituting the polyol composition (A).
  • a ketone resin-based tackifier at 160 ° C., preferably 80 to 100 ° C., or a rosin-based resin having a softening point of 80 to 160 ° C., preferably 90 to 110 ° C. and a hydrogenated derivative thereof are preferable, and a softening point is 70 to 160.
  • a ketone resin-based tackifier at ° C., preferably 80 to 100 ° C. is more preferable.
  • a ketone resin-based tackifier and a hydrogenated rosin-based tackifier having an acid value of 2 to 20 mgKOH / g and a hydroxyl value of 10 mgKOH / g or less are preferable, and an acid value of 2 to 20 mgKOH / g and a hydroxyl value is preferable.
  • a ketone resin-based tackifier having a value of 10 mgKOH / g or less is more preferable.
  • Phosphoric acids or derivatives thereof used here include phosphoric acids such as hypophosphoric acid, phosphoric acid, orthophosphoric acid, and hypophosphoric acid, such as metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, and ultraphosphoric acid.
  • phosphoric acids such as hypophosphoric acid, phosphoric acid, orthophosphoric acid, and hypophosphoric acid, such as metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, and ultraphosphoric acid.
  • condensed phosphoric acids such as monomethyl orthophosphate, monoethyl orthophosphate, monopropyl orthophosphate, monobutyl orthophosphate, mono-2-ethylhexyl orthophosphate, monophenyl orthophosphate, monomethyl phosphite, monoethyl phosphite, phosphite.
  • phosphoric acids or derivatives thereof may be used alone or in combination of two or more. As a method of containing, it is sufficient to simply mix.
  • an adhesion promoter can also be used in the adhesive of the present invention.
  • the adhesion accelerator include a silane coupling agent, a titanate-based coupling agent, an aluminum-based coupling agent, an epoxy resin, and the like.
  • silane coupling agent examples include ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, and N- ⁇ (aminoethyl) - ⁇ .
  • Aminosilanes such as -aminopropyltrimethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane; ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -gly Epoxysilanes such as sidoxylpropyltriethoxysilane; vinylsilanes such as vinyltris ( ⁇ -methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane; hexamethyldisilazane, ⁇ -mercapto Propyltrimethoxysilane and the like can be mentioned.
  • titanate-based coupling agent examples include tetraisopropoxytitanium, tetra-n-butoxytitanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate, titanium lactate, and tetrastearoxy. Titanium and the like can be mentioned.
  • aluminum-based coupling agent for example, acetalkoxyaluminum diisopropylate and the like can be mentioned.
  • the content (solid content) of the adhesion accelerator is preferably 0.1 part by mass or more, and preferably 0.3 part by mass or more, based on 100 parts by mass of the solid content of the polyol composition (A). It is more preferably 0.5 parts by mass or more, further preferably 0.7 parts by mass or more.
  • the content (solid content) of the adhesion accelerator is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and 5 parts by mass with respect to 100 parts by mass of the solid content of the polyol composition (A). More preferably, it is less than or equal to a portion.
  • the compounding ratio of the polyol composition (A) and the polyisocyanate composition (B) is the total number of moles [OH] of hydroxyl groups contained in the polyol composition (A) and the polyisocyanate composition.
  • the ratio [NCO] / [OH] to the number of moles [NCO] of the isocyanate group contained in (B) is preferably in the range of 1.5 to 15.0. As a result, it becomes a two-component adhesive having excellent moldability, heat resistance, and moisture heat resistance.
  • the excess amount of the isocyanate compound present in the two-component adhesive becomes a polymer or oligomer having a urea bond by moisture curing and contributes to the improvement of heat resistance and moisture heat resistance of the cured coating film. Therefore, when the [NCO] / [OH] ratio is relatively small, for example, when it is about 1.5, the heat resistance and the heat resistance to moisture and humidity may not be sufficient. In that case, for example, the resin (A) in the polyol composition (A) ( This can be dealt with by increasing the blending amount of A2).
  • the coating film may be too hard due to the influence of the crosslink density, the polymer having a urea bond, and the oligomer, and the moldability may be deteriorated.
  • it can be dealt with by increasing the blending amount of the polyester polyol (A1) in the polyol composition (A).
  • the [NCO] / [OH] ratio is 2.0 to 10 in order to surely improve the heat resistance and the heat resistance to moisture while ensuring the degree of freedom in designing the two-component adhesive. More preferably, it is 5.5 to 8.0.
  • the adhesive of the present invention may be in either a solvent type or a solventless type.
  • the "solvent type" adhesive referred to in the present invention means that the adhesive is applied to a base material and then heated in an oven or the like to volatilize the organic solvent in the coating film and then bonded to another base material.
  • Either one or both of the polyol composition (A) and the polyisocyanate composition (B) can dissolve the polyol composition (A) or the polyisocyanate composition (B) used in the present invention. Contains highly soluble organic solvent.
  • the organic solvent used as the reaction medium in the production of the constituent components of the polyol composition (A) or the polyisocyanate composition (B) may be further used as a diluent in coating.
  • highly soluble organic solvents 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 aromatics such as toluene and xylene.
  • groups thereof include group hydrocarbons, halogenated hydrocarbons such as methylene chloride and ethylene chloride, dimethyl sulfoxide, dimethyl sulfoamide and the like.
  • the “solvent-free” adhesive is substantially the highly soluble organic solvent as described above in the polyol composition (A) and the polyisocyanate composition (B), particularly ethyl acetate or methyl ethyl ketone.
  • a form of adhesive used in the so-called non-solvent laminating method which is a method in which an adhesive is applied to a base material and then bonded to another base material without a step of heating in an oven or the like to volatilize the solvent. Point to.
  • the constituent components of the polyol composition (A) or the polyisocyanate composition (B) and the organic solvent used as the reaction medium in the production of the raw material thereof could not be completely removed, and the polyol composition (A) or the polyisocyanate composition (A) or the polyisocyanate composition ( If a small amount of organic solvent remains in B), it is understood that the organic solvent is substantially not contained.
  • the polyol composition (A) contains a low molecular weight alcohol
  • the low molecular weight alcohol reacts with the polyisocyanate composition (B) and becomes a part of the coating film, so that it is not necessary to volatilize after coating. Therefore, such a form is also treated as a solvent-free adhesive.
  • the viscosity can be reduced by diluting the solvent, so that the polyol composition (A) or the polyisocyanate composition (B) to be used can be used even if it has a slightly high viscosity. ..
  • the polyisocyanate composition (B) has an aromatic concentration that induces an increase in viscosity. Reduced ones are often used.
  • the adhesive of the present invention contains various additives such as an ultraviolet absorber, an antioxidant, a silicon-based additive, a fluorine-based additive, a rheology control agent, a defoaming agent, an antistatic agent, and an antifogging agent. good.
  • the use of the adhesive of the present invention is not particularly limited, but it can be suitably used as a packaging material for batteries as an example because it is excellent in adhesive strength, moldability, moisture heat resistance, and heat resistance.
  • the laminate of the present invention can be obtained by laminating a plurality of base materials by a dry laminating method or a non-solvent laminating method using the adhesive of the present invention.
  • the base material paper, olefin resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, carbonate resin, polyamide resin, Examples thereof include polyimide resins, polyphenylene ether resins, synthetic resin films obtained from polyphenylene sulfide resins and polyester resins, copper foils, metal foils such as aluminum foils, and the like.
  • the film thickness of the base material is not particularly limited, and is selected from, for example, 10 to 400 ⁇ m.
  • the surface of the base material to which the adhesive is applied may be surface-treated. Examples of this surface treatment include corona treatment, plasma treatment, ozone treatment, flame treatment, radiation treatment and the like.
  • the packaging material for a battery is composed of at least a laminate in which an outer layer side base material layer 1, an adhesive layer 2, a metal layer 3, and a sealant layer 4 are sequentially laminated.
  • the outer layer side base material layer 1 is the outermost layer
  • the sealant layer 4 is the innermost layer. That is, when the battery is assembled, the sealant layers 4 located on the peripheral edge of the battery element are heat-sealed to seal the battery element, thereby sealing the battery element.
  • the adhesive of the present invention is used for the adhesive layer 2.
  • an adhesive layer 5 is provided between the metal layer 3 and the sealant layer 4 as needed for the purpose of enhancing their adhesiveness. You may.
  • the outer layer side base material layer 1 is a layer forming the outermost layer.
  • the material forming the outer layer side base material layer 1 is not particularly limited as long as it has insulating properties, and polyester resin, polyamide resin, epoxy resin, acrylic resin, fluororesin, polyurethane resin, silicon resin, phenol resin, etc. And resin films such as mixtures and copolymers thereof.
  • polyester resin and polyamide resin are preferable, and biaxially stretched polyester resin and biaxially stretched polyamide resin are more preferable.
  • polyester resin examples include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, copolymerized polyester, and polycarbonate.
  • polyamide resin examples include nylon 6, nylon 6, 6, a copolymer of nylon 6 and nylon 6, 6, nylon 6, 10, and polymethoxylylen adipamide (MXD6). Be done.
  • the outer layer side base material layer 1 may be formed of one layer of resin film, but may be formed of two or more layers of resin film in order to improve pinhole resistance and insulating property.
  • the resin films may be laminated via an adhesive component such as an adhesive or an adhesive resin, and the type and amount of the adhesive component used may be used. The same applies to the case of the adhesive layer 2 or the adhesive layer 5 described later.
  • the method of laminating two or more layers of resin films is not particularly limited, and a known method can be adopted. Examples thereof include a dry lamination method and a sand lamination method, and a dry lamination method is preferable. When laminating by the dry lamination method, it is preferable to use an adhesive as the adhesive layer. At this time, the thickness of the adhesive layer is, for example, about 0.5 to 10 ⁇ m.
  • the thickness of the outer layer side base material layer 1 is not particularly limited as long as the battery packaging material satisfies the above physical characteristics, but is, for example, about 10 to 50 ⁇ m, preferably about 15 to 35 ⁇ m. When a polyester film is used, the thickness is preferably 9 ⁇ m to 50 ⁇ m, and when a polyamide film is used, the thickness is preferably 10 ⁇ m to 50 ⁇ m. Sufficient strength can be secured as a packaging material, stress during overhang molding and draw molding can be reduced, and moldability can be improved.
  • the metal layer 3 is a layer that functions as a barrier layer for improving the strength of the battery packaging material and preventing water vapor, oxygen, light, etc. from entering the inside of the battery.
  • the metal constituting the metal layer 3 include aluminum, stainless steel, titanium, and the like, and aluminum is preferable.
  • the metal layer 3 can be formed by metal foil, metal vapor deposition, or the like, and is preferably formed of metal foil, and more preferably of aluminum foil. Further, it is preferable that at least one surface, preferably both sides, of the metal layer 3 is subjected to chemical conversion treatment in order to stabilize adhesion, prevent dissolution and corrosion, and the like.
  • the chemical conversion treatment refers to a treatment for forming an acid-resistant film on the surface of a metal layer.
  • the thickness of the metal layer 3 is not particularly limited as long as the battery packaging material satisfies the above physical characteristics, but can be, for example, about 10 to 50 ⁇ m, preferably about 25 to 45 ⁇ m.
  • the sealant layer 4 corresponds to the innermost layer, and is a layer in which the sealant layers are heat-sealed to each other when the battery is assembled to seal the battery element.
  • the resin component used in the sealant layer 4 is not particularly limited as long as it can be heat-fused, and examples thereof include polyolefins, cyclic polyolefins, carboxylic acid-modified polyolefins, and carboxylic acid-modified cyclic polyolefins.
  • polystyrene resin examples include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, and other polyethylene; homopolypropylene, polypropylene block copolymer (for example, propylene and ethylene block copolymer), and polypropylene.
  • Polypropylene such as random copolymers of propylene and ethylene (eg, random copolymers of propylene and ethylene); ethylene-butene-propylene tarpolymers; and the like.
  • polyethylene and polypropylene are preferable.
  • the cyclic polyolefin is a copolymer of an olefin and a cyclic monomer
  • examples of the olefin which is a constituent monomer of the cyclic polyolefin include ethylene, propylene, 4-methyl-1-pentene, styrene, butadiene, isoprene, and the like.
  • Examples of the cyclic monomer which is a constituent monomer of the cyclic polyolefin include cyclic alkenes such as norbornene; specific examples thereof include cyclic diene such as cyclopentadiene, dicyclopentadiene, cyclohexadiene, and norbornadiene.
  • cyclic alkene is preferable, and norbornene is more preferable.
  • the carboxylic acid-modified polyolefin is a polymer modified by block-polymerizing or graft-polymerizing the polyolefin with a carboxylic acid.
  • carboxylic acid used for modification include maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, itaconic anhydride and the like.
  • the carboxylic acid-modified cyclic polyolefin is obtained by copolymerizing a part of the monomers constituting the cyclic polyolefin in place of ⁇ , ⁇ -unsaturated carboxylic acid or its anhydride, or ⁇ , ⁇ with respect to the cyclic polyolefin.
  • -A polymer obtained by block-polymerizing or graft-polymerizing an unsaturated carboxylic acid or an anhydride thereof.
  • the carboxylic acid used for the modification is the same as that used for the modification of the acid-modified cycloolefin copolymer.
  • the sealant layer 4 may be formed by one kind of resin component alone, or may be formed by a blend polymer in which two or more kinds of resin components are combined. Further, the sealant layer 4 may be formed of only one layer, but may be formed of two or more layers with the same or different resin components.
  • the thickness of the sealant layer 4 is not particularly limited as long as the packaging material for the battery satisfies the above physical characteristics, but is, for example, about 10 to 100 ⁇ m, preferably about 20 to 90 ⁇ m.
  • the adhesive layer 5 is a layer provided between the metal layer 3 and the sealant layer 4 as necessary in order to firmly bond them.
  • the adhesive layer 5 is formed of an adhesive capable of adhering the metal layer 3 and the sealant layer 4.
  • the adhesive layer used for the adhesive layer 5 include an adhesive in which a polyolefin resin and a polyfunctional isocyanate are combined, an adhesive in which a polyol and a polyfunctional isocyanate are combined, a modified polyolefin resin, a heterocyclic compound and a curing agent.
  • the adhesive contained can be used.
  • an adhesive such as acid-modified polypropylene is melt-extruded onto a metal layer with a T-die extruder to form an adhesive layer 5, a sealant layer 4 is superposed on the adhesive layer 5, and the metal layer 3 and the sealant layer 4 are combined. Can also be pasted together. If both the adhesive layer 2 and the adhesive layer 5 require aging, they can be aged together. By setting the aging temperature to room temperature to 90 ° C., curing is completed in 2 days to 2 weeks, and moldability is exhibited.
  • the thickness of the adhesive layer 5 is not particularly limited as long as the packaging material for the battery satisfies the above physical characteristics, but is, for example, about 0.5 to 50 ⁇ m, preferably about 2 to 30 ⁇ m.
  • the coating layer 6 In the packaging material for batteries of the present invention, for the purpose of improving designability, electrolytic solution resistance, scratch resistance, moldability, etc., if necessary, above the outer layer side base material layer 1 (outer layer side base material layer).
  • the coating layer 6 may be provided on the side opposite to the metal layer 3 of 1.
  • the coating layer 6 is a layer located at the outermost layer when the battery is assembled.
  • the coating layer 6 can be formed of, for example, polyvinylidene chloride, polyester resin, urethane resin, acrylic resin, epoxy resin, or the like, and is preferably formed of a two-component curable resin.
  • the two-component curable resin forming the coating layer 6 include a two-component curable urethane resin, a two-component curable polyester resin, and a two-component curable epoxy resin.
  • the coating layer 6 may contain a matting agent.
  • Examples of the matting agent include fine particles having a particle size of about 0.5 nm to 5 ⁇ m.
  • the material of the matting agent is not particularly limited, and examples thereof include metals, metal oxides, inorganic substances, and organic substances.
  • the shape of the matting agent is also not particularly limited, and examples thereof include a spherical shape, a fibrous shape, a plate shape, an amorphous shape, and a balloon shape.
  • Specific examples of the matting agent include talc, silica, graphite, kaolin, montmoriloid, montmorillonite, synthetic mica, hydrotalcite, silica gel, zeolite, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, and aluminum oxide.
  • These matting agents may be used alone or in combination of two or more.
  • silica, barium sulfate, and titanium oxide are preferable from the viewpoint of dispersion stability and cost.
  • the matting agent may be subjected to various surface treatments such as an insulating treatment and a highly dispersible treatment on the surface.
  • the method for forming the coating layer 6 is not particularly limited, and examples thereof include a method of applying a two-component curable resin for forming the coating layer 6 on one surface of the outer layer side base material layer 1.
  • the matting agent may be added to the two-component curable resin, mixed, and then applied.
  • the method for producing the packaging material for a battery of the present invention is not particularly limited as long as a laminated body in which each layer having a predetermined composition is laminated can be obtained, but the following methods are exemplified.
  • laminate A a laminate in which the outer layer side base material layer 1, the adhesive layer 2, and the metal layer 3 are laminated in this order (hereinafter, may be referred to as "laminate A") is formed.
  • the laminate A is formed by applying the adhesive of the present invention onto the outer layer side base material layer 1 or the metal layer 3 whose surface has been chemically converted as needed, by an extrusion method, a gravure coating method, or a roll. It can be carried out by a dry lamination method in which the metal layer 3 or the outer layer side base material layer 1 is laminated and the adhesive layer 2 is cured after being applied and dried by a coating method such as a coating method.
  • the sealant layer 4 is laminated on the metal layer 3 of the laminated body A.
  • the resin component constituting the sealant layer 4 may be applied on the metal layer 3 of the laminated body A by a method such as a gravure coating method or a roll coating method. ..
  • the adhesive layer 5 and the sealant layer 4 are co-extruded onto the metal layer 3 of the laminated body A to be laminated ( Coextrusion lamination method), a method of separately forming a laminated body in which the adhesive layer 5 and the sealant layer 4 are laminated, and laminating this on the metal layer 3 of the laminated body A by the thermal lamination method, or the metal of the laminated body A.
  • An adhesive for forming an adhesive layer 5 is laminated on the layer 3 by an extrusion method, a solution-coated high-temperature drying method, a baking method, or the like, and a sheet-like film is formed on the adhesive layer 5 in advance.
  • the molten adhesive layer 5 is poured through the adhesive layer 5.
  • Examples thereof include a method of laminating the laminate A and the sealant layer 4 (sand lamination method).
  • the coating layer 6 is laminated on the surface of the outer layer side base material layer 1 opposite to the metal layer 3.
  • the coating layer 6 is formed by applying, for example, the above resin forming the coating layer 6 to the surface of the outer layer side base material layer 1.
  • the order of the step of laminating the metal layer 3 on the surface of the outer layer side base material layer 1 and the step of laminating the coating layer 6 on the surface of the outer layer side base material layer 1 is not particularly limited.
  • the metal layer 3 may be formed on the surface of the outer layer side base material layer 1 opposite to the coating layer 6.
  • a laminate composed of the sealant layer 4 is formed, but in order to strengthen the adhesiveness of the adhesive layer 2 and the adhesive layer 5 provided as needed, a hot roll contact type, a hot air type, near or far It may be subjected to heat treatment such as infrared type. Examples of the conditions for such heat treatment include 1 to 5 minutes at 80 to 250 ° C.
  • each layer constituting the laminated body improves or stabilizes film forming property, laminating process, aptitude for secondary processing (pouching, embossing) of the final product, etc., as necessary. Therefore, surface activation treatment such as corona treatment, blast treatment, oxidation treatment, ozone treatment and the like may be performed.
  • the battery container of the present invention can be obtained by molding the above-mentioned battery packaging material so that the outer layer side base material layer 1 forms a convex surface and the sealant layer 4 forms a concave surface.
  • a method for molding the concave portion there are the following methods. -Heat-compressed air molding method: The packaging material for batteries is sandwiched between a lower mold with holes for supplying high-temperature and high-pressure air and an upper mold with pocket-shaped recesses, and air is supplied while being heated and softened to form recesses. how to.
  • -Preheater flat plate type compressed air molding method After heating and softening the packaging material for batteries, air is supplied by sandwiching it between a lower mold with holes for supplying high-pressure air and an upper mold with pocket-shaped recesses. A method of forming a recess.
  • -Drum type vacuum forming method A method in which a battery packaging material is partially heated and softened with a heating drum, and then the concave portion of a drum having a pocket-shaped concave portion is evacuated to form the concave portion.
  • -Pin molding method A method in which the bottom material sheet is heat-softened and then crimped with a pocket-shaped uneven mold.
  • -Preheater plug assist compressed air molding method After heating and softening the packaging material for batteries, air is supplied by sandwiching it between a lower mold with holes for supplying high-pressure air and an upper mold with pocket-shaped recesses. A method of forming a concave portion, which assists molding by raising and lowering a convex plug at the time of molding.
  • the preheater plug assist compressed air molding method which is a heating vacuum forming method, is preferable in that the wall thickness of the bottom material after molding can be uniformly obtained.
  • the battery packaging material of the present invention is used as a battery container for sealing and accommodating battery elements such as a positive electrode, a negative electrode, and an electrolyte.
  • a battery element having at least a positive electrode, a negative electrode, and an electrolyte is used in the battery packaging material of the present invention, with metal terminals connected to each of the positive electrode and the negative electrode protruding outward.
  • a battery using a battery packaging material can be produced by covering the peripheral edge of the element so that a flange portion (a region where the sealant layers contact each other) can be formed, and heat-sealing the sealant layers of the flange portion to seal each other.
  • the sealant portion of the battery packaging material of the present invention is used so as to be inside (the surface in contact with the battery element).
  • the battery packaging material of the present invention may be used for either a primary battery or a secondary battery, but is preferably used for a secondary battery.
  • the type of the secondary battery to which the packaging material for the battery of the present invention is applied is not particularly limited, and for example, a lithium ion battery, a lithium ion polymer battery, a lead storage battery, a nickel / hydrogen storage battery, a nickel / cadmium storage battery, a nickel / Examples thereof include iron storage batteries, nickel / zinc storage batteries, silver oxide / zinc storage batteries, metal air batteries, polyvalent cation batteries, capacitors, and capacitors.
  • lithium ion batteries and lithium ion polymer batteries can be mentioned as suitable application targets of the packaging material for batteries of the present invention.
  • the use of the laminate of the present invention and the molded body of the laminate is not limited to the packaging material for batteries.
  • the laminate of the present invention may be used as a multilayer packaging material for the purpose of protecting foods, pharmaceuticals, and daily necessities. When used as a multi-layer packaging material, its layer structure may change depending on the contents, usage environment, and usage pattern.
  • the packaging material there is a material obtained by laminating the surfaces of the sealant films of the laminated body facing each other and then heat-sealing the peripheral end portions thereof.
  • the laminate of the present invention is bent or overlapped so that the inner layer surface (the surface of the sealant film) faces each other, and the peripheral end thereof is, for example, a side seal type or a two-way seal type.
  • the packaging material of the present invention can take various forms depending on the contents, the environment of use, and the form of use. Free-standing packaging materials (standing pouches), etc. are also possible.
  • a heat sealing method a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, and an ultrasonic seal can be used.
  • blister packs also called press-through packages or PTPs.
  • the blister pack seals the storage portion by joining the cover film to the laminate in which one or more storage portions are formed. Since the laminate of the present invention is excellent in moldability, it may be used as a laminate for forming a storage portion or as a cover film.
  • the present invention can also be used for applications other than packaging materials, and examples thereof include, but are not limited to, the base material of a decorative molded sheet. It can be suitably used for applications that require one or more functions of moldability, heat resistance, and moisture heat resistance.
  • polyester polyol (A1-1) 300.3 parts of isophthalic acid, 300.3 parts of terephthalic acid, 37.7 parts of neopentyl glycol, 101.0 parts of ethylene glycol, 260 of 1,9-nonanediol
  • a polyester polyol was synthesized according to a conventional method using 7 parts.
  • the obtained polyester polyol is diluted with ethyl acetate to a resin solid content of 60%, and the number average molecular weight (Mn) is 3000, the weight average molecular weight (Mw) is 16,000, and the resin hydroxyl value (solid content conversion) is 19.
  • a polyester polyol (A1-1) having a resin acid value (solid content equivalent) of 0.55 mgKOH / g and a glass transition temperature (Tg) of 10.7 ° C. was obtained at 2 mgKOH / g.
  • polyester polyol (A1-2) 424.8 parts of isophthalic acid, 182.0 parts of terephthalic acid, 57.1 parts of neopentyl glycol, 215.8 parts of 1,6-hexanediol, ethylene glycol 34
  • a polyester polyol was synthesized according to a conventional method using 0.0 part and 86.3 parts of 3-methyl-1,5-pentanediol.
  • the obtained polyester polyol is diluted with ethyl acetate to a resin solid content of 60%, and has a number average molecular weight (Mn) of 11,200, a weight average molecular weight (Mw) of 25,900, and a resin hydroxyl value (in terms of solid content).
  • polyester polyol (A1-3) 387.5 parts of isophthalic acid, 166.1 parts of terephthalic acid, 52.1 parts of neopentyl glycol, 167.4 parts of 1,6-hexanediol, 1,9 -A polyester polyol was synthesized according to a conventional method using 227.0 parts of nonanediol.
  • the obtained polyester polyol is diluted with ethyl acetate to a resin solid content of 60%, and has a number average molecular weight (Mn) of 3,050, a weight average molecular weight (Mw) of 19,640, and a resin hydroxyl value (in terms of solid content).
  • Polyester Polyol (A1-4) 303.3 parts of isophthalic acid, 303.3 parts of terephthalic acid, 37.7 parts of neopentyl glycol, 101.0 parts of ethylene glycol, 260 of 1,9-nonanediol
  • a polyester polyol was synthesized according to a conventional method using 7 parts.
  • the obtained polyester polyol is diluted with ethyl acetate to a resin solid content of 60%, and has a number average molecular weight (Mn) of 1,980, a weight average molecular weight (Mw) of 19,920, and a resin hydroxyl value (in terms of solid content).
  • a polyester polyol (A1-4) having a resin acid value (in terms of solid content) of 0.46 mgKOH / g and a glass transition temperature (Tg) of 22.5 ° C. was obtained at 13.8 mgKOH / g.
  • polyester polyol (A1-5) 303.3 parts of isophthalic acid, 303.3 parts of terephthalic acid, 37.7 parts of neopentyl glycol, 101.0 parts of ethylene glycol, 260 of 1,9-nonanediol
  • a polyester polyol was synthesized according to a conventional method using 7 parts.
  • the obtained polyester polyol is diluted with ethyl acetate to a resin solid content of 60% to obtain a number average molecular weight (Mn) of 2,600, a weight average molecular weight (Mw) of 11,000, and a resin hydroxyl value (in terms of solid content).
  • a polyester polyol (A1-5) having a resin acid value (solid content equivalent) of 0.51 mgKOH / g and a glass transition temperature (Tg) of 7.3 ° C. was obtained at 30.7 mgKOH / g.
  • polyester polyol (A1-6) A standard method using 365.7 parts of isophthalic acid, 156.7 parts of terephthalic acid, 49.1 parts of neopentyl glycol, and 428.4 parts of 1,9-nonanediol.
  • a polyester polyol was synthesized according to the above. The obtained polyester polyol is diluted with ethyl acetate to a resin solid content of 60%, and has a number average molecular weight (Mn) of 2,300, a weight average molecular weight (Mw) of 18,220, and a resin hydroxyl value (in terms of solid content).
  • polyester polyol (A1-7) A standard method using 261.2 parts of isophthalic acid, 261.2 parts of terephthalic acid, 49.1 parts of neopentyl glycol, and 428.4 parts of 1,9-nonanediol. A polyester polyol was synthesized according to the above. The obtained polyester polyol is diluted with ethyl acetate to a resin solid content of 60%, and has a number average molecular weight (Mn) of 3,000, a weight average molecular weight (Mw) of 25,160, and a resin hydroxyl value (in terms of solid content).
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • polyester polyol (A1-8) 273.9 parts of isophthalic acid, 273.9 parts of terephthalic acid, 51.5 parts of neopentyl glycol, 30.7 parts of ethylene glycol, 370 parts of 1,9-nonanediol Polyester polyol was synthesized according to a conventional method using 0.0 part.
  • the obtained polyester polyol is diluted with ethyl acetate to a resin solid content of 60%, and the number average molecular weight (Mn) is 5,440, the weight average molecular weight (Mw) is 26,220, and the resin hydroxyl value (solid content conversion) is determined.
  • polyester polyol (A3-1) 170.2 parts of isophthalic acid, 407.8 parts of terephthalic acid, 11.1 parts of trimellitic anhydride, 47.8 parts of neopentyl glycol, 1,6-hexane
  • a polyester polyol was synthesized according to a conventional method using 363.1 parts of diol.
  • the obtained polyester polyol is diluted with ethyl acetate to a resin solid content of 58%, and has a number average molecular weight (Mn) of 6,200, a weight average molecular weight (Mw) of 18,500, and a resin hydroxyl value (in terms of solid content).
  • a polyester polyol (A3-1) having a resin acid value (solid content equivalent) of 0.74 mgKOH / g and a glass transition temperature (Tg) of 7.3 ° C. was obtained at 21.9 mgKOH / g.
  • polyester polyol (A3-2) Synthesis of polyester polyol (A3-2) Using 900 parts of polyester polyol (A3-1) and 13.5 parts of hexamethylene diisocyanate, a chain extension reaction was carried out according to a conventional method to synthesize a polyester polyurethane polyol.
  • the obtained polyester polyurethane polyol is diluted with ethyl acetate to a resin solid content of 40%, and the number average molecular weight (Mn) is 14,500, the weight average molecular weight (Mw) is 117,500, and the resin hydroxyl value (solid content conversion).
  • a polyester polyol (A3-2) having a resin acid value (in terms of solid content) of 1.8 mgKOH / g and a glass transition temperature (Tg) of 10.0 ° C. was obtained.
  • polyester polyol (AH-1) 316.4 parts of isophthalic acid, 316.4 parts of terephthalic acid, 59.5 parts of neopentyl glycol, 225.0 parts of 1,6-hexanediol, ethylene glycol
  • a polyester polyol was synthesized according to a conventional method using 82.7 parts.
  • the obtained polyester polyol is diluted with ethyl acetate to a resin solid content of 60%, and has a number average molecular weight (Mn) of 7,700, a weight average molecular weight (Mw) of 17,900, and a resin hydroxyl value (solid content conversion).
  • a polyester polyol (AH-1) having a resin acid value (solid content equivalent) of 1.5 mgKOH / g and a glass transition temperature (Tg) of 25.3 ° C. was obtained at 18.3 mgKOH / g.
  • polyester polyol (AH-2) 395.4 parts of isophthalic acid, 179.7 parts of terephthalic acid, 29.2 parts of sebacic acid, 362.2 parts of 1,6-hexanediol, ethylene glycol 33
  • a polyester polyol was synthesized according to a conventional method using 6 parts.
  • the obtained polyester polyol is diluted with ethyl acetate to a resin solid content of 60%, and has a number average molecular weight (Mn) of 9,200, a weight average molecular weight (Mw) of 20,600, and a resin hydroxyl value (in terms of solid content).
  • a polyester polyol (AH-2) having a resin acid value (in terms of solid content) of 0.9 mgKOH / g and a glass transition temperature (Tg) of ⁇ 0.7 ° C. was obtained at 17.2 mgKOH / g.
  • the physical characteristics of the polyester polyols obtained in Synthesis Examples 1-11 and Comparative Synthesis Examples 1 and 2 were measured as follows and summarized in Tables 1 and 2.
  • the blending amount of the polyhydric alcohol (a2-1), the blending amount of the polyhydric alcohol (a2-2) and the polyhydric alcohol (a2-3) are the polyhydric alcohol used for the synthesis of the polyester polyol (a2-3). It is each ratio to a).
  • the polyester polyols (A1-1), (A1-3), (A1-5) to (A1-8) 50 parts of the polyester polyol (A1), 50 parts of the resin (A2), and trimethylolpropane of toluene diisocyanate.
  • the dynamic viscoelasticity of the composition of 30 parts of the adduct body was measured, and it was confirmed that a peak derived from the polyester polyol (A1) and a peak derived from the resin (A2) were present in the loss tangent (tan ⁇ ).
  • Glass transition temperature measurement method 5 mg of the sample was heated from room temperature to 200 ° C. at 10 ° C./min under a nitrogen stream of 30 mL / min using DSC, cooled to -80 ° C. at 10 ° C./min, and again 10 ° C./to 150 ° C. The temperature was raised in min and the DSC curve was measured. In the measurement results observed in the second temperature rise step, the straight line extending the baseline on the low temperature side to the high temperature side and the tangent line drawn at the point where the slope of the curve of the stepped part of the glass transition is maximized. The intersection of the above was taken as the glass transition point, and the temperature at this time was taken as the glass transition temperature.
  • Example 1 KBM-403 was added to a solution of polyester polyol (A1-1) having a resin solid content of 100.0 parts by adding 1.6 parts of KBM-403 (silane coupling agent non-volatile content manufactured by Shin-Etsu Chemical Co., Ltd .: 100%). Stir well until is completely dissolved. To this, KW-75 (polyisocyanate non-volatile content manufactured by DIC Corporation: 75% NCO%: 13.3) was added so that the non-volatile content was 30.3 parts, and ethyl acetate was further added so that the non-volatile content was 25%. Was added and stirred well to prepare the adhesive of Example 1.
  • Example 2 (Example 2) to (Example 12)
  • the adhesives of Examples 2 to 12 were produced in the same manner as in Example 1 except that the materials and formulations used for adjusting the adhesive were adjusted to the values shown in Tables 3 and 4.
  • Comparative Example 1 (Comparative Example 2)
  • Comparative Example 2 The adhesives of Comparative Example 1 and Comparative Example 2 were produced in the same manner as in Example 1 except that the materials and formulations used for adjusting the adhesive were adjusted to the values shown in Table 5.
  • the values shown in Tables 3 to 5 are the solid content (nonvolatile content).
  • Example 1 ⁇ Manufacturing of laminated body Configuration of Fig. 2> (Example 1)
  • the adhesive of Example 1 as the adhesive layer 2 is applied to the matte surface of the aluminum foil having a thickness of 40 ⁇ m as the metal layer 3 with a dry laminator in an amount of 4 g / square meter, and after the solvent is volatilized, the outer layer is formed.
  • a stretched polyamide film having a thickness of 25 ⁇ m was laminated as the side base material layer 1.
  • the adhesive for the adhesive layer 5 was applied to the glossy surface of the aluminum foil of the metal layer 3 of the obtained laminated film with a dry laminator in an amount of 4 g / square meter to volatilize the solvent.
  • An unstretched polypropylene film having a thickness of 40 ⁇ m was laminated as the sealant layer 4, and then cured (aged) at 60 ° C. for 5 days to cure the adhesive to obtain the laminate of Example 1.
  • Example 2 Example 2 to (Example 12) In the same manner as in Example 1, the adhesives of Examples 2 to 12 were used as the adhesive layer 2, and the laminates of Examples 2 to 12 were obtained.
  • the evaluation of the laminate was performed as follows. The results are shown in Tables 3-5. ⁇ Adhesive strength> Using "Autograph AGS-J" manufactured by Shimadzu Corporation, the outer layer side base material layer 1 of the laminate of Example or Comparative Example under the conditions of peeling speed 100 mm / min, peeling width 15 mm, and peeling form 180 ° peeling. And the adhesive strength at the interface of the metal layer 3 was evaluated. The higher the value, the more suitable as an adhesive.
  • the punch shape of the mold used was a square with a side of 30 mm, a corner R2 mm, and a punch shoulder R1 mm.
  • the die hole shape of the mold used is a square with a piece of 34 mm, a die hole corner R2 mm, a die hole shoulder R: 1 mm, and a clearance between the punch and the die hole is 0.3 mm on one side.
  • the clearance causes an inclination according to the molding height.
  • the following three stages of evaluation were performed according to the height of molding. ⁇ : 5.5 mm or more (especially excellent in practical use) ⁇ : 5.0 mm or more (excellent in practical use) ⁇ : 4.5 mm (practical range)
  • X At 4.5 mm, breakage of aluminum foil and floating between each layer occur.
  • the tray was taken out from the constant temperature and humidity chamber, and the appearance at 15 locations near the boundary between the flange portion and the side wall portion was confirmed, and it was evaluated whether or not floating was generated between the stretched polyamide film and the aluminum foil.
  • ⁇ No floating after standing for 168 hours (especially excellent in practical use)
  • ⁇ No floating after 72 hours of standing (excellent in practical use)
  • ⁇ Floating occurred after 72 hours of standing, but 3 or less (practical range)
  • X Floating occurs at 4 or more places after 72 hours of standing.
  • the adhesive of the present invention it has excellent moldability, and after heat fusion between the sealant layers performed to seal the stored material, and for a long period of time under high temperature and high humidity. It is clear that even after the durability test, there is no decrease in the adhesive strength between the layers, and it is possible to obtain a packaging material in which appearance defects such as floating between layers are suppressed.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention concerne un adhésif de type à deux composants qui présente une excellente aptitude au moulage, une excellente résistance à la chaleur et une excellente résistance à la chaleur humide. L'invention concerne un adhésif de type à deux composants qui se caractérise en ce qu'il contient (A) une composition de polyol qui contient (A1) un polyester polyol et (B) une composition de polyisocyanate qui contient (B1) un composé isocyanate, et qui se caractérise également : en ce que le polyester polyol (A1) est un produit de réaction (a1) d'un acide polybasique ou d'un dérivé de celui-ci et (a2) d'un alcool polyhydrique ; et en ce que l'alcool polyhydrique (a2) contient (a2-1) un alcool polyhydrique, le nombre d'atomes de carbone dans une chaîne de méthylène entre deux groupes hydroxyle étant un nombre impair de 5 à 19.
PCT/JP2020/030110 2019-08-26 2020-08-06 Adhésif de type à deux composants, corps multicouche, corps moulé et matériau d'emballage WO2021039338A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2021509231A JP6892036B1 (ja) 2019-08-26 2020-08-06 ２液型接着剤、積層体、成型体、包装材
CN202080042194.5A CN113993966A (zh) 2019-08-26 2020-08-06 2液型粘接剂、层叠体、成型体、包装材

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JP2019-153752 2019-08-26
JP2019153752 2019-08-26

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JP (1) JP6892036B1 (fr)
CN (1) CN113993966A (fr)
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CN115975578A (zh) * 2022-12-13 2023-04-18 江西省盛纬材料有限公司 聚氨酯胶黏剂及其制备方法，铝塑膜及其制备方法

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JP2023006643A (ja) * 2021-06-30 2023-01-18 東洋インキＳｃホールディングス株式会社 蓄電デバイス包装材用ポリウレタン接着剤、蓄電デバイス用包装材、蓄電デバイス用容器及び蓄電デバイス
CN115975578A (zh) * 2022-12-13 2023-04-18 江西省盛纬材料有限公司 聚氨酯胶黏剂及其制备方法，铝塑膜及其制备方法

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TW202113021A (zh) 2021-04-01

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