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WO2013005767A1 - Film multicouche présentant des propriétés de barrière aux gaz, adhésif et matériau de revêtement - Google Patents

Film multicouche présentant des propriétés de barrière aux gaz, adhésif et matériau de revêtement Download PDF

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Publication number
WO2013005767A1
WO2013005767A1 PCT/JP2012/067067 JP2012067067W WO2013005767A1 WO 2013005767 A1 WO2013005767 A1 WO 2013005767A1 JP 2012067067 W JP2012067067 W JP 2012067067W WO 2013005767 A1 WO2013005767 A1 WO 2013005767A1
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WO
WIPO (PCT)
Prior art keywords
gas barrier
polyester polyol
acid
film
resin composition
Prior art date
Application number
PCT/JP2012/067067
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English (en)
Japanese (ja)
Inventor
武田　博之
下口　睦弘
圭一 尾薗
Original Assignee
Dic株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2011149977A external-priority patent/JP5543408B2/ja
Priority claimed from JP2011154774A external-priority patent/JP5273219B2/ja
Priority claimed from JP2011154773A external-priority patent/JP5201429B2/ja
Application filed by Dic株式会社 filed Critical Dic株式会社
Publication of WO2013005767A1 publication Critical patent/WO2013005767A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising 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
    • 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
    • B32B27/08—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 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
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • 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
    • 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
    • C08G18/4219—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 aromatic dicarboxylic acids and dialcohols in combination with polycarboxylic acids and/or polyhydroxy compounds which are at least trifunctional
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
    • C08G18/7642—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the aromatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate groups, e.g. xylylene diisocyanate or homologues substituted on the aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
    • C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
    • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
    • C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
    • B32B2307/7244—Oxygen barrier
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging

Definitions

  • the present invention relates to a gas barrier multilayer film, an adhesive, and a coating material, and further relates to a polyester resin composition that can provide the gas barrier multilayer film, the adhesive, and the coating material.
  • Packaging materials used for packaging food and beverages have functions such as strength, resistance to cracking, retort resistance, and heat resistance to protect the contents from various distribution, storage such as refrigeration and heat sterilization. In addition to this, a wide variety of functions are required such as excellent transparency so that the contents can be confirmed.
  • an unstretched polyolefin film having excellent heat processability is essential, but the unstretched polyolefin film has many functions that are insufficient as a packaging material. In particular, a high barrier property is required for the purpose of maintaining the quality of the contents.
  • Such a barrier packaging material is usually used as a composite flexible film in which different polymer materials are laminated.
  • a barrier function is often imparted to various films (polyester resins such as polyethylene terephthalate (hereinafter abbreviated as PET), polyamide resins, stretched polyolefin resins) used on the outer layer side.
  • PET polyethylene terephthalate
  • polyamide resins polyamide resins
  • stretched polyolefin resins used on the outer layer side.
  • Patent Document 1 a gas barrier property using an aqueous dispersion containing a gas barrier polyurethane resin having a urethane group and a urea group and having a total of a urethane group concentration and a urea group concentration of 15% by mass or more.
  • a polyurethane resin and a gas barrier film containing the same are described.
  • the aqueous dispersion has no water resistance, there is a problem in using it in foods, beverages and the like containing water.
  • thermosetting gas barrier polyurethane resin containing a cured resin obtained by reacting an active hydrogen-containing compound (A) and an organic polyisocyanate compound (B),
  • the skeleton structure derived from meta-xylene diisocyanate is contained in an amount of 20% by mass or more, and the ratio of the trifunctional or higher compound in the (A) and (B) is based on the total amount of (A) and (B).
  • the composition has poor workability because a highly polar solvent must be used.
  • a highly soluble solvent such as acetone
  • the viscosity of the preparation is likely to increase due to the reaction between water and isocyanate because the boiling point is low and the water in the outside air is easily taken up.
  • Patent Document 3 discloses that an oxygen-absorbing resin component having a carbon-carbon unsaturated bond and a reactive functional group, and reacting with the reactive functional group to form a cross-linked structure with the oxygen-absorbing resin component.
  • An oxygen-absorbing paint containing the resulting cross-linking agent is described.
  • the purpose of the present invention is the same as that of the present invention in the sense that the contents are protected from deterioration, but this cited reference is a technique for preventing deterioration of the contents by absorbing oxygen, and blocks the oxygen of the present application. It is different from the method.
  • a film having an oxygen barrier property is indispensable, and deterioration of contents cannot be prevented without a film having a high oxygen barrier property.
  • an organic polymer polyol compound selected from the group consisting of polyester polyol, polyether polyol, polyether ester polyol and polyurethane polyol, and a carboxylic acid anhydride is added to one end of the organic polymer polyol compound.
  • a solventless composite laminate adhesive composition characterized by comprising an organic polymer polyol compound having a carboxyl group introduced at one end and a polyisocyanate compound.
  • Patent Document 4 has a description on workability and adhesiveness, but does not have a description on oxygen barrier properties and does not have oxygen barrier properties.
  • Japanese Patent No. 4524463 Japanese Patent No. 4054972 JP 2003-268310 A Japanese Unexamined Patent Publication No. 7-97557
  • the problem to be solved by the present invention is to provide a gas barrier multilayer film having excellent gas barrier properties.
  • Another object of the present invention is to provide a gas barrier polyester resin composition mainly comprising a polyester resin used as a gas barrier layer in the gas barrier multilayer film, a gas barrier multilayer film in which the resin composition is applied to the film, and a coating material. .
  • a gas barrier multilayer film having a gas barrier layer obtained by curing a polyester resin composition obtained by reacting a polyester polyol and a curing agent.
  • a polyester resin composition having a specific structure solves the problems of the present invention, and the present invention has been completed.
  • the present invention In a gas barrier multilayer film having a gas barrier layer obtained by curing a polyester resin composition obtained by reacting a polyester polyol and a curing agent, the present invention provides a gas barrier multilayer film in which the polyester resin composition is any one selected from the following (I) to (III).
  • the polyester resin composition is any one selected from the following (I) to (III).
  • R 1 to R 3 each independently represents a hydrogen atom, or a compound represented by the general formula (2)
  • n represents an integer of 1 to 5
  • X represents an optionally substituted 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group
  • 2 represents an arylene group selected from the group consisting of 1,3-anthraquinonediyl group and 2,3-anthracenediyl group
  • Y represents an alkylene group having 2 to 6 carbon atoms.
  • R 1 to R 3 represents a group represented by the general formula (2).
  • a resin composition for an oxygen barrier adhesive comprising a polyester polyol (C) and a polyisocyanate (D) having two or more isocyanate groups,
  • the polyester polyol (C) has at least one carboxy group and two or more hydroxyl groups obtained by reacting a carboxylic anhydride or a polyvalent carboxylic acid with a polyester polyol having three or more hydroxyl groups.
  • a gas barrier multilayer film having excellent gas barrier properties is provided. Also provided are a gas barrier polyester resin composition mainly composed of a polyester resin excellent in gas barrier properties used as a gas barrier layer in the gas barrier multilayer film, a gas barrier multilayer film in which the resin composition is applied to the film, and a coating material. can do.
  • Polyester resin composition according to (I) (polyester resin compound having a glycerol skeleton)
  • R 1 to R 3 are a hydrogen atom or a general formula (2)
  • n represents an integer of 1 to 5
  • X represents an optionally substituted 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group
  • 2 represents an arylene group selected from the group consisting of 1,3-anthraquinonediyl group and 2,3-anthracenediyl group
  • Y represents an alkylene group having 2 to 6 carbon atoms.
  • at least one of R 1 to R 3 represents a group represented by the general formula (2). ).
  • R 1 , R 2 and R 3 needs to be a group represented by the general formula (2). Among them, it is preferable that all of R 1 , R 2 and R 3 are groups represented by the general formula (2).
  • R 1, any one of R 2 and R 3 is a group represented by the general formula (2) compound, R 1, R 2, and any two of the general formula R 3 (2) Any two or more compounds of the compound represented by the general formula (2) and the compound in which all of R 1 , R 2 and R 3 are groups represented by the general formula (2) are mixed. Also good.
  • X is selected from the group consisting of 1,2-phenylene group, 1,2-naphthylene group, 2,3-naphthylene group, 2,3-anthraquinonediyl group, and 2,3-anthracenediyl group,
  • the arylene group which may have is represented.
  • X When X is substituted with a substituent, it may be substituted with one or more substituents, which are attached to any carbon atom on X that is different from the free radical.
  • substituents examples include chloro group, bromo group, methyl group, ethyl group, i-propyl group, hydroxyl group, methoxy group, ethoxy group, phenoxy group, methylthio group, phenylthio group, cyano group, nitro group, amino group, Examples thereof include a phthalimide group, a carboxyl group, a carbamoyl group, an N-ethylcarbamoyl group, a phenyl group, and a naphthyl group.
  • Y represents an ethylene group, propylene group, butylene group, neopentylene group, 1,5-pentylene group, 3-methyl-1,5-pentylene group, 1,6-hexylene group, methylpentylene.
  • Y is preferably a propylene group or an ethylene group, and most preferably an ethylene group.
  • the polyester resin compound having a glycerol skeleton represented by the general formula (1) is essential for glycerol, an aromatic polyvalent carboxylic acid in which the carboxylic acid is substituted in the ortho position, or an anhydride thereof, and a polyhydric alcohol component. Obtained by reacting as a component.
  • the aromatic polyvalent carboxylic acid in which the carboxylic acid is substituted in the ortho position or its anhydride includes orthophthalic acid or its anhydride, naphthalene 2,3-dicarboxylic acid or its anhydride, naphthalene 1,2-dicarboxylic acid or its An anhydride, anthraquinone 2,3-dicarboxylic acid or its anhydride, 2,3-anthracene carboxylic acid or its anhydride, etc. are mentioned. These compounds may have a substituent on any carbon atom of the aromatic ring.
  • substituents examples include chloro group, bromo group, methyl group, ethyl group, i-propyl group, hydroxyl group, methoxy group, ethoxy group, phenoxy group, methylthio group, phenylthio group, cyano group, nitro group, amino group, Examples thereof include a phthalimide group, a carboxyl group, a carbamoyl group, an N-ethylcarbamoyl group, a phenyl group, and a naphthyl group.
  • examples of the polyhydric alcohol component include alkylene diols having 2 to 6 carbon atoms.
  • diols such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol, etc. Can be illustrated.
  • a polyester resin compound having a glycerol skeleton represented by the general formula (1) a polyester resin (orthophthalic anhydride as an aromatic polycarboxylic acid and ethylene glycol as a polyhydric alcohol ( GLY (oPAEG) m, where m represents the total number of groups in parentheses contained in the polyester resin of the present invention), naphthalene 2,3-dicarboxylic acid as an aromatic polycarboxylic acid, and polyhydric alcohol as Examples thereof include polyester resins using ethylene glycol (abbreviated as GLY (oNAEG) m, where m is as defined above).
  • GLY (oNAEG) m ethylene glycol
  • P represents a polyester resin compound having a glycerol skeleton.
  • the present invention is characterized by having a glycerol residue of 5% by mass or more in the polyester resin composition in order to express a high barrier property.
  • the mass excluding the mass of the diluent solvent, the mass of the volatile component contained in the curing agent and the inorganic component from the mass part of the gas barrier polyester resin composition is defined as the mass of the total solid content of the adhesive resin.
  • the aromatic polyvalent carboxylic acid in which the acyl group as the raw material of the polyester component is substituted in the ortho position or its anhydride has an asymmetric structure. Therefore, it is presumed that the rotation of the molecular chain of the resulting polyester is suppressed, and thus it is presumed that the gas barrier property is excellent.
  • the crystallinity that inhibits the adhesion to the substrate is low, so that it exhibits high solubility in solvents such as ethyl acetate and methyl ethyl ketone and is excellent in gas barrier properties.
  • polyhydric alcohol In the polyester resin compound used in the present invention, a polyhydric alcohol component other than an alkylene diol having 2 to 6 carbon atoms may be copolymerized as a polyhydric alcohol as long as the effects of the present invention are not impaired.
  • aliphatic polyhydric alcohols such as glycerol, erythritol, pentaerythritol, dipentaerythritol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetraethylene glycol, tripropylene glycol, Cycloaliphatic polyhydric alcohols such as cyclohexanedimethanol and tricyclodecanedimethanol, aromatic polyhydric phenols such as hydroquinone, resorcinol, catechol, naphthalene diol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol, or the like Examples thereof include ethylene oxide elongated products and hydrogenated alicyclic groups.
  • polyester resin of the present invention essentially comprises an aromatic polyvalent carboxylic acid in which the carboxylic acid is substituted in the ortho position or an anhydride thereof as the polyvalent carboxylic acid component, but within the range not impairing the effects of the present invention, A polyvalent carboxylic acid component may be copolymerized.
  • aliphatic polyvalent carboxylic acid succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, etc.
  • unsaturated bond-containing polyvalent carboxylic acid maleic anhydride, maleic acid, Fumaric acid, etc., 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid etc.
  • succinic acid 1,3-cyclopentanedicarboxylic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,8-naphthalic acid and diphenic acid are preferred.
  • glycerol used as a raw material, an aromatic polycarboxylic acid in which the carboxylic acid is substituted in the ortho position, or an anhydride thereof, and a polyhydric alcohol component are collectively charged,
  • the temperature is raised while stirring and mixing to cause a dehydration condensation reaction.
  • 1 mgKOH / g or less by the acid value measuring method described in JIS-K0070, and the hydroxyl value ZmgKOH / g obtained by the hydroxyl value measuring method described in JIS-K0070 is the numerical value on the right side of the following formula (b) (mgKOH /
  • the desired polyester resin can be obtained by continuing the reaction until it is within ⁇ 5% of g).
  • Mn represents a set number average molecular weight of a predetermined trifunctional polyester resin.
  • each raw material may be reacted in multiple stages. Moreover, you may prepare so that a hydroxyl value may enter into less than +/- 5%, adding the diol component which volatilized at reaction temperature.
  • Catalysts used in the reaction include acids such as tin-based catalysts such as monobutyltin oxide and dibutyltin oxide, titanium-based catalysts such as tetra-isopropyl-titanate and tetra-butyl-titanate, and zirconia-based catalysts such as tetra-butyl-zirconate.
  • acids such as tin-based catalysts such as monobutyltin oxide and dibutyltin oxide
  • titanium-based catalysts such as tetra-isopropyl-titanate and tetra-butyl-titanate
  • zirconia-based catalysts such as tetra-butyl-zirconate.
  • a catalyst is mentioned. It is preferable to use a combination of the titanium-based catalyst such as tetra-isopropyl-titanate or tetra-butyl-titanate, which has high activity for este
  • the amount of the catalyst is 1 to 1000 ppm, more preferably 10 to 100 ppm, based on the total mass of the reaction raw material used. If it is less than 1 ppm, it is difficult to obtain an effect as a catalyst, and if it exceeds 1000 ppm, the subsequent urethanization reaction tends to be inhibited. However, a catalyst is not essential if the reaction can proceed without catalyst.
  • the number average molecular weight of the polyester resin compound having a glycerol skeleton is preferably 450 to 5,000, and more preferably 450 to 2,000.
  • the polyisocyanate described below is most preferable, can give an appropriate reaction time, and is particularly excellent in solubility and oxygen barrier ability.
  • the urethane group concentration at this time is preferably in the range of 1.0 to 6.0 mmol / g.
  • the polyester resin compound having a glycerol skeleton used in the present invention preferably has a glass transition temperature in the range of ⁇ 30 ° C. to 70 ° C. More preferably, it is ⁇ 20 ° C. to 50 ° C.
  • the glass transition temperature is too higher than 70 ° C., the flexibility of the polyester resin near room temperature tends to be low, and the adhesion to the substrate tends to be poor.
  • the temperature is too low at about -30 ° C., there is a risk that sufficient gas barrier properties may not be obtained due to the intense molecular motion of the polyester resin near room temperature.
  • the resin composition according to (II) is obtained by reacting a polyvalent carboxylic acid and a polyhydric alcohol, and is a component of polyvalent carboxylic acid and polyhydric alcohol.
  • a component having a polymerizable carbon-carbon double bond a polymerizable carbon double bond is introduced into the molecule of the polyester polyol (A).
  • the polyester polyol (A) of the present invention is a polyvalent carboxylic acid component, specifically, an aliphatic polyvalent carboxylic acid such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, etc. 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, etc.
  • aromatic polycarboxylic acids and orthophthalic acid, terephthalic acid, isophthalic acid, pyromellitic acid, trimellitic as aromatic polycarboxylic acids Acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid And anhydrides or ester-forming derivatives of these dicarboxylic acids; p-hydroxybenzoic acid, p- (2 Polyhydroxy acids such as -hydroxyethoxy) benzoic acid and ester-forming derivatives of these dihydroxycarboxylic acids can be used alone or in a mixture of two or more.
  • succinic acid, 1,3-cyclopentanedicarboxylic acid, orthophthalic acid, acid anhydride of orthophthalic acid, and isophthalic acid are preferable, and orthophthalic acid and its acid anhydride are more preferable.
  • the polyhydric alcohol used in the present invention includes, as the aliphatic diol, ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, cyclohexanedimethanol, 1,5-pentanediol, 3-methyl-1 , 5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, aromatic polyphenol , Hydroquinone, resorcinol, catechol, naphthalene diol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol, ethylene oxide De extension product, there can be mentioned hydrogenated alicyclic.
  • ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexane Methanol is preferable, and ethylene glucol is more preferable.
  • polyhydric alcohol with polymerizable carbon-carbon double bond examples include 2-butene-1,4-diol.
  • a polymerizable double bond is introduced into the polyester polyol (A) by using a polyvalent carboxylic acid having a polymerizable carbon-carbon double bond and a polyhydric alcohol, but has a hydroxyl group. It may be a reaction between a polyester polyol and a carboxylic acid having a polymerizable double bond, or a carboxylic acid anhydride.
  • a carboxylic acid having a polymerizable double bond such as maleic acid, maleic anhydride or fumaric acid, an unsaturated fatty acid such as oleic acid or sorbic acid, or the like can be used.
  • the polyester polyol in this case is preferably a polyester polyol having two or more hydroxyl groups, but it is more preferable to have three or more hydroxyl groups in consideration of molecular elongation due to crosslinking with polyisocyanate.
  • the polyester polyol has 1 or 2 hydroxyl groups
  • the polyester polyol (A) obtained by reacting with a carboxylic acid having a polymerizable double bond has 0 or 1 hydroxyl group and reacts with the polyisocyanate (B). It becomes difficult to cause molecular elongation due to, and it becomes difficult to obtain properties such as laminate strength, seal strength, and heat resistance as an adhesive.
  • polyester polyols (A) having a number average molecular weight of 450 to 5,000 are particularly preferable because a crosslinking density with an excellent balance between adhesive ability and oxygen barrier ability can be obtained.
  • the polyisocyanate described below is most preferable, can give an appropriate reaction time, and is particularly excellent in adhesive strength and oxygen barrier ability.
  • the molecular weight is less than 450, the cohesive force of the adhesive at the time of coating becomes too small, causing the problem that the film shifts during lamination or the bonded film rises.
  • the molecular weight is higher than 5000, The problem is that the viscosity at the time of construction is too high to be applied, and that the lamination is impossible due to low adhesiveness.
  • the number average molecular weight was obtained by calculation from the obtained hydroxyl value and the number of functional groups of the designed hydroxyl group.
  • the polyester polyol (A) used in the present invention preferably has a glass transition temperature in the range of ⁇ 30 ° C. to 80 ° C. More preferably, it is 0 ° C to 60 ° C. More preferably, it is 25 ° C to 60 ° C.
  • the glass transition temperature is too higher than 80 ° C.
  • the flexibility of the polyester polyol near room temperature is lowered, and thus the adhesiveness to the substrate may be deteriorated due to poor adhesion to the substrate.
  • the temperature is lower than ⁇ 30 ° C., there is a possibility that sufficient oxygen barrier properties may not be obtained due to intense molecular motion of the polyester polyol at around room temperature.
  • the polyester polyol (A) has a hydroxyl value of 20 to 250 mgKOH / g and an acid value of 0 to 100 mgKOH / g.
  • the hydroxyl value can be measured by the hydroxyl value measuring method described in JIS-K0070, and the acid value can be measured by the acid value measuring method described in JIS-K0070.
  • the hydroxyl value is smaller than 20 mgKOH / g, the molecular weight is too large, the viscosity becomes high, and good coating suitability cannot be obtained.
  • the hydroxyl value exceeds 250 mgKOH / g the molecular weight becomes too small, so that the crosslinking density of the cured coating film becomes too high, and good adhesive strength cannot be obtained.
  • the monomer component having a polymerizable carbon-carbon double bond is 5 to 60 parts by mass with respect to 100 parts by mass of all monomer components constituting the polyester polyol (A). If it is lower than this range, the number of crosslinking points between the polymerizable double bonds will be reduced, and it will be difficult to obtain barrier properties. If it is higher, the number of crosslinking points will be increased, and the flexibility of the cured coating will be significantly reduced, resulting in a laminate strength. This is not preferable because it is difficult to be performed. For this reason, the amount of polyvalent carboxylic acid and polyhydric alcohol component used other than the polyvalent carboxylic acid and polyhydric alcohol component having a polymerizable carbon-carbon double bond must be kept below a certain level.
  • polyester polyol (A) of the present invention examples include a drying oil or a semi-drying oil.
  • the drying oil or semi-drying oil examples include publicly known and commonly used drying oils having a carbon double bond and semi-drying oils.
  • a polyol having a number average molecular weight of 1000 to 15000 by urethane elongation by reaction of the polyester polyol (A) with a diisocyanate compound may be used as an adhesive. Since the polyol has a certain molecular weight component and a urethane bond, the polyol has an excellent oxygen barrier property, an excellent initial cohesive force, and is further excellent as an adhesive used during lamination.
  • the polyester polyol (A) according to (III) includes at least one carboxy group obtained by reacting a polyester polyol (I) having three or more hydroxyl groups with a carboxylic acid anhydride or a polyvalent carboxylic acid. It has two or more hydroxyl groups.
  • the polyester polyol (I) having three or more hydroxyl groups can be obtained by making a part of the polyvalent carboxylic acid or polyhydric alcohol trivalent or higher.
  • the polyvalent carboxylic acid component and the polyhydric alcohol component of the polyester polyol (A) are preferably a polyvalent carboxylic acid component containing at least one or more of orthophthalic acid and its anhydride, ethylene glycol, propylene glycol, butylene glycol, neo Carboxylic anhydride or polycarboxylic acid is reacted with polyester polyol (I) having three or more hydroxyl groups comprising at least one polyhydric alcohol component selected from the group consisting of pentyl glycol and cyclohexanedimethanol. And having at least one carboxy group and two or more hydroxyl groups.
  • Orthophthalic acid and its anhydride have an asymmetric structure in the skeleton. Therefore, it is presumed that the rotation of the molecular chain of the resulting polyester is suppressed, and it is presumed that this provides excellent oxygen barrier properties. Further, it is presumed that due to this asymmetric structure, it exhibits non-crystallinity, imparts sufficient substrate adhesion, and is excellent in adhesion and oxygen barrier properties. Furthermore, when used as a dry laminate adhesive, the solvent solubility, which is essential, is also high, so that it has excellent handling characteristics.
  • polyester polyol (I) of the present invention may be copolymerized with other polyvalent carboxylic acid components as long as the effects of the present invention are not impaired.
  • the aliphatic polyvalent carboxylic acid succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, etc.
  • the unsaturated bond-containing polyvalent carboxylic acid maleic anhydride, maleic acid, Fumaric acid, etc., 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid etc.
  • Trivalent or higher polyvalent carboxylic acids include trimellitic acid and its acid anhydride, pyromellitic acid and its acid anhydride, etc. In order to prevent gelation during synthesis, a trivalent or higher polyvalent carboxylic acid may be used. A trivalent carboxylic acid is preferred as the divalent carboxylic acid.
  • the polyhydric alcohol used in the present invention preferably contains at least one selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and cyclohexanedimethanol.
  • ethylene glycol is most preferably used because it is presumed that the smaller the number of carbon atoms between oxygen atoms, the less the molecular chain becomes excessively flexible and the less oxygen permeates.
  • polyhydric alcohol and other ingredients are preferably used, but other polyhydric alcohol components may be copolymerized within a range not impairing the effects of the present invention.
  • aliphatic diols include 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, Triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, aromatic polyphenols, hydroquinone, resorcinol, catechol, naphthalene diol, biphenol, bisphenol A, hisphenol F, tetramethylbiphenol, and ethylene Examples thereof include an oxide extension product and a hydrogenated alicyclic group.
  • trihydric or higher polyhydric alcohol examples include glycerin, trimethylolpropane, trimethylolethane, tris (2-hydroxyethyl) isocyanurate, 1,2,4-butanetriol, pentaerythritol, dipentaerythritol and the like.
  • the trihydric or higher polyhydric alcohol is preferably a trihydric alcohol.
  • polyester polyol (I) can be obtained by reacting the polyester polyol (I) with a polyvalent carboxylic acid or an acid anhydride thereof with a hydroxyl group of the polyester polyol (I).
  • the ratio between the polyester polyol (I) and the polyvalent carboxylic acid is that 1 or more hydroxyl groups of the polyester polyol (A) after the reaction are required, so that the polyvalent carboxylic acid is 1/3 of the hydroxyl groups of the polyester polyol (I).
  • carboxylic acid anhydride or polyhydric carboxylic acid used here when the gelatinization at the time of reaction with polyhydric carboxylic acid and polyester polyol (I) is considered, it is a bivalent or trivalent carboxylic acid anhydride. Is preferably used.
  • Divalent carboxylic acid anhydrides include succinic anhydride, maleic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic acid Anhydride, phthalic anhydride, 2,3-naphthalenedicarboxylic acid anhydride, and the like can be used, and trimellitic acid anhydride can be used as the trivalent carboxylic acid anhydride.
  • the number average molecular weight of the polyester polyol (A) is particularly preferably from 450 to 5,000 because a crosslinking density with an excellent balance between adhesion ability and oxygen barrier ability can be obtained.
  • the polyisocyanate described below is most preferable, can give an appropriate reaction time, and is particularly excellent in adhesive strength and oxygen barrier ability.
  • the molecular weight is less than 450, the cohesive force of the adhesive at the time of coating becomes too small, causing the problem that the film shifts during lamination or the bonded film rises.
  • the molecular weight is higher than 5000, The problem is that the viscosity at the time of construction is too high to be applied, and that the lamination is impossible due to low adhesiveness.
  • the number average molecular weight was obtained by calculation from the obtained hydroxyl value and the number of functional groups of the designed hydroxyl group.
  • the polyester polyol (A) used in the present invention preferably has a glass transition temperature in the range of ⁇ 30 ° C. to 80 ° C. More preferably, it is 0 ° C to 60 ° C. More preferably, it is 25 ° C to 60 ° C.
  • the glass transition temperature is higher than 80 ° C.
  • the flexibility of the polyester polyol near room temperature is lowered, and thus the adhesiveness to the substrate may be deteriorated due to poor adhesion to the substrate.
  • the temperature is lower than ⁇ 30 ° C., there is a possibility that sufficient oxygen barrier properties may not be obtained due to the intense molecular motion of the polyester polyol near room temperature.
  • the polyester polyol (A) has a hydroxyl value of 20 to 250 and an acid value of 20 to 200.
  • the hydroxyl value can be measured by the hydroxyl value measuring method described in JIS-K0070, and the acid value can be measured by the acid value measuring method described in JIS-K0070.
  • the hydroxyl value is smaller than 20 mgKOH / g, the molecular weight is too large, the viscosity becomes high, and good coating suitability cannot be obtained.
  • the hydroxyl value exceeds 250 mgKOH / g, the molecular weight becomes too small, so that the crosslinking density of the cured coating film becomes too high, and good adhesive strength cannot be obtained.
  • a polyol having a number average molecular weight of 1000 to 15000 by urethane elongation by reaction of the polyester polyol (A) with a diisocyanate compound may be used as an adhesive. Since the polyol has a certain molecular weight component and a urethane bond, the polyol has an excellent oxygen barrier property, an excellent initial cohesive force, and is further excellent as an adhesive used during lamination.
  • the curing agent used in the present invention is not particularly limited as long as it is a curing agent capable of reacting with the hydroxyl group of the polyester resin, and known curing agents such as polyisocyanates and epoxy compounds can be used. Among these, it is preferable to use polyisocyanate from the viewpoints of adhesiveness and retort resistance.
  • Polyisocyanate compounds include aromatic and aliphatic diisocyanates and trivalent or higher polyisocyanates, which may be either low molecular compounds or high molecular compounds.
  • the isocyanate compound may be a blocked isocyanate.
  • the isocyanate blocking agent for example, phenols such as phenol, thiophenol, methylthiophenol, ethylthiophenol, cresol, xylenol, resorcinol, nitrophenol, chlorophenol, acetoxime, methyl ethyl ketoxime, cyclohexanone oxime oximes, methanol, Alcohols such as ethanol, propanol and butanol; halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol; tertiary alcohols such as t-butanol and t-pentanol; Examples include lactams such as caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam, ⁇ -propylolactam, and other aromatic amines, imides, acetylacetate.
  • the blocked isocyanate can be obtained by subjecting the above isocyanate compound and an isocyanate blocking agent to an addition reaction by a conventionally known appropriate method.
  • Epoxy compounds include bisphenol A diglycidyl ether and oligomers thereof, hydrogenated bisphenol A diglycidyl ether and oligomers thereof, orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, and p-oxybenzoic acid diglyceride.
  • Glycidyl ester tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1 , 4-Butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether and polyalkylene glycol Cole diglycidyl ethers, trimellitic acid triglycidyl ester, triglycidyl isocyanurate, 1,4-diglycidyloxybenzene, diglycidyl propylene urea, glycerol triglycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl
  • a general-purpose known epoxy curing accelerator may be appropriately added for the purpose of accelerating curing as long as the gas barrier property which is the object of the present invention is not impaired.
  • the curing agent is preferably the polyisocyanate, and when the polyisocyanate includes the metaxylene skeleton, the gas barrier property can be improved by not only hydrogen bonding of the urethane group but also ⁇ - ⁇ stacking of aromatic rings. It is preferable because it can be done.
  • Examples of the polyisocyanate containing a metaxylene skeleton include xylene diisocyanate trimer, burette synthesized by reaction with amine, and adduct formed by reaction with alcohol.
  • the adduct body is more preferable because the solubility of the polyisocyanate in the organic solvent used for the dry laminate adhesive is easily obtained.
  • an adduct obtained by reacting with an alcohol appropriately selected from the above low molecular active hydrogen compounds can be used. Among them, addition of ethylene oxide of trimethylolpropane, glycerol, triethanolamine, metaxylenediamine, etc. Adduct bodies with objects are particularly preferred.
  • the ratio of the polyester resin compound having a glycerol skeleton and the curing agent is that the ratio of the polyester resin compound having a glycerol skeleton and the curing agent is a hydroxyl group of the polyester resin compound having a glycerol skeleton and curing. It is preferable to blend such that the reaction component of the agent is 1 / 0.5 to 1/5 (equivalent ratio), more preferably 1/1 to 1/3. If the curing agent component is excessive beyond this range, the excess curing agent component may be left out and bleed out from the adhesive layer after bonding. On the other hand, if the curing agent component is insufficient, the adhesive strength is insufficient. There is a fear.
  • the above-mentioned curing agent can be used in combination with a known curing agent or accelerator selected according to the type.
  • the adhesion promoter include silane coupling agents such as hydrolyzable alkoxysilane compounds, titanate coupling agents, aluminum coupling agents, and epoxy resins. Silane coupling agents and titanate coupling agents are also preferred in terms of improving the adhesive to various film materials.
  • the polyester polyol (A) and the curing agent are such that the ratio of the polyester polyol (A) and the curing agent is a hydroxyl group of the polyester polyol (A) and a reaction component of the curing agent. It is preferably blended so as to be 1 / 0.5 to 1/10 (equivalent ratio), more preferably 1/1 to 1/5. If the curing agent component is excessive beyond this range, the excess curing agent component may be left out and bleed out from the adhesive layer after bonding. On the other hand, if the curing agent component is insufficient, the adhesive strength may be insufficient. There is.
  • a known polymerization catalyst can be used as a catalyst for promoting polymerization of a polymerizable double bond.
  • the polymerization catalyst include transition metal complexes. Although a transition metal complex will not be specifically limited if it is a compound provided with the capability to oxidatively polymerize a polymerizable double bond, A various metal or its complex can be used.
  • metals such as cobalt, manganese, lead, calcium, cerium, zirconium, zinc, iron, copper, octyl acid, naphthenic acid, neodecanoic acid, stearic acid, resin acid, tall oil fatty acid, tung oil fatty acid, linseed oil fatty acid, A salt with soybean oil fatty acid or the like can be used.
  • the transition metal complex is preferably 0 to 10 parts by mass, more preferably 0 to 3 parts by mass with respect to the polyester polyol (A).
  • the above-mentioned curing agent can be used in combination with a known curing agent or accelerator selected according to the type.
  • the adhesion promoter include silane coupling agents such as hydrolyzable alkoxysilane compounds, titanate coupling agents, aluminum coupling agents, and epoxy resins. Silane coupling agents and titanate coupling agents are also preferred in terms of improving the adhesive to various film materials.
  • the polyester polyol (A) and the curing agent are such that the ratio of the polyester polyol (A) and the curing agent is a reaction component of the hydroxyl group of the polyester polyol (A) and the curing agent. Is preferably 1 / 0.5 to 1/10 (equivalent ratio), more preferably 1/1 to 1/5. If the curing agent component is excessive beyond this range, the excess curing agent component may be left out and bleed out from the adhesive layer after bonding. On the other hand, if the curing agent component is insufficient, the adhesive strength is insufficient. There is a fear.
  • the above-mentioned curing agent can be used in combination with a known curing agent or accelerator selected according to the type.
  • the adhesion promoter include silane coupling agents such as hydrolyzable alkoxysilane compounds, titanate coupling agents, aluminum coupling agents, and epoxy resins. Silane coupling agents and titanate coupling agents are also preferred in terms of improving the adhesive to various film materials.
  • the polyester resin composition of the present invention may contain various additives as long as the gas barrier property is not impaired.
  • additives include inorganic fillers such as silica, alumina, mica, talc, aluminum flakes, and glass flakes, layered inorganic compounds, stabilizers (antioxidants, heat stabilizers, ultraviolet absorbers, etc.), plasticizers, Examples thereof include an antistatic agent, a lubricant, an antiblocking agent, a colorant, a filler, and a crystal nucleating agent.
  • swellable inorganic layered compounds examples include hydrous silicates (phyllosilicate minerals, etc.), kaolinite group clay minerals (halloysite, kaolinite, enderite, dickite, nacrite, etc.), antigolite group clay minerals (anti Golite, chrysotile, etc.), smectite group clay minerals (montmorillonite, beidellite, nontronite, saponite, hectorite, soconite, stevensite, etc.), vermiculite group clay minerals (vermiculite etc.), mica or mica group clay minerals (white mica, Mica such as phlogopite, margarite, tetrasilic mica, teniolite, etc.). These minerals may be natural clay minerals or synthetic clay minerals.
  • the swellable inorganic layered compounds are used alone or in combination of two or more.
  • known acid anhydrides can be used in combination as a method for improving the acid resistance of the cured coating film.
  • the acid anhydride include phthalic acid anhydride, succinic acid anhydride, het acid anhydride, hymic acid anhydride, maleic acid anhydride, tetrahydrophthalic acid anhydride, hexahydraphthalic acid anhydride, tetraprom phthalic acid Anhydride, tetrachlorophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenotetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 5- (2 , 5-oxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, styrene maleic anhydride copolymer and the like.
  • a compound having an oxygen scavenging function may be added.
  • the compound having an oxygen scavenging function include low molecular organic compounds that react with oxygen such as hindered phenols, vitamin C, vitamin E, organic phosphorus compounds, gallic acid, pyrogallol, cobalt, manganese, nickel, iron, Examples include transition metal compounds such as copper.
  • a tackifier such as a xylene resin, a terpene resin, a phenol resin, or a rosin resin may be added as necessary.
  • a tackifier such as a xylene resin, a terpene resin, a phenol resin, or a rosin resin may be added as necessary.
  • the range of 0.01 to 5 parts by mass is preferable with respect to 100 parts by mass of the total amount of the epoxy resin and the epoxy resin curing agent.
  • an active energy ray can also be used as a method of reacting a polymerizable double bond.
  • a known technique can be used as the active energy ray, and it can be cured by irradiation with ionizing radiation such as electron beam, ultraviolet ray, or ⁇ ray.
  • ionizing radiation such as electron beam, ultraviolet ray, or ⁇ ray.
  • a known ultraviolet irradiation device equipped with a high pressure mercury lamp, an excimer lamp, a metal halide lamp or the like can be used.
  • Radical-generating photo (polymerization) initiators include hydrogen abstraction types such as benzyl, benzophenone, Michler's ketone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, benzoin ethyl ether, diethoxyacetophenone, benzylmethyl ketal, hydroxy
  • photocleavage types such as cyclohexyl phenyl ketone and 2-hydroxy-2-methylphenyl ketone. These can be used alone or in combination.
  • the glass transition temperature of the cured coating film of the polyester polyol (A) and the polyisocyanate (B) is preferably in the range of ⁇ 30 ° C. to 80 ° C. More preferably, it is 0 ° C to 60 ° C. More preferably, it is 25 ° C to 60 ° C.
  • the glass transition temperature is too higher than 80 ° C., the flexibility of the polyester polyol near the room temperature is lowered, which may reduce the adhesion to the substrate.
  • the temperature is lower than ⁇ 30 ° C., there is a possibility that sufficient oxygen barrier properties may not be obtained due to intense molecular motion of the polyester polyol at around room temperature.
  • the gas barrier multilayer film obtained by curing the polyester resin composition of the present invention is obtained by applying and curing a polyester resin composition coating liquid on a film serving as a base material.
  • the coating liquid may be either a solvent type or a solventless type.
  • the solvent is used as a reaction medium during the production of the polyester resin and the curing agent, and is further used as a diluent during coating.
  • solvents examples include esters such as ethyl acetate, butyl acetate and cellosolve acetate, ketones such as acetone, methyl ethyl ketone, isobutyl ketone and cyclohexanone, ethers such as tetrahydrofuran and dioxane, and aromatic hydrocarbons such as toluene and xylene. , Halogenated hydrocarbons such as methylene chloride and ethylene chloride, dimethyl sulfoxide, dimethyl sulfoamide and the like.
  • polyester resin composition of the present invention is excellent in solubility in ethyl acetate or methyl ethyl ketone solvent, it is preferable to use ethyl acetate or methyl ethyl ketone.
  • the method for applying the polyester resin of the present invention is not particularly limited, and may be performed by a known method.
  • a solvent type whose viscosity can be adjusted, it is often applied by a gravure roll coating method or the like.
  • it when it is a solventless type and has a high viscosity at room temperature and is not suitable for gravure roll coating, it can be coated with a roll coater while heating.
  • the coating is preferably performed in a state where the gas barrier polyester resin composition of the present invention is heated from room temperature to about 120 ° C. so that the viscosity is about 500 to 2500 mPa ⁇ s.
  • the polyester resin composition of the present invention can be used as a gas barrier polyester resin composition for various applications that require gas barrier properties against polymers, paper, metals, etc. as a gas barrier polyester resin composition.
  • a gas barrier polyester resin composition for film lamination will be described as one specific application.
  • the gas barrier multilayer film obtained by curing the polyester resin composition of the present invention can be used as a gas barrier multilayer film for film lamination.
  • the film for lamination used in the present invention is not particularly limited, and a thermoplastic resin film can be appropriately selected according to a desired application.
  • a thermoplastic resin film can be appropriately selected according to a desired application.
  • PET film polystyrene film, polyamide film, polyacrylonitrile film
  • polyethylene film LLDPE: low density polyethylene film
  • HDPE high density polyethylene film
  • polypropylene film CPP: unstretched polypropylene film
  • OPP examples thereof include polyolefin films such as biaxially stretched polypropylene film), polyvinyl alcohol films, and ethylene-vinyl alcohol copolymer films. These may be subjected to stretching treatment.
  • the stretching treatment method it is common to perform simultaneous biaxial stretching or sequential biaxial stretching after the resin is melt-extruded by extrusion film forming method or the like to form a sheet. Further, in the case of sequential biaxial stretching, it is common to first perform longitudinal stretching and then perform lateral stretching. Specifically, a method of combining longitudinal stretching using a speed difference between rolls and transverse stretching using a tenter is often used.
  • the surface of the film may be subjected to various surface treatments such as flame treatment and corona discharge treatment as necessary so that an adhesive layer free from defects such as film breakage and repellency is formed.
  • a gas barrier multilayer film can be obtained by laminating another thermoplastic resin film and laminating them together by lamination using a known dry laminate adhesive.
  • known lamination such as dry lamination, non-solvent lamination, extrusion lamination, etc. can be used.
  • the dry lamination method is a dry lamination (dry lamination method) in which the gas barrier polyester resin composition of the present invention is applied to one of the base films by a gravure roll method, and the other base film is stacked. Paste together.
  • the temperature of the laminate roll is preferably about room temperature to 60 ° C.
  • Non-solvent lamination is applied immediately after applying the gas barrier polyester resin composition of the present invention, which has been heated to room temperature to about 120 ° C., on a base film with a roll such as a roll coater heated to room temperature to about 120 ° C.
  • a laminate film can be obtained by pasting a new film material on the surface.
  • the laminating pressure is preferably about 10 to 300 kg / cm 2 .
  • an organic solvent solution of the gas barrier polyester resin composition of the present invention is applied to a base film as an adhesion aid (anchor coating agent) with a roll such as a gravure roll, and the solvent is used at room temperature to 140 ° C.
  • a laminated film can be obtained by laminating the polymer material melted by the extruder.
  • the polymer material to be melted is preferably a polyolefin resin such as a low density polyethylene resin, a linear low density polyethylene resin, or an ethylene-vinyl acetate copolymer resin.
  • the gas barrier multilayer film of the present invention is preferably subjected to aging after production. If polyisocyanate is used as a curing agent, the aging condition is from room temperature to 80 ° C. for 12 to 240 hours, during which the polyester resin and the curing agent react to produce adhesive strength.
  • a film in which a vapor deposition layer of a metal such as aluminum or a metal oxide such as silica or alumina may be laminated as necessary.
  • the gas barrier polyester resin composition of the present invention can be preferably used as a gas barrier polyester resin composition for a laminated film formed by bonding a plurality of the same or different resin films.
  • the resin film may be appropriately selected depending on the purpose.
  • the outermost layer is a thermoplastic resin film selected from PET, OPP, and polyamide, and the innermost layer is unstretched polypropylene.
  • CPP a composite film consisting of two layers using a thermoplastic resin film selected from a low density polyethylene film (hereinafter abbreviated as LLDPE), or an outermost layer selected from, for example, PET, polyamide and OPP
  • LLDPE low density polyethylene film
  • a three-layer composite using a thermoplastic resin film, a thermoplastic resin film that forms an intermediate layer selected from OPP, PET, and polyamide, and a thermoplastic resin film that forms an innermost layer selected from CPP and LLDPE Heat to form an outermost layer selected from a film, for example, OPP, PET, polyamide Selected from a plastic film, a thermoplastic film forming a first intermediate layer selected from PET and nylon, and a thermoplastic film forming a second intermediate layer selected from PET and polyamide, LLDPE, and CPP
  • a composite film composed of four layers using a thermoplastic resin film forming the innermost layer can be preferably used as a food packaging material as an oxygen and water vapor barrier film.
  • a laminate film formed from the gas barrier polyester resin composition includes a PVDC coat layer, a polyvinyl alcohol (PVA) coat layer, Without using commonly used gas barrier materials such as ethylene-vinyl alcohol copolymer (EVOH) film layer, metaxylylene adipamide film layer, inorganic vapor-deposited film layer deposited with alumina, silica, etc.
  • gas barrier materials such as ethylene-vinyl alcohol copolymer (EVOH) film layer, metaxylylene adipamide film layer, inorganic vapor-deposited film layer deposited with alumina, silica, etc.
  • EVOH ethylene-vinyl alcohol copolymer
  • metaxylylene adipamide film layer metaxylylene adipamide film layer
  • a high level of gas barrier properties is manifested.
  • the gas barrier property of the film obtained can also be remarkably improved by using together as a gas
  • the resin composition according to (II) and (III) of the present invention can be used as a gas barrier adhesive.
  • the adhesive of the present invention may be either a solvent type or a solventless type.
  • the solvent may be used as a reaction medium during the production of the polyester polyol and the curing agent. Furthermore, it is used as a diluent during painting.
  • the solvent that can be used include esters such as ethyl acetate, butyl acetate, and cellosolve acetate, ketones such as acetone, methyl ethyl ketone, isobutyl ketone, and cyclohexanone, ethers such as tetrahydrofuran and dioxane, and aromatic hydrocarbons such as toluene and xylene.
  • Halogenated hydrocarbons such as methylene chloride and ethylene chloride, dimethyl sulfoxide, dimethyl sulfoamide and the like. Of these, it is usually preferable to use ethyl acetate or methyl ethyl ketone.
  • Sex when used without a solvent, it is not always necessary to be soluble in an organic solvent, but considering the washing of a reaction kettle during synthesis and the washing of a coating machine during lamination, Sex is necessary.
  • the adhesive of the present invention can be used by being applied to a substrate film or the like.
  • the coating method is not particularly limited and may be performed by a known method.
  • a solvent type whose viscosity can be adjusted
  • it is often applied by a gravure roll coating method.
  • it when it is a solventless type and has a high viscosity at room temperature and is not suitable for gravure roll coating, it can be coated with a roll coater while heating.
  • the adhesive of the present invention can be used as an oxygen barrier adhesive for various applications that require oxygen barrier properties against polymers, paper, metals, and the like.
  • an adhesive for film lamination will be described as one of specific applications.
  • the adhesive of the present invention can be used as an adhesive for film lamination. Since the laminated film is excellent in oxygen barrier properties, it can be used as an oxygen barrier laminated film.
  • the film for lamination used in the present invention is not particularly limited, and a thermoplastic resin film can be appropriately selected according to a desired application.
  • a thermoplastic resin film can be appropriately selected according to a desired application.
  • PET film polystyrene film, polyamide film, polyacrylonitrile film
  • polyethylene film LLDPE: low density polyethylene film
  • HDPE high density polyethylene film
  • polypropylene film CPP: unstretched polypropylene film
  • OPP examples thereof include polyolefin films such as biaxially stretched polypropylene film), polyvinyl alcohol films, and ethylene-vinyl alcohol copolymer films. These may be subjected to stretching treatment.
  • the stretching treatment method it is common to perform simultaneous biaxial stretching or sequential biaxial stretching after the resin is melt-extruded by extrusion film forming method or the like to form a sheet. Further, in the case of sequential biaxial stretching, it is common to first perform longitudinal stretching and then perform lateral stretching. Specifically, a method of combining longitudinal stretching using a speed difference between rolls and transverse stretching using a tenter is often used.
  • a transparent vapor-deposited film having a high oxygen barrier property is used on both sides of the adhesive, polymerization of the polymerizable double bond of the polyester polyol (A) as an adhesive component is inhibited and good barrier properties are not exhibited.
  • the oxygen barrier property of the oxygen barrier laminate film is preferably such that the oxygen permeability of at least one laminate film is 0.1 cc / m 2 ⁇ day ⁇ atm or more.
  • the surface of the film may be subjected to various surface treatments such as flame treatment and corona discharge treatment as necessary so that an adhesive layer free from defects such as film breakage and repellency is formed.
  • the other thermoplastic resin film is overlaid and bonded by lamination to obtain the oxygen barrier laminate film of the present invention.
  • lamination method known lamination such as dry lamination, non-solvent lamination, extrusion lamination, etc. can be used.
  • the adhesive of the present invention is applied to one of the base films by the gravure roll method, and the other base film is stacked and bonded by dry lamination (dry lamination method).
  • the temperature of the laminate roll is preferably about room temperature to 60 ° C.
  • non-solvent lamination is applied to the surface immediately after applying the adhesive of the present invention, which has been heated to room temperature to about 120 ° C., with a roll such as a roll coater heated to room temperature to about 120 ° C.
  • a laminate film can be obtained by laminating various film materials.
  • the laminating pressure is preferably about 10 to 300 kg / cm 2 .
  • the organic solvent solution of the adhesive of the present invention is applied to the base film as an adhesion aid (anchor coating agent) by a roll such as a gravure roll, and the solvent is dried and cured at room temperature to 140 ° C.
  • a laminate film can be obtained by laminating the polymer material melted by the extruder.
  • the polymer material to be melted is preferably a polyolefin resin such as a low density polyethylene resin, a linear low density polyethylene resin, or an ethylene-vinyl acetate copolymer resin.
  • the oxygen barrier laminate film of the present invention is preferably subjected to aging after production. If polyisocyanate is used as a curing agent, the aging condition is from room temperature to 80 ° C. for 12 to 240 hours, during which adhesive strength is generated.
  • a barrier film containing a gas barrier layer such as a polymer or vinylidene chloride may be used in combination.
  • the adhesive of the present invention can be preferably used as an adhesive for a laminated film formed by bonding a plurality of the same or different resin films.
  • the resin film may be appropriately selected depending on the purpose.
  • the outermost layer is a thermoplastic resin film selected from PET, OPP, and polyamide, and the innermost layer is unstretched polypropylene.
  • CPP a composite film consisting of two layers using a thermoplastic resin film selected from a low density polyethylene film (hereinafter abbreviated as LLDPE), or an outermost layer selected from, for example, PET, polyamide and OPP
  • LLDPE low density polyethylene film
  • a three-layer composite using a thermoplastic resin film, a thermoplastic resin film that forms an intermediate layer selected from OPP, PET, and polyamide, and a thermoplastic resin film that forms an innermost layer selected from CPP and LLDPE Heat to form an outermost layer selected from a film, for example, OPP, PET, polyamide Selected from a plastic film, a thermoplastic film forming a first intermediate layer selected from PET and nylon, and a thermoplastic film forming a second intermediate layer selected from PET and polyamide, LLDPE, and CPP
  • a composite film composed of four layers using a thermoplastic resin film forming the innermost layer can be preferably used as a food packaging material as an oxygen and water vapor barrier film.
  • the laminate film formed by the adhesive is a PVDC coat layer, a polyvinyl alcohol (PVA) coat layer, an ethylene-vinyl alcohol copolymer. (EVOH)
  • PVDC coat layer a polyvinyl alcohol (PVA) coat layer
  • EVOH ethylene-vinyl alcohol copolymer.
  • a very high level of gas barrier properties is achieved without using commonly used gas barrier materials such as film layers, metaxylylene adipamide film layers, and inorganic vapor deposited film layers deposited with alumina, silica, etc. To do.
  • the gas barrier property of the obtained film can also be remarkably improved by using together as an adhesive agent which bonds these conventional gas barrier material and sealant material together.
  • polyester resin “GLY (oPAEG) 3” having a number average molecular weight of 668.60.
  • the mass% of glycerol contained in this polyester resin was 13.32%.
  • Production Example 6 Production Method of Polyester Polyol “TMP (oPAEG) 3” Composed of Trimethylolpropane, Orthophthalic Anhydride, and Ethylene Glycol, except that instead of glycerol 92.09 in Production Example 3, it was replaced with 134.17 parts of trimethylolpropane In the same manner as in Production Example 3, a number average molecular weight 710.68 polyester polyol “TMP (oPAEG) 3” was obtained. The mass% of glycerol contained in this polyester polyol was 0.0%.
  • Polyester polyol “TMP (oPAEG) 6" comprising trimethylolpropane, orthophthalic anhydride and ethylene glycol Production method Production Example 4 was replaced with 134.17 parts of trimethylolpropane instead of 92.09 parts of glycerol.
  • the polyester polyol “TMP (oPAEG) 6” having a number average molecular weight of 1287.18 was obtained in the same manner as in Production Example 4 except for the above.
  • the mass% of glycerol contained in this polyester polyol was 0.0%.
  • the non-volatile content of the curing agent a is 87.5% and NCO% 28.05%.
  • Examples 1 to 8 Comparative Examples 1 to 4
  • the polyester polyol obtained by the above production method is diluted with methyl ethyl ketone to obtain a resin solution having a non-volatile content of 50%, and further, curing agents a, b, c, d are blended as shown in Tables 1 to 3, and will be described later.
  • a polyester resin coating solution used in the coating method was obtained.
  • the gas barrier multilayer film that has been aged is used in an atmosphere of 23 ° C., 0% RH and 90% RH in accordance with JIS-K7126 (isobaric method) using an oxygen permeability measuring device OX-TRAN2 / 21MH manufactured by Mocon. It was measured.
  • the oxygen barrier multilayer films coated with the resin compositions of Examples 1 to 8 all had an oxygen permeability of 30 cc / m 2 ⁇ day ⁇ atm or less.
  • Comparative Examples 1 to 3 did not contain glycerol, the oxygen permeability remained at 35 to 45 cc / m 2 ⁇ day ⁇ atm. Further, in Comparative Example 4, when the phthalic acid of the polyester resin was changed to isophthalic acid, the solvent solubility was lost and the film could not be applied to the film.
  • the esterification reaction was terminated to obtain a polyester polyol having a number average molecular weight of about 600, a hydroxyl value of 182 mgKOH / g, and an acid value of 0.9 mgKOH / g.
  • the temperature was lowered to 120 ° C., and 421.8 parts of maleic anhydride was added thereto, and maintained at 120 ° C.
  • the esterification reaction is terminated to obtain a polyester polyol having a number average molecular weight of about 500, a hydroxyl value of 216 mgKOH / g, and an acid value of 96 mgKOH / g. It was.
  • Polyester polyol Production example of EGSucA In Production Example 13, 98.1 parts of maleic anhydride is 118.1 parts of succinic acid, 78.5 parts of ethylene glycol is 71.6 parts, and the internal temperature is 205 ° C. A polyester polyol having a number average molecular weight of about 1000, a hydroxyl value of 112.2 mgKOH / g, and an acid value of 0.4 mgKOH / g was obtained in the same manner as in Production Example 13 except that the temperature was 220 ° C.
  • polyester polyol (Example 9) to (Example 15) According to the examples in Table 4 to Table 6, polyester polyol, curing agent, catalyst and solvent were mixed to obtain an adhesive.
  • the coating method and the evaluation method were as follows.
  • the solvent-type adhesive is a corona of a PET film (“E-5102” manufactured by Toyobo Co., Ltd.) having a thickness of 12 ⁇ m so that the coating amount is 5.0 g / m 2 (solid content). It was applied to the treated surface, and the solvent was volatilized and dried with a dryer set at a temperature of 70 ° C., and the adhesive surface of the PET film on which the adhesive was applied, and a 70 ⁇ m thick CPP film (“ZK93KM, manufactured by Toray Industries, Inc.) ]) was laminated with the corona-treated surface to prepare a composite film having a layer structure of PET film / adhesive layer / CPP film. Next, this composite film was aged at 40 ° C. for 3 to 5 days to cure the adhesive, and the oxygen barrier laminate film of the present invention was obtained.
  • a PET film (“E-5102” manufactured by Toyobo Co., Ltd.) having a thickness of 12 ⁇ m so that the coating amount is 5.0 g
  • Coating method 2 The solventless adhesive is heated to about 100 ° C. and applied to a PET film so that the coating amount is 5.0 g / m 2 using a roll coater manufactured by Polytype Co., Ltd.
  • a composite film having a layer structure of PET film / adhesive layer / CPP film was prepared by laminating with the film. Subsequently, this composite film was subjected to aging at 40 ° C. for 3 days to cure the adhesive, thereby obtaining the oxygen barrier laminate film of the present invention.
  • Adhesive strength The oxygen barrier laminate film after aging was cut into a width of 15 mm parallel to the coating direction, and a PET / CPP film was used with a Tensilon universal testing machine manufactured by Orientec Co., Ltd. Then, the atmospheric temperature was set to 25 ° C., the peeling speed was set to 300 mm / min, and the tensile strength when peeling by the 180 ° peeling method was defined as the adhesive strength.
  • the unit of adhesive strength was N / 15 mm.
  • Oxygen transmission rate Oxygen barrier laminated film after aging was used in an atmosphere of 23 ° C. and 90% RH in accordance with JIS-K7126 (isobaric method) using an oxygen transmission rate measuring device OX-TRAN2 / 21MH manufactured by Mocon. Measured below. Note that RH represents humidity.
  • the polyester polyol shown in the production example was mixed with ethyl acetate and methyl ethyl ketone (described as MEK) so as to have a nonvolatile content of 50%, and the solubility was confirmed.
  • MEK methyl ethyl ketone
  • the monomer refers to the polyvalent carboxylic acid and polyhydric alcohol.
  • Production Examples 23 to 29, Examples 16 to 22 and Comparative Examples 9 and 10 relate to the polyester resin composition according to (III).
  • Production Example 23 Production Example of Polyester Polyol (A): Gly (OPAEG) 2MA In the same manner as in Production Example 13, the title compound was obtained.
  • Production Example 24 Production Example of Polyester Polyol (A): Gly (OPAEG) 2OPA 1316.8 parts of phthalic anhydride in Production Example 23 is 1023.7 parts, 573.9 parts of ethylene glycol is 446.2 parts, and glycerin A polyester polyol having a hydroxyl value of 309.8 mgKOH / g was obtained in the same manner as in Production Example 23 except that 409.3 parts was changed to 318.2 parts.
  • polyester polyol was obtained. Polyester polyol (A) Number of functional groups designed per molecule: 2 hydroxyl groups, 1 carboxy group
  • polyester polyol had a number average molecular weight of about 720, a hydroxyl value of 156 mgKOH / g, and an acid value of 77.8 mgKOH / g. Got.
  • polyester polyol was obtained. Polyester polyol (A) Number of functional groups designed per molecule: 2 hydroxyl groups, 1 carboxy group
  • Production Example 27 Production Example of Polyester Polyol (A): Gly (OPAEG) 2TMT 1316.8 parts of phthalic anhydride in Production Example 23 is 274.0 parts, 573.9 parts of ethylene glycol is 119.4 parts, and glycerin A polyester polyol having a hydroxyl value of 306.8 mgKOH / g was obtained in the same manner as in Production Example 1 except that 409.3 parts were changed to 85.2 parts.
  • polyester polyol having a number average molecular weight of about 860, a hydroxyl value of 195.4 mgKOH / g, and an acid value of 0.9 mgKOH / g.
  • Polyester polyol (A) Number of functional groups designed per molecule Hydroxyl groups: 3, carboxy groups: 0
  • polyester polyol having a number average molecular weight of about 650, a hydroxyl value of 261.2 mgKOH / g, and an acid value of 0.8 mgKOH / g.
  • Polyester polyol (A) Number of functional groups designed per molecule Hydroxyl groups: 3, carboxy groups: 0
  • the solvent-type adhesive is a corona of a PET film (“E-5102” manufactured by Toyobo Co., Ltd.) having a thickness of 12 ⁇ m so that the coating amount is 5.0 g / m 2 (solid content). It was applied to the treated surface, and the solvent was volatilized and dried with a dryer set at a temperature of 70 ° C., and the adhesive surface of the PET film on which the adhesive was applied, and a 70 ⁇ m thick CPP film (“ZK93KM, manufactured by Toray Industries, Inc.) ]) was laminated with the corona-treated surface to prepare a composite film having a layer structure of PET film / adhesive layer / CPP film. Next, this composite film was aged at 40 ° C. for 3 days to cure the adhesive, and the oxygen barrier laminate film of the present invention was obtained.
  • a PET film (“E-5102” manufactured by Toyobo Co., Ltd.) having a thickness of 12 ⁇ m so that the coating amount is 5.0 g /
  • the solventless adhesive is heated to about 100 ° C., and a corona of a 12 ⁇ m thick PET film (“E-5102” manufactured by Toyobo Co., Ltd.) using a roll coater manufactured by Polytype Co., Ltd. After coating the treated surface so that the coating amount is 5.0 g / m 2 , the coated surface is laminated with a corona-treated surface of a 70 ⁇ m thick CPP film (“ZK93KM” manufactured by Toray Industries, Inc.), and a PET film / adhesive layer / A composite film having a layer structure of a CPP film was produced. Subsequently, this composite film was subjected to aging at 40 ° C. for 3 days to cure the adhesive, thereby obtaining the oxygen barrier laminate film of the present invention.
  • a corona of a 12 ⁇ m thick PET film (“E-5102” manufactured by Toyobo Co., Ltd.) using a roll coater manufactured by Polytype Co., Ltd.
  • the coated surface is
  • Adhesive strength The oxygen barrier laminate film after aging was cut into a width of 15 mm parallel to the coating direction, and a PET / CPP film was used with a Tensilon universal testing machine manufactured by Orientec Co., Ltd. Then, the atmospheric temperature was set to 25 ° C., the peeling speed was set to 300 mm / min, and the tensile strength when peeling by the 180 ° peeling method was defined as the adhesive strength.
  • the unit of adhesive strength was N / 15 mm.
  • the atmosphere temperature was set to 25 ° C.
  • the peeling speed was set to 300 mm / min
  • one end in the length direction of the obtained test piece was PET film A and the other end was Fixed the PET film B, conducted a tensile test, and determined the obtained strength as the initial cohesive force.
  • the unit was N / cm 2 .
  • the evaluation value was the maximum measured intensity, and the results are shown in the table.
  • Laminate suitability As an assessment of laminate suitability, the appearance of the film immediately after lamination was evaluated according to the following criteria. ⁇ : Uniformly wet and good appearance. (Triangle
  • Oxygen transmission rate Oxygen barrier laminate film after aging was measured at 23 ° C. and 90% RH in accordance with JIS-K7126 (isobaric method) using an oxygen transmission rate measuring device OX-TRAN2 / 21MH manufactured by Mocon. Measured under atmosphere.
  • the oxygen barrier laminated film using the adhesives of Examples 16 to 22 has a high oxygen barrier property and initial cohesive strength under 90% RH compared with the polyester polyol (A) not containing a carboxy group. And also had good adhesive strength.
  • the oxygen permeability was relatively good but not at a sufficient level, and the initial cohesion was also at a significantly low level.
  • gas barrier multilayer film of the present invention has gas barrier properties, it can be suitably used as various packaging materials. Further, since the barrier coating material and the gas barrier adhesive constituting the gas barrier multilayer film of the present invention have gas barrier properties, in the case of the gas barrier coating material, in addition to the film laminating primer for the packaging material, for display elements In addition to coating agents for electronic materials such as coating agents for gas barrier substrates, coating materials for building materials, coatings for industrial materials, and gas barrier properties can be suitably used. In addition, in the case of gas barrier adhesives, it is suitable for adhesives for film laminates for packaging materials, primers for film laminates, adhesives for protective films for solar cells, sealing materials for display elements, etc. Can be used for

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Abstract

La présente invention concerne un film multicouche présentant des propriétés de barrière aux gaz, un adhésif et un matériau de revêtement, et concerne en outre une composition de résine polyester permettant d'obtenir le film multicouche présentant des propriétés de barrière aux gaz, l'adhésif et le matériau de revêtement. La présente invention a pour but de produire un film multicouche formant barrière aux gaz présentant d'excellentes propriétés de barrière aux gaz. L'invention a également pour but de produire : une composition de résine polyester présentant des propriétés de barrière aux gaz et comportant, à titre de composant principal, la résine polyester qui est employée en tant que couche formant barrière aux gaz dans le film multicouche présentant des propriétés de barrière aux gaz ; un film multicouche présentant des propriétés de barrière aux gaz comprenant un film revêtu de la composition de résine ; et un matériau de revêtement. La production d'un film multicouche présentant des propriétés de barrière aux gaz, comportant une couche formant barrière aux gaz obtenue en durcissant une composition de résine polyester formée par la mise en réaction d'un polyester polyol avec un agent de durcissement, permet d'atteindre ce but à l'aide d'une composition de résine polyester possédant une structure spécifique.
PCT/JP2012/067067 2011-07-06 2012-07-04 Film multicouche présentant des propriétés de barrière aux gaz, adhésif et matériau de revêtement WO2013005767A1 (fr)

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JP2011149977A JP5543408B2 (ja) 2011-07-06 2011-07-06 ガスバリア性ポリエステル樹脂組成物、及びガスバリア性フィルム
JP2011-149977 2011-07-06
JP2011-154773 2011-07-13
JP2011154774A JP5273219B2 (ja) 2011-07-13 2011-07-13 酸素バリア性接着剤用樹脂組成物、及び接着剤
JP2011-154774 2011-07-13
JP2011154773A JP5201429B2 (ja) 2011-07-13 2011-07-13 酸素バリア性接着剤用樹脂組成物、接着剤、及び積層体

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WO2014103994A1 (fr) * 2012-12-26 2014-07-03 Dic株式会社 Composition de résine de polyester, adhésif et film
JP5790981B1 (ja) * 2014-07-11 2015-10-07 Dic株式会社 シーラントフィルムを有する積層体
WO2016006125A1 (fr) * 2014-07-11 2016-01-14 Dic株式会社 Corps stratifié comportant une pellicule d'agent d'étanchéité
WO2016104510A1 (fr) * 2014-12-24 2016-06-30 東洋インキＳｃホールディングス株式会社 Composition adhésive et stratifié
CN106536197A (zh) * 2014-07-24 2017-03-22 凸版印刷株式会社 层叠膜及层叠体、以及波长转换片材、背光单元及电致发光单元
CN107636035A (zh) * 2015-06-18 2018-01-26 Dic株式会社 双液固化型组合物、双液型粘合剂、双液型涂布剂、层压体
JPWO2018110190A1 (ja) * 2016-12-16 2019-10-24 ソニー株式会社 光学素子、撮像素子パッケージ、撮像装置および電子機器
CN112236494A (zh) * 2018-08-01 2021-01-15 Dic株式会社 粘合剂组合物和表面保护膜
WO2024101165A1 (fr) * 2022-11-10 2024-05-16 Dic株式会社 Composition de barrière contre les gaz, agent de revêtement et corps multicouche
EP4245527A4 (fr) * 2020-11-10 2024-08-14 DIC Corporation Stratifié barrière aux gaz et matériau d?emballage
CN118638401A (zh) * 2024-08-15 2024-09-13 福建满山红新材料科技股份公司 一种高强度高寿命抗拉伸环保塑料包装袋

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WO2014103994A1 (fr) * 2012-12-26 2014-07-03 Dic株式会社 Composition de résine de polyester, adhésif et film
JPWO2014103994A1 (ja) * 2012-12-26 2017-01-12 Dic株式会社 ポリエステル樹脂組成物、接着剤、及びフィルム
US9777149B2 (en) 2012-12-26 2017-10-03 Dic Corporation Polyester resin composition, adhesive and film
JP5790981B1 (ja) * 2014-07-11 2015-10-07 Dic株式会社 シーラントフィルムを有する積層体
WO2016006125A1 (fr) * 2014-07-11 2016-01-14 Dic株式会社 Corps stratifié comportant une pellicule d'agent d'étanchéité
EP3173230A4 (fr) * 2014-07-24 2017-12-20 Toppan Printing Co., Ltd. Film multicouche, stratifié, feuille de conversion de longueur d'onde, unité de rétroéclairage et unité d'émission de lumière électroluminescente
CN106536197B (zh) * 2014-07-24 2019-09-20 凸版印刷株式会社 层叠膜及层叠体、以及波长转换片材、背光单元及电致发光单元
CN106536197A (zh) * 2014-07-24 2017-03-22 凸版印刷株式会社 层叠膜及层叠体、以及波长转换片材、背光单元及电致发光单元
US9951259B2 (en) 2014-12-24 2018-04-24 Toyo Ink Sc Holdings Co., Ltd. Adhesive composition and laminate
JP2016121351A (ja) * 2014-12-24 2016-07-07 東洋インキＳｃホールディングス株式会社 接着剤組成物および積層体
WO2016104510A1 (fr) * 2014-12-24 2016-06-30 東洋インキＳｃホールディングス株式会社 Composition adhésive et stratifié
CN107636035A (zh) * 2015-06-18 2018-01-26 Dic株式会社 双液固化型组合物、双液型粘合剂、双液型涂布剂、层压体
CN107636035B (zh) * 2015-06-18 2021-03-12 Dic株式会社 双液固化型组合物、双液型粘合剂、双液型涂布剂、层压体
JPWO2018110190A1 (ja) * 2016-12-16 2019-10-24 ソニー株式会社 光学素子、撮像素子パッケージ、撮像装置および電子機器
JP7006617B2 (ja) 2016-12-16 2022-01-24 ソニーグループ株式会社 光学素子、撮像素子パッケージ、撮像装置および電子機器
CN112236494A (zh) * 2018-08-01 2021-01-15 Dic株式会社 粘合剂组合物和表面保护膜
CN112236494B (zh) * 2018-08-01 2022-07-26 Dic株式会社 粘合剂组合物和表面保护膜
EP4245527A4 (fr) * 2020-11-10 2024-08-14 DIC Corporation Stratifié barrière aux gaz et matériau d?emballage
WO2024101165A1 (fr) * 2022-11-10 2024-05-16 Dic株式会社 Composition de barrière contre les gaz, agent de revêtement et corps multicouche
JP7533813B1 (ja) 2022-11-10 2024-08-14 Dic株式会社 ガスバリア用組成物、コーティング剤および積層体
CN118638401A (zh) * 2024-08-15 2024-09-13 福建满山红新材料科技股份公司 一种高强度高寿命抗拉伸环保塑料包装袋

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