Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
• • 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
• • 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
  • 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
  • C08G18/4216—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 mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids 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
  • 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
  • C08G18/4263—Polycondensates having carboxylic or carbonic ester groups in the main chain containing carboxylic acid 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
  • C08G18/7806—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
  • C08G18/7806—Nitrogen containing -N-C=0 groups
  • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
  • C08G18/7837—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing allophanate 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
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
  • C09J175/06—Polyurethanes from polyesters

Definitions

• the present invention relates to a polyester resin composition excellent in adhesiveness, moist heat resistance and corrosion resistance, and an adhesive composition using the same. More particularly, the present invention relates to an adhesive composition for aluminum laminate films and decorative sheets used for building materials, home appliances, and the like.
• Solvent-based two-component dry laminating adhesive is mainly used for laminating various plastic films such as home appliance exteriors and building materials and metal foils such as aluminum.
• the two-component dry laminate adhesive is an adhesive that uses polyurethane and polyester having a hydroxyl group at the end as a main ingredient and a curing agent having an isocyanate group that reacts with the hydroxyl group, and is used for durability such as wet heat.
• a formulation in which an epoxy compound is added has been proposed.
• Patent Document 1 In order to reduce the moisture permeability, a prescription in which an inorganic moisture-proof layer is provided with silicon oxide or magnesium oxide has been developed (for example, Patent Document 1).
• Patent Document 1 a prescription in which an inorganic moisture-proof layer is provided with silicon oxide or magnesium oxide has been developed.
• Patent Document 1 In order to reduce the moisture permeability, a prescription in which an inorganic moisture-proof layer is provided with silicon oxide or magnesium oxide has been developed (for example, Patent Document 1).
• Patent Document 1 In order to reduce the moisture permeability, a prescription in which an inorganic moisture-proof layer is provided with silicon oxide or magnesium oxide has been developed (for example, Patent Document 1).
• Patent Document 1 In order to reduce the moisture permeability, a prescription in which an inorganic moisture-proof layer is provided with silicon oxide or magnesium oxide has been developed (for example, Patent Document 1).
• Patent Document 1 In order to reduce the moisture permeability, a prescription in which an inorganic moisture-proof layer is provided with silicon oxide or magnesium oxide has been
• a decorative sheet has been proposed in which a transparent resin film is provided as a backing layer of a metal foil, and the color tone of the metal surface is not changed by corrosion by using a transparent resin film having a linear expansion coefficient as close as possible to the metal foil (for example, Patent Document 2).
• JP 2004-42343 A Japanese Patent No. 4616634
• Patent Document 2 requires special production and a base material, and requires complicated steps, which cannot be put to practical use.
• the present invention provides a polyester resin composition excellent in adhesiveness, moist heat resistance and corrosion resistance, and an adhesive composition using the same, without requiring a special device or substrate.
• the present inventors diligently studied and came to propose the following invention. That is, the present invention is as follows.
• the storage elastic modulus at 60 ° C. of the thin film is 4.8 ⁇ 10 6 Pa or less.
• the storage elastic modulus of the thin film at 200 ° C. is 2.0 ⁇ 10 5 Pa or more.
• the polyester resin composition preferably contains 1.5 to 20 parts by mass of polyisocyanate (B) with respect to 100 parts by mass of the polyester resin (A).
• the gel fraction after the wet heat test is preferably 50% or more.
• the polyisocyanate (B) is preferably biuret type hexamethylene diisocyanate or allophanate type hexamethylene diisocyanate.
• the epoxy resin (C) is preferably a bisphenol A type epoxy resin.
• An adhesive composition containing the polyester resin composition is an adhesive composition containing the polyester resin composition.
• a laminate of an aluminum foil or aluminum vapor-deposited layer and a plastic film bonded with the adhesive composition is provided.
• the polyester resin composition of the present invention is suitable for an adhesive for an aluminum laminate film because it is excellent in adhesiveness, moist heat resistance and corrosion resistance.
• it is suitable for use as a decorative sheet used in building materials and home appliances that require high design properties.
• the polyester resin (A) used in the present invention is preferably a polyester having a polyvalent carboxylic acid component and a polyhydric alcohol component as a copolymer component, and more preferably a dicarboxylic acid component and a glycol component as a copolymer component. preferable.
• Aromatic dicarboxylic acid, aliphatic dicarboxylic acid, or alicyclic dicarboxylic acid is mentioned, Especially using aromatic dicarboxylic acid and aliphatic dicarboxylic acid together It is preferable to do.
• the copolymerization amount of the aromatic dicarboxylic acid is preferably 50 mol% or more, more preferably 60 mol% or more, when the total amount of carboxylic acid components is 100 mol%. If the amount is too small, the ester group concentration may be too high to obtain a polyester resin (A) excellent in heat-and-moisture resistance. Moreover, 90 mol% or less is preferable and 80 mol% or less is more preferable. If the amount is too large, the storage elastic modulus at 60 ° C. becomes too large, and the adhesion to the substrate may be lowered.
• aromatic dicarboxylic acid examples include, but are not limited to, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalic acid, 2,6-naphthalic acid, 4,4′-diphenyldicarboxylic acid, 2,2 '-Diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid and the like can be mentioned, and these can be used alone or in combination of two or more.
• terephthalic acid and isophthalic acid are preferably used from the viewpoint of heat and humidity resistance.
• the aliphatic dicarboxylic acid is not particularly limited, but it is preferable to use an aliphatic dicarboxylic acid having 4 to 10 carbon atoms.
• the more preferable carbon number of the aliphatic dicarboxylic acid is 5 or more, and further preferably 6 or more carbon atoms. Moreover, carbon number 10 or less is more preferable.
• the copolymerization amount of the aliphatic dicarboxylic acid is preferably 50 mol% or less, more preferably 40 mol% or less, when the total amount of carboxylic acid components is 100 mol%.
• 10 mol% or more is preferable, More preferably, it is 20 mol% or more. If the amount is too small, the storage elastic modulus at 60 ° C. becomes too large, and the adhesion to the substrate may be lowered. If the amount is too large, the ester group concentration becomes too high, and the polyester resin (A) having excellent heat and heat resistance may not be obtained.
• aliphatic dicarboxylic acid examples include, but are not limited to, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, octadecanedioic acid, etc., and these may be used alone or in combination of two or more. Can do. Of these, use of adipic acid or sebacic acid is preferable from the viewpoint of availability.
• the copolymerization amount of the alicyclic dicarboxylic acid is preferably 50 mol% or less, more preferably 40 mol% or less, further preferably 30 mol% or less when the total amount of the carboxylic acid components is 100 mol%. In particular, it is preferably 20 mol% or less, most preferably 10 mol% or less, and may be 0 mol%. If the amount is too large, it may not be possible to obtain a polyester resin excellent in moisture and heat resistance.
• alicyclic dicarboxylic acid examples include, but are not limited to, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid An acid, a dimer acid, etc. are mentioned, These can be used individually or in combination of 2 or more types. Of these, 1,4-cyclohexanedicarboxylic acid is particularly preferred from the viewpoint of availability.
• Anhydrous polyvalent carboxylic acid can be used for the purpose of imparting acid value or branching to the polyester resin (A). By imparting an acid value or branching, it is expected that the reactivity with the polyisocyanate (B) is improved and the adhesion to a substrate such as aluminum is improved.
• the polyvalent carboxylic anhydride is not particularly limited, but aromatic anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, ethylene glycol bis (anhydrotrimellitate), glycerol trisanhydrotrimellitate, etc.
• Polyhydric carboxylic acid aliphatic polyhydric carboxylic acid such as fumaric anhydride, maleic anhydride, succinic anhydride, itaconic anhydride, dodecenyl succinic anhydride; hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, etc. Mention may be made of alicyclic polyhydric carboxylic acids. These can be used alone or in combination of two or more.
• polyhydric carboxylic anhydrides aromatic polyhydric carboxylic acids are preferred because they have higher acid value and branching effect than aliphatic polyhydric carboxylic acids and alicyclic polyhydric anhydrides.
• trimellitic anhydride ethylene glycol bis (anhydro trimellitate) and glycerol tris anhydro trimellitate are preferable, and trimellitic anhydride is more preferable from the viewpoint of availability.
• the method for imparting branching is not particularly limited, and a trifunctional or higher polyhydric anhydride is used as a copolymerization component of the polyester resin (A), followed by a dehydration esterification step together with other polyhydric carboxylic acids and polyhydric alcohols. There is a way to polymerize.
• the acid value imparting method is not particularly limited, and examples thereof include a method in which after the polyester resin (A) is polymerized, a trifunctional or higher polyhydric anhydride carboxylic acid is introduced into the system to impart an acid value.
• the copolymerization amount of the polyvalent carboxylic anhydride is preferably 5 mol% or less, more preferably 2 mol% or less, and more preferably 1 mol% or less when the total amount of the carboxylic acid components is 100 mol%. More preferably. If the amount is too large, mechanical properties such as a thin film may be deteriorated, and gelation may occur during polymerization.
• the acid value of the polyester resin (A) may be 0 equivalent / 10 6 g or more, preferably 0.5 equivalent / 10 6 g or more, and more preferably 1 equivalent / 10 6 g or more. More preferably, it is 5 equivalents / 10 6 g or more. On the other hand, it is preferably 200 equivalents / 10 6 g or less, more preferably 180 equivalents / 10 6 g or less, further preferably 160 equivalents / 10 6 g or less, and 140 equivalents / 10 6 g or less. It is particularly preferred that If it is too high, the polyester resin (A) may be hydrolyzed and the heat and humidity resistance may be lowered.
• the aliphatic glycol may be either a linear aliphatic glycol or a branched aliphatic glycol. Although it does not specifically limit as aliphatic glycol, C2-C10 glycol is preferable. A more preferable carbon number of the aliphatic glycol is 2 or more. The number of carbon atoms is preferably 9 or less, more preferably 8 or less, even more preferably 7 or less, and particularly preferably 6 or less.
• the copolymerization amount of the aliphatic glycol is preferably 40 mol% or more, more preferably 50 mol% or more, still more preferably 60 mol% or more, when the total amount of the glycol components is 100 mol%.
• the copolymerization amount of the aliphatic glycol is too small, the glass transition temperature rises and the flexibility is lowered, so that the adhesion to a substrate such as aluminum may be lowered.
• aliphatic glycol examples include, but are not limited to, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,2-butanediol, neopentyl glycol, methyl Pentanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecanediol and the like can be mentioned, and these can be used alone or in combination of two or more. Of these, ethylene glycol, neopentyl glycol, 1,4-butanediol, and 1,6-hexanediol are preferably used.
• the alicyclic glycol is not particularly limited, and examples thereof include cyclohexanediol, cyclohexanedimethanol, and hydrogenated xylylene glycol.
• the aromatic glycol is not particularly limited, but includes xylylene glycol.
• the glass transition temperature (hereinafter also referred to as Tg) of the polyester resin (A) needs to be 15 ° C. or less.
• the glass transition temperature is more preferably 14 ° C. or lower, further preferably 13 ° C. or lower, and particularly preferably 12 ° C. or lower. If the glass transition temperature is too high, the flexibility is lowered, and the adhesiveness may be lowered.
• the lower limit is not particularly limited, but is preferably ⁇ 10 ° C. or higher, more preferably ⁇ 5 ° C. or higher.
• the glass transition temperature in the present invention is measured with a differential scanning calorimeter (SII, DSC-200). Specifically, about 5 mg of a sample (sample) is put in an aluminum press-lid container, sealed, cooled to ⁇ 50 ° C. using liquid nitrogen, and then heated to 150 ° C. at 20 ° C./min. In the endothermic curve obtained in the process, the temperature at the intersection of the baseline before the endothermic peak and the tangent line toward the endothermic peak is defined as the glass transition temperature (Tg, unit: ° C.).
• the ester group concentration of the polyester resin (A) needs to be 8500 equivalent / 10 6 g or more and 11000 equivalent / 10 6 g or less.
• the ester group concentration is preferably 8600 equivalent / 10 6 g or more, more preferably 8700 equivalent / 10 6 g or more, further preferably 8800 equivalent / 10 6 g or more, and particularly preferably 8900 equivalent / 10 6 g. Above, most preferably 9000 equivalents / 10 6 g or more.
• 10900 equivalent / 10 ⁇ 6 > g or less is preferable, 10800 equivalent / 10 ⁇ 6 > g or less is more preferable, 10700 equivalent / 10 ⁇ 6 > g or less is more preferable, 10600 equivalent / 10 ⁇ 6 > g or less is especially preferable, 10500 equivalent / 10 ⁇ 6 > Most preferred is g or less. If the ester group concentration is too low, the reactivity with the polyisocyanate (B) may be insufficient and the adhesiveness may be lowered. If the ester group concentration is too high, the polyester resin (A) may be hydrolyzed and the heat and humidity resistance may be lowered.
• the unit of the ester group concentration in the present invention is a value calculated from the composition of the polyester resin (A) and its copolymerization ratio, expressed as the number of equivalents per 1 t of the polyester resin (A).
• the number average molecular weight of the polyester resin (A) is preferably 5000 or more, more preferably 6000 or more, further preferably 7000 or more, particularly preferably 8000 or more, and 10,000 or more. Is most preferred. Further, it is preferably 50000 or less, more preferably 45000 or less, further preferably 40000 or less, particularly preferably 35000 or less, and most preferably 30000 or less.
• the number average molecular weight is lower than 5,000, the mechanical properties as an adhesive are insufficient, and sufficient adhesion to a substrate such as aluminum, workability, and wet heat resistance may not be obtained.
• the number average molecular weight is higher than 50000, when the adhesive is used after being dissolved in a solvent, the solution viscosity becomes too high, and there may be a problem that it cannot be actually used.
• the polyisocyanate (B) used in the present invention is not particularly limited as long as it has two or more isocyanate groups in the molecule, but is preferably an aliphatic polyisocyanate or an alicyclic polyisocyanate from the viewpoint of weather resistance.
• Specific examples of the polyisocyanate compound are not particularly limited, but 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, hexamethylene diisocyanate (hereinafter referred to as HDI).
• aliphatic polyisocyanate compound examples include hexamethylene diisocyanate
• examples of the alicyclic polyisocyanate compound include isophorone diisocyanate.
• a burette type HDI polyisocyanate having a burette structure and an allophanate type HDI polyisocyanate having an allophanate structure are preferred. By using a polyisocyanate having such a structure, it can be expected that the adhesive strength at a high temperature is increased.
• the polyisocyanate (B) is preferably 1.5 parts by mass or more with respect to 100 parts by mass of the polyester resin (A). More preferably, it is 2 parts by mass or more, further preferably 2.5 parts by mass or more, particularly preferably 3 parts by mass or more, and most preferably 3.5 parts by mass or more. Moreover, it is preferable that it is 20 mass parts or less, More preferably, it is 19 mass parts or less, More preferably, it is 18 mass parts or less, Especially preferably, it is 17 mass parts or less, Most preferably, it is 16 mass parts or less. is there. If the amount is too small, the polyester resin (A) cannot be sufficiently reacted, and the heat and moisture resistance may be lowered. When the amount is too large, the coating film becomes hard and cannot follow the change of the substrate under wet heat, and a gap may be formed between the substrate and the adhesive composition. As a result, corrosive components may enter and corrosion resistance may be reduced.
• the polyester resin composition of the present invention contains the polyester resin (A) and the polyisocyanate (B), and (1) when a thin film is produced with the polyester resin composition, the storage elastic modulus of the thin film at 60 ° C. 4.8 ⁇ 10 6 Pa or less, (2) When a thin film is produced with the polyester resin composition, the storage elastic modulus at 200 ° C. of the thin film is 2.0 ⁇ 10 5 Pa or more. It is a satisfactory composition.
• an additive etc. may be mix
• the polyester resin composition has a storage elastic modulus of 4.8 ⁇ 10 6 Pa or less at 60 ° C. at a dynamic viscoelastic tension of 10 Hz when a thin film having a thickness of 25 ⁇ m is produced from the polyester resin composition. It is necessary.
• a preferable storage elastic modulus is 3.5 ⁇ 10 6 Pa or less.
• Corrosion resistance (acid resistance, alkali resistance, soy sauce resistance, salt water resistance) and moisture resistance under high-temperature wet heat (60 ° C. and 95% RH) by setting the storage elastic modulus at 60 ° C. to 4.8 ⁇ 10 6 Pa or less. Thermal properties can be expressed.
• the lower limit is not particularly limited, but is preferably 2.0 ⁇ 10 6 Pa or more, and more preferably 2.5 ⁇ 10 6 Pa or more.
• the polyester resin composition has a storage elastic modulus of 2.0 ⁇ 10 5 Pa or more at 200 ° C. at a dynamic viscoelastic tension of 10 Hz when a thin film of 25 ⁇ m is produced from the polyester resin composition. It is necessary.
• a preferable storage elastic modulus is 5.0 ⁇ 10 5 Pa or more.
• the solvent that can be used in the present invention is not particularly limited as long as it can dissolve the polyester resin composition.
• toluene, xylene, tetramethylbenzene, Solvesso 100, Solvesso 150, Solvesso 200 Aromatic hydrocarbons such as tetralin, aliphatic hydrocarbons such as decalin, hexane, heptane, octane, decane, esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, methanol, ethanol, propanol, butanol, Alcohols such as 2-ethylhexanol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, (di) ethylene glycol dimethyl ether, diethylene glycol monoethyl ether, dipropylene glycol di Various solvent
• a corrosive substance refers to a substance that causes a chemical reaction when in contact with a metal, melts the base material, generates a corrosion product, decreases the thickness of the base material, or opens a hole.
• a corrosive substance in this invention, Water, salt water, the substance containing an alkaline component, the substance containing an acid component, soy sauce, etc. can be illustrated.
• excellent corrosion resistance is exhibited against such a corrosive substance, but particularly excellent corrosion resistance is exhibited against soy sauce.
• the polyester resin composition is applied to the non-corona surface of a polypropylene film (thickness 50 ⁇ m) with an applicator so that the film thickness after drying is 25 ⁇ m.
• the solvent is evaporated by drying at about 120 ° C. for about 1 minute.
• the polyester resin composition is cured by aging for 7 days in an environment of 25 ° C. and a humidity of 30% RH or less. After curing, a film having a thickness of 25 ⁇ m obtained by peeling off the polyester resin composition layer from the polypropylene film is used as a thin film.
• the polyester resin composition of the present invention preferably has a gel fraction after the wet heat test of 50% or more. More preferably, it is 60% or more. By setting the gel fraction after the wet heat test to 50% or more, deformation can be maintained during the Erichsen processing, and excellent heat and heat resistance can be exhibited.
• the gel fraction after the wet heat test refers to that performed by the following procedure. That is, the polyester resin composition is applied to a 50 ⁇ m polypropylene film with an applicator so that the film thickness after drying is 25 ⁇ m. After application, the solvent is evaporated by drying at about 120 ° C. for about 3 minutes. After drying, the polyester resin composition is cured by aging for 7 days in an environment of 25 ° C. and a humidity of 30% RH or less.
• An epoxy resin (C) can further be mix
• blending an epoxy resin (C) decomposition
• the epoxy equivalent of the epoxy resin (C) is preferably 300 g / eq or more, more preferably 500 g / eq or more, further preferably 700 g / eq or more, and 900 g / eq or more. Particularly preferred. If it is less than 300 g / eq, the contribution to curing is small and the effect of improving adhesiveness may not be recognized. Further, it is preferably 3000 g / eq or less, more preferably 2800 g / eq or less, further preferably 2600 or less, and particularly preferably 2400 g / eq or less. If it is greater than 3000 g / eq, the adhesion to the substrate may be reduced.
• the epoxy resin (C) is preferably 0 part by mass or more, more preferably 1 part by mass or more, still more preferably 5 parts by mass or more, with respect to 100 parts by mass of the polyester resin (A).
• it is 10 mass parts or more.
• it is preferable that it is 45 mass parts or less, More preferably, it is 44 mass parts or less, More preferably, it is 43 mass parts or less. If the amount is too small, decomposition of the polyester resin composition in a wet heat environment may not be suppressed. On the other hand, if the amount is too large, the adhesive layer becomes too hard and the corrosion resistance may be lowered.
• epoxy resin (C) examples are not particularly limited.
• glycidyl ether types such as bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, novolac glycidyl ether, dicyclopentanediene, and brominated bisphenol A diglycidyl ether.
• Glycidyl ester types such as hexahydrophthalic acid glycidyl ester and dimer acid glycidyl ester; triglycidyl isocyanurate, tetraglycidyl diaminodiphenylmethane, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3- Glycidylamine such as bis (N, N-diglycidylaminomethyl) cyclohexane; 3,4-epoxycyclohexylmethylcarboxylate, epoxidized polybutadiene, Alicyclic or aliphatic epoxides of carboxymethyl soybean oil, and the like.
• An epoxy resin (C) having a hydroxyl group in the molecule is preferable because adhesion with a metal and reactivity of the polyisocyanate (B) are improved.
• the crosslinking reaction with the polyisocyanate (B) is more likely to proceed, and a curing reaction at a lower temperature becomes possible. For this reason, it is preferable to use bisphenol A diglycidyl ether.
• the adhesive composition of the present invention is widely used as an additive to the polyester resin composition and, if necessary, the epoxy resin (C) and the adhesive composition within a range that does not impair the characteristics of the present invention. Can be blended. Although it does not specifically limit as an additive, for example, well-known additives, such as a ultraviolet absorber, antioxidant, a silane coupling agent, a plasticizer, various adhesive resin components, can be mentioned, These are individual or Two or more types can be used in combination.
• a curing catalyst may be used to control the reactivity.
• the catalyst is not particularly limited, but a polyisocyanate curing catalyst is preferable, and a tin-based or amine-based polyisocyanate curing catalyst is more preferable.
• tin such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin bisbismaleic acid monobutyl ester, dioctyltin bisbismaleic acid monobutyl ester, tetrabutyldiacetoxy distanoxane Catalyst: tributylamine, triethylenediamine, N′-methyl-N- (2-dimethylaminoethyl) piperazine, 1,8-diazabicyclo (5,4,0) -7-undecene, 1,5-diazabicyclo (4 Examples include amine-based catalysts such as 3,0) -nonene-5,6-dibutylamino-1,8-diazabicyclo (5,4,0) -7-undecene, 1,2-dimethylimidazole.
• free polyisocyanate those obtained by forming salts of these
• An adhesive layer can be produced using the adhesive composition according to the present invention.
• the adhesive layer of the present invention refers to a layer of the adhesive composition after the adhesive composition is applied to the substrate 1, dried and cured by aging or the like.
• the preferred film thickness of the adhesive layer is 4 ⁇ m or more, more preferably 5 ⁇ m or more. If it is too thin, the effect as an adhesive may not be exhibited. Moreover, 30 micrometers or less are preferable, More preferably, it is 25 micrometers or less.
• the adhesive layer preferably has a storage elastic modulus at 60 ° C. in a dynamic viscoelastic tension method of 10 Hz of 4.8 ⁇ 10 6 Pa or less, and more preferably 3.5 ⁇ 10 6 Pa or less. Corrosion resistance (acid resistance, alkali resistance, soy sauce resistance, salt water resistance) and moisture resistance under high-temperature wet heat (60 ° C. and 95% RH) by setting the storage elastic modulus at 60 ° C. to 4.8 ⁇ 10 6 Pa or less. Thermal properties can be expressed. If it is too high, the adhesive layer will be hard, and it will not be possible to follow the change of the base material due to acid or the like under high-temperature wet heat, so that the corrosion resistance tends to decrease.
• the lower limit is not particularly limited, but is preferably 2.0 ⁇ 10 6 Pa or more, and more preferably 2.5 ⁇ 10 6 Pa or more.
• the storage elastic modulus in 200 degreeC in the dynamic viscoelastic tension method 10Hz is 2.0 * 10 ⁇ 5 > Pa or more, and it is preferable that it is 5.0 * 10 ⁇ 5 > Pa or more.
• the upper limit is not particularly limited, but is preferably 9.0 ⁇ 10 5 Pa or less.
• the laminate of the present invention is a two-layer laminate (base material 1 / adhesive layer) of the adhesive layer and the base material 1, or a three-layer laminate in which the base material 2 is bonded to the surface of the adhesive layer.
• Body base material 1 / adhesive layer / base material 2
• further laminated body base material 1 / adhesive layer / base material 2 / adhesive layer / This refers to the base material 3).
• the base material 1, the base material 2, and the base material 3 that can be used in the present invention are not particularly limited, and examples thereof include metals, plastics, wood, cloth, and papers.
• a metal raw material Various metals, such as aluminum, SUS, copper, iron, zinc, metal plates, such as each alloy and plating products, metal foil, a vapor deposition layer, etc. can be illustrated.
• plastic sheet or plastic films such as polyvinyl chloride, polyester, polyolefin, polyamide, a poval, or a polyurethane, can be illustrated.
• Synthetic fibers such as polyester other than cotton, silk, hemp, etc. can be illustrated.
• the paper is not particularly limited, and examples thereof include high-quality paper, craft paper, roll paper, and glassine paper.
• the base material 1, the base material 2, and the base material 3 may be of the same type or different. Moreover, you may laminate
• the substrate 1 is an aluminum foil and the substrate 2 is a plastic film, and this three-layer laminate of aluminum foil / adhesive layer / plastic film is referred to as an aluminum laminate film.
• a laminated film imparted with design properties is called a decorative sheet.
• Example of production of polyester resin (A) (a-1)
• a reaction vessel equipped with a thermometer, stirrer, reflux condenser and distillation tube, 49.8 parts terephthalic acid, 49.8 parts isophthalic acid, 58.4 parts adipic acid, 35.4 parts ethylene glycol, neopentyl glycol 69.3 parts, 1,4-butanediol 60.0 parts, and tetra-n-butyl titanate (hereinafter sometimes abbreviated as TBT) as a catalyst was charged in an amount of 0.03 mol% with respect to the total acid component, The ester exchange reaction was carried out while raising the temperature from 0 ° C. to 240 ° C. over 4 hours.
• TBT tetra-n-butyl titanate
• polyester resin (a-1) The results of the obtained polyester resin (a-1) are shown in Table 1.
• Polyester Resins (a-2) to (a-8) According to the production examples of polyester resins (a-1), except that the types and blending ratios of the raw materials are changed, and polyester resins (a-2) To (a-8) were produced. The results are shown in Table 1.
• composition of polyester resin (A) The composition and composition ratio of the polyester resin (A) were determined by 1 H-NMR measurement (proton nuclear magnetic resonance spectroscopy) at a resonance frequency of 400 MHz.
• a 1 H-NMR apparatus 400-MR manufactured by VARIAN was used, and deuterated chloroform was used as a solvent.
• Glass transition temperature (Tg) The measurement was made with a differential scanning calorimeter (DSC-200, manufactured by SII). The sample used was a sample (polyester resin) 5 mg sealed in an aluminum press-lid container. First, the sample was cooled to ⁇ 50 ° C. using liquid nitrogen, and then heated to 150 ° C. at 20 ° C./min. In the endothermic curve obtained in this process, the glass transition temperature (Tg, unit: ° C) was defined as the temperature at the intersection of the baseline before the endothermic peak and the tangent toward the endothermic peak.
• Acid value A sample (polyester resin) 0.2 g was precisely weighed and dissolved in chloroform 40 ml, and titrated with an ethanol solution of 0.01-N potassium hydroxide. Phenolphthalein was used as an indicator. The measured value was converted to the equivalent per 10 6 g of the sample, and the unit was equivalent / 10 6 g.
• Ester group concentration This is a value calculated from the composition of the polyester resin (A) and its copolymerization ratio, expressed as the number of equivalents per 1 ton of the polyester resin (A). Obtained by a method in which a polyester resin (A) is polymerized through a dehydration esterification step together with other polyvalent carboxylic acids and polyhydric alcohols using a trifunctional or higher polyhydric anhydride as a copolymer component of the polyester resin (A). If it is, the value is used as it is.
• Number average molecular weight (Mn) A sample (polyester resin) was dissolved or diluted in tetrahydrofuran so that the resin concentration was about 0.5%, and filtered through a polytetrafluoroethylene membrane filter having a pore size of 0.5 ⁇ m as a measurement sample.
• the molecular weight was measured by gel permeation chromatography using tetrahydrofuran as a mobile phase and a differential refractometer as a detector. The flow rate was 1 mL / min and the column temperature was 30 ° C. KF-802, 804L and 806L manufactured by Showa Denko were used for the column. Monodisperse polystyrene was used as the molecular weight standard. However, when the measurement sample did not dissolve in tetrahydrofuran, N, N-dimethylformamide was used instead of tetrahydrofuran.
• TPA terephthalic acid residue Terephthalic acid molecular weight: 166.14 IPA: Isophthalic acid residue Isophthalic acid molecular weight: 166.14 AA: Adipic acid residue Adipic acid molecular weight: 146.14 SA: Sebacic acid residue Sebacic acid molecular weight: 202.25
• TMA trimellitic anhydride residue trimellitic anhydride molecular weight: 192.13 EG: ethylene glycol residue ethylene glycol molecular weight: 62.07 2MG: 2-methyl-1,3-propanediol residue 2-methyl-1,3-propanediol Molecular weight: 90.12 NPG: Neopentyl glycol residue Neopentyl glycol Molecular weight: 104.15 BD: 1,4-butanediol residue 1,4-butanediol Molecular weight: 90.12 HD:
• Example 1 In a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 100 parts of polyester resin (a-3) and 270 parts of methyl ethyl ketone were charged and dissolved. Thereafter, 11 parts of epoxy resin (c-1) was charged and dissolved. 4 parts of polyisocyanate (b-2) was added to this solution to obtain an adhesive composition 1. The results are shown in Table 2.
• ⁇ Laminated body sample (X)> The polyester resin composition was applied to a 50 ⁇ m PET film with an applicator so that the film thickness after drying was 8 ⁇ m. After coating, the solvent was evaporated by drying at about 120 ° C. for about 1 minute. After drying, the coated surface of the polyester resin composition was pressure bonded to the aluminum foil using a dry laminator. The pressure bonding was performed at a roll temperature of 60 ° C., a roll load of 3 kg / cm, and a pressure-bonded object speed of 1 m / min. Next, the polyester resin composition was cured for 7 days in an environment of 25 ° C. and humidity of 30% RH or less to obtain a laminate sample (X) of aluminum foil / adhesive layer / PET film.
• ⁇ Laminated body sample (Y)> The polyester resin composition was applied to a 50 ⁇ m polypropylene film with an applicator so that the film thickness after drying was 25 ⁇ m. After coating, the solvent was evaporated by drying at about 120 ° C. for about 1 minute. After drying, aging was performed for 7 days in an environment of 25 ° C. and a humidity of 30% RH or less to cure the polyester resin composition to obtain a laminate sample (Y) of a polypropylene film / adhesive layer.
• the laminated body sample (X) cut into a strip shape with a width of 25 mm was subjected to an environmental load of 60 ° C., 95% RH, 1000 hours using a thermo-hygrostat (manufactured by Yamato Co., Ltd.), and then aluminum foil And the peel strength (T-peel peel, pulling speed 50 mm / min) of the PET film were measured and used as the adhesive strength after wet heat. It can be said that the heat and moisture resistance is better as the initial adhesive strength is higher and the adhesive strength of the adhesive strength after wet heat does not change.
• the measurement temperatures were 25 ⁇ 3 ° C. and 60 ⁇ 3 ° C.
• Adhesive strength retention rate adhesive strength after wet heat / initial adhesive strength ⁇ 100 Evaluation criteria of adhesiveness In both environments of 25 ⁇ 3 ° C. and 60 ° C. ⁇ 3 ° C. ⁇ : Initial adhesive strength is 7 N / 25 mm or higher and adhesive strength retention after wet heat is 80% or higher ⁇ : Initial adhesive strength Is 5 N / 25 mm or more and less than 7 N / 25 mm and the adhesive strength retention after wet heat is 80% or more. ⁇ : The initial adhesive strength is 5 N / 25 mm or more and the adhesive strength retention after wet heat is 50% or more and less than 80%. X: Initial adhesive strength is less than 5 N / 25 mm, or adhesive strength retention after wet heat is less than 50%
• the adhesive composition of the present invention is excellent in adhesiveness, moist heat resistance and corrosion resistance, it can be used as an adhesive for laminating with aluminum members such as food retort packaging and building materials.

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