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
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
• • 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
  • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
• • 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
  • B32B7/02—Physical, chemical or physicochemical properties
  • B32B7/022—Mechanical properties
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • 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
  • C09J163/00—Adhesives based on epoxy resins; Adhesives based on 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
  • 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
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/35—Heat-activated

Definitions

• the present invention relates to an adhesive film that is used by laminating it to a die-forming substrate, an adhesive layer that is laminated to a resin film that is used to create the adhesive film, a die-forming laminate in which the adhesive film and die-forming substrate are laminated together, and a die-formed product obtained from the die-forming laminate.
• a known method for protecting and decorating the surfaces of interior and exterior automotive parts, home appliance parts, and building materials involves applying paint to the surface of the part, drying it, and then heating it to harden it.
• the paint used for painting contains volatile organic solvents, which poses a problem of volatile organic solvent emissions.
• vacuum forming is another known method for decorating (decorating) the surface of a molded body.
• Vacuum forming is a lamination method in which a decorative film is heated and softened while being stretched, the space on the adherend side of the decorative film is depressurized, and, if necessary, the space on the opposite side of the decorative film from the adherend side is pressurized, thereby forming and bonding the decorative film to a molded body that has been molded into a three-dimensional shape.
• a decorative film used in this vacuum forming method is disclosed in Patent Document 1, and a cured adhesive used in vacuum forming is disclosed in Patent Document 2.
• the adherend With vacuum forming, the forming of the adherend and the lamination of the decorative film are carried out separately, making it difficult to position the decorative film relative to the formed body. Furthermore, with vacuum forming, the adherend needs to be strong enough to prevent deformation or warping even when high pressure is applied during forming, which limits its scope of application. Therefore, if the decorative film is bonded to the adherend and then the adherend is squeezed, the position of the decorative film relative to the adherend can be accurately determined before molding, which is thought to make proper positioning easier.
• An object of the present invention is to provide an adhesive film in which an adhesive layer is laminated to a resin film, the adhesive layer being easy to stretch but resistant to breaking during drawing, yet difficult to separate from the adherend, and which is used by being stuck to a drawing substrate.
• Another object of the present invention is to provide an adhesive layer laminated to a resin film used to make the above adhesive film, the adhesive layer being easy to stretch but resistant to breaking during drawing, yet difficult to separate from the adherend.
• Another object of the present invention is to provide a laminate in which a resin film is stuck to a drawing substrate via an adhesive layer, the laminate having good adhesion between the drawing substrate and the resin film, and the resin film being difficult to peel from the drawing substrate even during drawing, and a drawing-formed product obtained from the laminate.
• An adhesive film for laminating squeeze-molded substrates comprising a resin film and an adhesive layer laminated thereon, the adhesive layer comprising a crosslinked polyester resin (C) having a structure in which a side chain carboxy group of a polyester resin (A) having a carboxy group at its side chain is crosslinked with an epoxy-based crosslinking agent (B) having a plurality of epoxy groups in the molecule, and a transesterification catalyst (D).
• a crosslinked polyester resin C
• A side chain carboxy group of a polyester resin
• B epoxy-based crosslinking agent having a plurality of epoxy groups in the molecule
• D transesterification catalyst
• the polyester resin (A) is a polymer polyol (a) obtained by reacting a polycarboxylic acid component with a polyhydric alcohol component, and reacting the polymer polyol (a) with a trifunctional or higher polycarboxylic acid component to provide a carboxyl group.
• An adhesive layer used for laminating a resin film to form an adhesive film for bonding a squeeze-molded substrate comprising: a crosslinked polyester resin (C) having a structure in which the side chain carboxy groups of a polyester resin (A) having carboxy groups in the side chain are crosslinked with an epoxy-based crosslinking agent (B) having multiple epoxy groups in the molecule; and a transesterification catalyst (D).
• the present invention provides an adhesive layer that stretches easily and is resistant to tearing during drawing, and an adhesive film that has the adhesive layer and is used by being attached to a drawing substrate.
• the present invention also provides a laminate in which a drawing substrate and a resin film are attached via the adhesive layer, and this laminate has good adhesion between the drawing substrate and the resin film, and the resin film is not easily peeled off from the drawing substrate even during drawing.
• the present invention also provides a draw-formed product obtained from the laminate, and this draw-formed product has good designability because the resin film does not peel off.
• the adhesive film of the present invention comprises a resin film with an adhesive layer laminated thereon, and is used by laminating it to a die-formed substrate.
• the adhesive layer comprises a crosslinked polyester resin (C) having a structure in which the side-chain carboxy groups of a polyester resin (A) having carboxy groups at the side chains are crosslinked with an epoxy-based crosslinking agent (B) having multiple epoxy groups within the molecule, and an ester exchange catalyst (D).
• an adhesive layer that is easy to stretch during die-formed molding and is resistant to breakage can be achieved.
• an adhesive film with this adhesive layer By laminating an adhesive film with this adhesive layer to a die-formed substrate, good adhesion between the die-formed substrate and the resin film is achieved, making the resin film less likely to peel from the die-formed substrate even during die-formed molding.
• the present invention is described below.
• polyester resin (A) Polyester Resin Having Carboxy Group in Side Chain
• the polyester resin (A) has a carboxy group in the side chain (hereinafter also referred to as a branched structure) of the polyester resin.
• the polyester resin (A) also has an ester bond in the molecule.
• polyester resin (A) having a carboxy group in the side chain
• polyester resin (A) may be a structure in which a carboxy group is in a substituent (e.g., an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an alicyclic hydrocarbon group, etc.) branched from the main chain of the polyester resin, or a structure in which a carboxy group is directly in the main chain of the polyester resin, with a structure in which a carboxy group is directly in the main chain of the polyester resin being preferred.
• a substituent e.g., an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an alicyclic hydrocarbon group, etc.
• the number average molecular weight (Mn) of the polyester resin (A) is preferably, for example, 5,000 to 50,000. Having the number average molecular weight (Mn) of the polyester resin (A) within the above range makes it easier to control the acid value of the polyester resin (A).
• the number average molecular weight (Mn) of the polyester resin (A) is more preferably 10,000 to 25,000, and even more preferably 12,000 to 20,000.
• the acid value of the polyester resin (A) is preferably, for example, 5 to 40 mgKOH/g.
• the acid value of the polyester resin (A) is 5 mgKOH/g or more, crosslinking with the epoxy-based crosslinking agent (B) proceeds sufficiently, improving the heat resistance of the adhesive layer.
• the acid value of the polyester resin (A) is 40 mgKOH/g or less, the crosslinking density is optimized, and ester bond exchange occurs more easily without inhibiting the movement of the molecules themselves, resulting in sufficient stress relaxation and softening, resulting in good adhesion.
• the acid value of the polyester resin (A) is more preferably 7 to 30 mgKOH/g, and even more preferably 10 to 20 mgKOH/g.
• the glass transition temperature of the polyester resin (A) is, for example, preferably 0 to 110°C, more preferably 5 to 85°C, even more preferably 10 to 65°C, and particularly preferably 10 to 45°C.
• the copolymerization components that serve as its raw materials may also have a branched structure.
• the polyester resin (A) can be produced by reacting a polycarboxylic acid component with a polyhydric alcohol component, and may be obtained by adding a monomer having a carboxy group to a polyester having a reactive site obtained by reacting a polycarboxylic acid component with a polyhydric alcohol component.
• the polyester resin (A) is obtained by reacting a polycarboxylic acid component with a polyhydric alcohol component, and then reacting (copolymerizing) the polymer polyol (a) obtained by reacting a polycarboxylic acid component with a polyhydric alcohol component with a trifunctional or higher polycarboxylic acid component to impart a carboxy group.
• the polymer polyol (a) may be a polymer of a polycarboxylic acid component and a polyhydric alcohol component (polymer polyester polyol).
• the polymer polyol (a) may also contain a tri- or higher functional polycarboxylic acid component or a tri- or higher functional polyhydric alcohol component.
• the polycarboxylic acid component used in the polymer polyol (a) may be an aromatic dicarboxylic acid component and/or a polycarboxylic acid component other than an aromatic dicarboxylic acid component, and it is preferable to use at least an aromatic dicarboxylic acid component.
• the polycarboxylic acid component used in polymer polyol (a) is preferably an aromatic dicarboxylic acid component, from the viewpoint of increasing the cohesive force and improving the strength of the resin.
• aromatic dicarboxylic acid components include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and diphenic acid.
• Sulfonate-containing aromatic dicarboxylic acids such as sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and 5-(4-sulfophenoxy)isophthalic acid, as well as sulfonate salt groups such as their metal salts and ammonium salts, may also be used. These may be used alone or in combination of two or more. Among these, terephthalic acid, isophthalic acid, and mixtures thereof are preferred.
• polycarboxylic acid components other than aromatic dicarboxylic acid components include alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and their anhydrides; aliphatic dicarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, and dimer acid; unsaturated bond-containing dicarboxylic acids such as fumaric acid, maleic acid, and their anhydrides; thiomalic acid, which has a thiol group in its molecular structure; and biomass-derived 2,5-furandicarboxylic acid (FDCA). These may be used alone or in combination of two or more.
• alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohex
• the polyhydric alcohol component used in the polymer polyol (a) is preferably a glycol component, such as an aliphatic glycol, an alicyclic glycol, an aromatic group-containing glycol, or an ether bond-containing glycol.
• Aliphatic glycols include, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 2-methyl-1,3-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-ethyl-2-butylpropanediol (DMH), hydroxypivalic acid neopentyl glycol ester, dimethylolheptane, and 2,2,4-trimethyl-1,3-pentanediol.
• DMH 2-ethyl-2-butylpropanediol
• alicyclic glycols examples include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, tricyclodecanediol, tricyclodecanedimethylol, spiroglycol, hydrogenated bisphenol A, ethylene oxide adducts and propylene oxide adducts of hydrogenated bisphenol A, and dimer diol.
• Aromatic-containing glycols include, for example, paraxylene glycol, metaxylene glycol, orthoxylene glycol, p-hydroxyphenethyl alcohol, 1,4-phenylene glycol, ethylene oxide adduct of 1,4-phenylene glycol, glycols obtained by adding one to several moles of ethylene oxide or propylene oxide to two phenolic hydroxyl groups of bisphenols, such as bisphenol A, ethylene oxide adduct and propylene oxide adduct of bisphenol A.
• Glycol-modified aromatic dicarboxylic acids may also be used, and specific examples include bis-2-hydroxyethyl terephthalate (BHET), which is an ethylene glycol-modified terephthalic acid, propylene glycol-modified terephthalic acid, ethylene glycol-modified isophthalic acid, propylene glycol-modified isophthalic acid, ethylene glycol-modified orthophthalic acid, and propylene glycol-modified orthophthalic acid.
• BHET bis-2-hydroxyethyl terephthalate
• glycol-modified aromatic dicarboxylic acids include glycol-modified aromatic dicarboxylic acids having a sulfonic acid group or sulfonate salt group, such as naphthalenedicarboxylic acid, biphenyldicarboxylic acid, diphenic acid, 5-hydroxyisophthalic acid, sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5-(4-sulfophenoxy)isophthalic acid, sulfoterephthalic acid, and/or their metal salts or ammonium salts.
• a sulfonic acid group or sulfonate salt group such as naphthalenedicarboxylic acid, biphenyldicarboxylic acid, diphenic acid, 5-hydroxyisophthalic acid, sulfoterephthalic acid, 5-sulfoisophthalic
• ether bond-containing glycols include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, neopentyl glycol ethylene oxide adduct, and neopentyl glycol propylene oxide adduct.
• aliphatic glycols are preferred, with ethylene glycol, 2-methyl-1,3-butanediol, 2,2-dimethyl-1,3-propanediol, and 1,6-hexanediol being more preferred.
• Tri- or higher functional polycarboxylic acid component examples include trimellitic acid, trimesic acid, ethylene glycol bis(anhydrotrimellitate), glycerol tris(anhydrotrimellitate), trimellitic anhydride, pyromellitic anhydride (PMDA), oxydiphthalic dianhydride (ODPA), 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 3,3',4,4'-diphenyltetracarboxylic dianhydride (BPDA), 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA), 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride (6FDA), and 2,2'-bis[(dicarboxyphenoxy)phenyl]propane dianhydride
• Tri- or higher functional polyhydric alcohol component examples include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, etc. These may be used alone or in combination of two or more.
• the polymer polyol (a) may also contain other components such as hydroxycarboxylic acid compounds having hydroxyl and carboxyl groups in their molecular structure, such as 5-hydroxyisophthalic acid, p-hydroxybenzoic acid, p-hydroxyphenylpropionic acid, p-hydroxyphenylacetic acid, 6-hydroxy-2-naphthoic acid, and 4,4-bis(p-hydroxyphenyl)valeric acid.
• hydroxycarboxylic acid compounds having hydroxyl and carboxyl groups in their molecular structure such as 5-hydroxyisophthalic acid, p-hydroxybenzoic acid, p-hydroxyphenylpropionic acid, p-hydroxyphenylacetic acid, 6-hydroxy-2-naphthoic acid, and 4,4-bis(p-hydroxyphenyl)valeric acid.
• the number average molecular weight (Mn) of the polymer polyol (a) is, for example, preferably 1,000 to 30,000, more preferably 2,000 to 25,000, and even more preferably 3,000 to 20,000.
• the polymer polyol (a) may contain two or more polymer polyol components with different number average molecular weights (Mn).
• Mn number average molecular weights
• the polymer polyol (a) may contain two or more polymer polyol components with different number average molecular weights (Mn)
• it may contain a long-chain polymer polyol (a1) with a number average molecular weight (Mn) of 7,000 or more and a short-chain polymer polyol (a2) with a number average molecular weight (Mn) of 1,000 or more but less than 7,000.
• the long-chain molecules of the long-chain polymer polyol (a1) block contribute to heat resistance
• the introduction of the short-chain polymer polyol (a2) block can introduce a sufficient amount of carboxylic acid to impart heat resistance.
• the upper limit of the number average molecular weight (Mn) of the long-chain polymer polyol (a1) is not particularly limited, but it may be, for example, 20,000 or less.
• the polymerization ratio of the long-chain high molecular weight polyol (a1) to the short-chain high molecular weight polyol (a2) is preferably 5 to 50 parts by mass of the short-chain high molecular weight polyol (a2) per 100 parts by mass of the long-chain high molecular weight polyol (a1) and the short-chain high molecular weight polyol (a2) combined.
• the amount of the short-chain high molecular weight polyol (a2) is more preferably 10 to 40 parts by mass, and even more preferably 20 to 30 parts by mass, per 100 parts by mass of the long-chain high molecular weight polyol (a1) and the short-chain high molecular weight polyol (a2) combined.
• the polymerization amount of the long-chain polymer polyol (a1) is preferably 50 to 90% by mass when the polymer polyol (a) is taken as 100% by mass.
• the adhesive layer exhibits good heat resistance and adhesion due to the balance with the polymerization amounts of the short-chain polymer polyol (a2) and the trifunctional or higher polycarboxylic acid component.
• the polymerization amount of the long-chain polymer polyol (a1) is more preferably 60 to 85% by mass, and even more preferably 70 to 80% by mass, when the polymer polyol (a) is taken as 100% by mass.
• the tri- or higher functional polycarboxylic acid component to be reacted (polymerized) with the polymer polyol (a) is not particularly limited as long as it is a compound having three or more carboxy groups in the molecule.
• the carboxy groups may form acid anhydride groups in the molecule, in which case one acid anhydride group is counted as two carboxy groups.
• trifunctional or higher polyvalent carboxylic acid components include trimellitic acid, trimesic acid, ethylene glycol bis(anhydrotrimellitate), glycerol tris(anhydrotrimellitate), trimellitic anhydride, pyromellitic anhydride (PMDA), oxydiphthalic dianhydride (ODPA), 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 3,3',4,4'-diphenyltetracarboxylic dianhydride (BPDA), 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA), 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride (6FDA), and 2,2'-bis[(dicarboxyphenoxy)phenyl]propane dianhydride (BSAA). These may be used alone or in combination. Of these, pyromellitic anhydride (
• the ratio of the tri- or higher functional polycarboxylic acid component in the adhesive layer may be 0.1 to 3 molar parts, more preferably 0.3 to 2 molar parts, and even more preferably 0.5 to 1.5 molar parts, of the tri- or higher functional polycarboxylic acid component per 100 molar parts of polyester resin (A).
• the polymerization ratio of the high molecular weight polyol (a) to the tri- or higher functional polycarboxylic acid component in the polyester resin (A) is preferably 0.5 to 10 parts by mass, more preferably 1 to 8 parts by mass, and even more preferably 2 to 5 parts by mass, of the tri- or higher functional polycarboxylic acid component per 100 parts by mass of the high molecular weight polyol (a).
• the polymerization ratio of the tri- or higher functional polycarboxylic acid component is at or above the lower limit, the amount of crosslinking is sufficient, and the heat resistance of the adhesive layer is improved.
• the polymerization ratio of the tri- or higher functional polycarboxylic acid component is at or below the upper limit, the crosslink density does not become too high, ester bond exchange occurs easily, and sufficient softening occurs, resulting in improved adhesion.
• the acid value of the polymer polyol (a) is, for example, preferably 0.1 to 20 mgKOH/g, more preferably 0.2 to 15 mgKOH/g, and even more preferably 0.3 to 10 mgKOH/g.
• the acid value of the long-chain polymer polyol (a1) is, for example, preferably 1 to 20 mgKOH/g, more preferably 2 to 15 mgKOH/g, and even more preferably 3 to 10 mgKOH/g.
• the acid value of the short-chain polymer polyol (a2) is, for example, preferably 0.1 to 10 mgKOH/g, more preferably 0.2 to 8 mgKOH/g, and even more preferably 0.3 to 5 mgKOH/g.
• the glass transition temperature of the polymer polyol (a) is, for example, preferably -10 to 100°C, more preferably 0 to 80°C, and even more preferably 5 to 60°C.
• the glass transition temperature of the long-chain polymer polyol (a1) is, for example, preferably -10 to 60°C, more preferably -5 to 30°C, and even more preferably 0 to 15°C.
• the glass transition temperature of the short-chain polymer polyol (a2) is, for example, preferably 5 to 100°C, more preferably 20 to 90°C, and even more preferably 30 to 80°C.
• reaction catalyst In producing the polyester resin (A), a reaction catalyst may be used within a range that does not impair the above-mentioned effects.
• the reaction catalyst include imidazole compounds such as 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, and 1-cyanoethyl-2-ethyl-4-methylimidazole; triethylamine, triethylenediamine, N'-methyl-N-(2-dimethylaminoethyl)piperazine, N,N-diisopropylethylamine, N,N-dimethylaminopyridine, 1,8-diazabicyclo(5,4,0)-undecene-7, 1,5-diazabicyclo(4,3,0)-nonene-5, and 6-dibutylamine.
• Suitable amine salts include tertiary amines such as 1,8-dimethylamino-1,8-diazabicyclo(5,4,0)-undecene-7, and compounds prepared by converting these tertiary amines into amine salts with phenol, octylic acid, quaternized tetraphenylborate, and the like; and quaternary ammonium salts such as tetramethylammonium bromide, tetraethylammonium bromide, tetra-n-butylammonium bromide, tetramethylammonium chloride, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tetramethylammonium hydroxide, trimethylbenzylammonium hydroxide, and tetra-n-butylammonium hydroxide.
• tertiary amines such as 1,8-dimethylamino
• the epoxy-based crosslinking agent (B) is an epoxy compound having multiple epoxy groups in the molecule. That is, the epoxy compound is a compound having two or more epoxy groups in the molecule.
• the epoxy compound may contain oxygen atoms and sulfur atoms in the molecule as necessary.
• epoxy compounds makes it easier to form three-dimensional crosslinks, improving the heat resistance of the adhesive layer. Furthermore, by crosslinking the side chain carboxyl groups of the polyester resin (A) with epoxy compounds, it is possible to achieve both high crosslink density and high high-temperature fluidity in the presence of the transesterification catalyst (D). As a result, it is possible to achieve an adhesive layer that is easy to stretch during drawing and is resistant to breakage, while still maintaining heat resistance.
• the number of epoxy groups in the epoxy compound molecule is preferably 2 to 4, more preferably 2 or 3, and even more preferably 2.
• Aliphatic epoxy compounds may also be used as the epoxy compound.
• Aliphatic epoxy compounds are compounds composed of an aliphatic saturated hydrocarbon group and an epoxy group, and may contain oxygen atoms or sulfur atoms in the molecule as necessary. Examples of aliphatic epoxy compounds include compounds in which multiple epoxy group-containing groups are bonded to an aliphatic saturated hydrocarbon group via oxygen atoms or sulfur atoms. Examples of epoxy group-containing groups include epoxy groups and glycidyl groups.
• epoxy compounds include polytetramethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A diglycidyl ether, and bisphenol S diglycidyl ether. These may be used alone or in combination of two or more. Of these, 1,4-butanediol diglycidyl ether is preferred.
• the epoxy-based crosslinking agent (B) may be an epoxy amine compound having multiple epoxy groups in the molecule and further having a tertiary amino group.
• an epoxy amine compound having multiple epoxy groups and one or more tertiary amino groups in the molecule may be used as the epoxy-based crosslinking agent (B).
• the epoxy amine compound may contain oxygen atoms and sulfur atoms in the molecule as necessary.
• the number of epoxy groups contained in the molecule of the epoxy amine compound is preferably 2 to 4, and more preferably 3 or 4.
• the number of tertiary amino groups contained in the molecule of the epoxy amine compound may be 2 or more, and is preferably 3 or less.
• the epoxy amine compound may have one or more epoxidized amino groups formed by bonding a tertiary amino group to an epoxy group via an alkylene group having 1 to 4 carbon atoms.
• the alkylene group bonding the tertiary amino group to the epoxy group preferably has 3 or fewer carbon atoms, even more preferably 2 or fewer carbon atoms, and particularly preferably 1 carbon atom.
• the nitrogen atom of the tertiary amino group may have one epoxy group bonded to it via an alkylene group having 1 to 4 carbon atoms, or two epoxy groups bonded to it via alkylene groups having 1 to 4 carbon atoms; a diepoxidized amino group having two epoxy groups bonded to it via an alkylene group having 1 to 4 carbon atoms is preferred.
• the number of epoxidized amino groups contained in the molecule of an epoxy amine compound may be two or more, three or more, five or less, or four or less. That is, the number of epoxidized amino groups contained in the molecule of an epoxy amine compound may be two to five, or three or four.
• the number of diepoxidized amino groups contained in the molecule of an epoxy amine compound may be one, two, or three, preferably one or two, and more preferably two, i.e., diglycidyl amino groups.
• the epoxy amine compound may have an aromatic ring to which a diepoxidized amino group is bonded.
• the number of diepoxidized amino groups bonded to the aromatic ring may be one or two, and preferably three or less.
• the diepoxidized amino group may be bonded to the aromatic ring via an alkylene group having 1 to 4 carbon atoms.
• the number of carbon atoms in the alkylene group bonding the aromatic ring to the diepoxidized amino group is more preferably three or less, even more preferably two or less, and particularly preferably one.
• the epoxy amine compound has an aromatic ring
• the number of aromatic rings may be one or two, and preferably three or less.
• the aromatic rings may be bonded directly to each other, or two or more aromatic rings may be bonded via an alkylene group having 1 to 4 carbon atoms.
• epoxy amine compounds include 4-(oxiran-2-ylmethoxy)-N,N-bis(oxiran-2-ylmethyl)aniline (hereinafter sometimes referred to as triglycidyl para-aminophenol), N,N,N',N'-tetraglycidyl-m-xylylenediamine, and 4,4'-methylenebis(N,N-diglycidylaniline). These may be used alone or in combination of two or more. Of these, triglycidyl para-aminophenol is preferred.
• an epoxy compound and an epoxy amine compound may be used alone or in combination.
• the ratio of the epoxy-based crosslinking agent (B) in the adhesive layer may be 30 to 60 molar parts per 100 molar parts of carboxy groups in the polyester resin (A). Having the ratio of the epoxy-based crosslinking agent (B) in the adhesive layer within the above range ensures an appropriate crosslink density, enabling stress relaxation in the adhesive layer after crosslinking.
• the ratio of the epoxy-based crosslinking agent (B) in the adhesive layer is more preferably 25 to 58 molar parts, and even more preferably 30 to 55 molar parts, per 100 molar parts of carboxy groups in the polyester resin (A).
• the crosslinked polyester resin (C) is a resin having a structure in which the side chain carboxy groups of the polyester resin (A) are crosslinked with an epoxy-based crosslinking agent (B) having multiple epoxy groups in the molecule, and the side chain carboxy groups of the polyester resin (A) may be crosslinked with an epoxy compound having multiple epoxy groups in the molecule, or with an epoxy amine compound having multiple epoxy groups and one or more tertiary amino groups in the molecule, or with both an epoxy compound having multiple epoxy groups but no tertiary amino groups in the molecule and an epoxy amine compound having multiple epoxy groups and one or more tertiary amino groups in the molecule.
• transesterification catalyst (D) examples include zinc acetate, zinc acetate anhydride, zinc(II) acetylacetonate, aluminum(III) acetylacetonate, triphenylphosphine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, and 1,8-diazabicyclo[5.4.0]undecene-7. These may be used alone or in combination of two or more. Of these, zinc acetate anhydride and 1,5,7-triazabicyclo[4.4.0]dec-5-ene are preferred.
• the quantitative ratio of the transesterification catalyst (D) in the adhesive layer is preferably 1 to 70 molar parts per 100 molar parts of the carboxy groups of the polyester resin (A). By having the quantitative ratio of the transesterification catalyst (D) in the adhesive layer within the above range, stress relaxation in the adhesive layer after crosslinking can be achieved.
• the quantitative ratio of the transesterification catalyst (D) in the adhesive layer is more preferably 3 to 65 molar parts, and even more preferably 5 to 60 molar parts, per 100 molar parts of the carboxy groups of the polyester resin (A).
• the adhesive layer can be produced by mixing a polyester resin (A) having a carboxyl group in its side chain, an epoxy-based crosslinking agent (B), and an ester exchange catalyst (D), heating the mixture, and carrying out a crosslinking reaction via an epoxy ring-opening reaction.
• the heating temperature is preferably, for example, 80 to 200°C, more preferably 85 to 180°C, and even more preferably 90 to 150°C.
• the heating time varies depending on the heating temperature, but is preferably, for example, 30 minutes to 10 hours, more preferably 1 to 8 hours, and even more preferably 2 to 5 hours.
• the reaction between the polyester resin (A) and the epoxy-based crosslinking agent (B) may be carried out in the absence of a solvent or in the presence of an organic solvent.
• an organic solvent is used, the organic solvent is not particularly limited as long as it does not react with the polyester resin (A) and the epoxy-based crosslinking agent (B).
• Examples include aromatic organic solvents such as toluene and xylene, aliphatic organic solvents such as heptane and octane, ketone-based solvents such as methyl ethyl ketone, ether-based solvents such as tetrahydrofuran and diethyl ether, and amide-based solvents such as dimethylformamide, N-methylpyrrolidone, and N,N-dimethylformamide. These may be used alone or in combination of two or more. Of these, aromatic organic solvents, ketone-based solvents, and amide-based solvents are preferred.
• the quantitative ratio of the polyester resin (A) having a carboxy group in its side chain to the epoxy-based crosslinking agent (B) in the crosslinked polyester resin (C) can be determined based on the functional group molar ratio between the carboxy group in the side chain of the polyester resin (A) and the epoxy group in the epoxy-based crosslinking agent (B). From the standpoint of crosslinking reaction efficiency and stress relaxation in the crosslinked polyester resin (C) after crosslinking, the ratio of the carboxy groups in the polyester resin (A) to the epoxy groups in the epoxy-based crosslinking agent (B) (carboxy groups:epoxy groups) is preferably 100:50 to 100:150 (mol parts), and more preferably 100:80 to 100:120 (mol parts).
• the adhesive film is formed by laminating an adhesive layer containing a crosslinked polyester resin (C) having a structure in which the side chain carboxy groups of a polyester resin (A) having carboxy groups in its side chains are crosslinked with the above-mentioned epoxy-based crosslinking agent (B) having multiple epoxy groups in the molecule, and an ester exchange catalyst (D) on a resin film.
• C crosslinked polyester resin
• polyester resin examples include polyester resin, polyamide resin, polyimide resin, polyamide-imide resin, liquid crystal polymer, polyphenylene sulfide, syndiotactic polystyrene, polyolefin resin, and fluororesin.
• polyester resin is preferred.
• Adhesive films can be produced, for example, by applying a coating liquid containing the epoxy-based crosslinking agent (B) having multiple epoxy groups in its molecule, the polyester resin (A) having carboxyl groups in its side chains, and the transesterification catalyst (D) to a resin film using standard methods, followed by drying.
• a coating liquid containing the epoxy-based crosslinking agent (B) having multiple epoxy groups in its molecule, the polyester resin (A) having carboxyl groups in its side chains, and the transesterification catalyst (D) to a resin film using standard methods, followed by drying.
• the film can be wound without offset, improving operability.
• the adhesive layer is protected, improving storage stability and ease of use.
• release substrates include paper such as fine paper, kraft paper, roll paper, and glassine paper, with a coating layer of clay, polyethylene, polypropylene, or other filler applied to one or both sides of the paper, and then a silicone-, fluorine-, or alkyd-based release agent applied to the coating layer.
• Other examples include various olefin films, such as polyethylene, polypropylene, ethylene- ⁇ -olefin copolymer, and propylene- ⁇ -olefin copolymer, as well as films such as polyethylene terephthalate and polyethylene naphthalate, coated with the above-mentioned release agents.
• the method for applying the coating liquid to the resin film is not particularly limited, but examples include methods using a coating machine such as a comma coater, lip coater, die coater, or reverse roll coater.
• the present invention also encompasses an adhesive layer that is laminated on a resin film to form an adhesive film for laminating a draw-molded substrate.
• the adhesive layer contains a crosslinked polyester resin (C) having a structure in which the side chain carboxy groups of a polyester resin (A) having a carboxy group in its side chain are crosslinked with an epoxy-based crosslinking agent (B) having multiple epoxy groups in the molecule, and a transesterification catalyst (D).
• the thickness of the adhesive layer can be appropriately changed as needed, but is preferably 0.01 to 0.8 mm, for example. By making the thickness of the adhesive layer 0.01 mm or more, sufficient adhesive strength can be obtained.
• the adhesive layer preferably has a stress of 1 MPa or less when elongated 100% in the longitudinal direction at both 170°C and 250°C. This makes it difficult for the resin film to peel from the die-formed substrate when die-formed on a laminate in which the die-formed substrate and resin film are bonded together via the adhesive layer.
• the stress of the adhesive layer when elongated 100% in the longitudinal direction at 170°C is more preferably 0.8 MPa or less, and even more preferably 0.5 MPa or less.
• the stress of the adhesive layer when elongated 100% in the longitudinal direction at 250°C is more preferably 0.5 MPa or less, and even more preferably 0.3 MPa or less.
• the adhesive layer preferably has a stress of 1 MPa or less when stretched 200% in the longitudinal direction at both 170°C and 250°C. This makes it difficult for the resin film to peel from the die-formed substrate when die-formed on a laminate in which the die-formed substrate and resin film are bonded together via the adhesive layer.
• the stress of the adhesive layer when stretched 200% in the longitudinal direction at 170°C is more preferably 0.8 MPa or less, and even more preferably 0.5 MPa or less.
• the stress of the adhesive layer when stretched 200% in the longitudinal direction at 250°C is more preferably 0.5 MPa or less, and even more preferably 0.3 MPa or less.
• the adhesive layer preferably has a breaking elongation of 100% or more and 1200% or less at 170°C and 250°C. This makes it difficult for the resin film to peel from the die-formed substrate when die-formed on a laminate in which the die-formed substrate and resin film are bonded together via the adhesive layer.
• the breaking elongation of the adhesive layer at 170°C is more preferably 110 to 1180%, and even more preferably 120 to 1150%.
• the breaking elongation of the adhesive layer at 250°C is more preferably 105 to 1180%, and even more preferably 110 to 1150% or less.
• the adhesive layer have a stress of 1 MPa or less when elongated by 100% in the longitudinal direction at both 170°C and 250°C, a stress of 1 MPa or less when elongated by 200% in the longitudinal direction at both 170°C and 250°C, and a breaking elongation of 100% or more and 1200% or less at 170°C and 250°C.
• the present invention also encompasses a laminate in which the adhesive film and a drawing substrate are bonded together, and this laminate can be suitably used for deep drawing.
• the drawing laminate is a laminate in which a resin film, an adhesive layer, and a drawing substrate are laminated in this order.
• drawing substrates include metal substrates such as metal plates, and resin substrates such as film-like resins.
• materials for metal substrates include various metals such as SUS, copper, aluminum, iron, steel, zinc, and nickel, as well as their alloys, plated products, and metals treated with other metals such as zinc or chromium compounds.
• resin substrates examples include polyester resins, polyamide resins, polyimide resins, polyamideimide resins, liquid crystal polymers, polyphenylene sulfide, syndiotactic polystyrene, polyolefin resins, and fluororesins.
• metal substrates are preferred from the viewpoint of adhesion strength and durability with the adhesive layer of the adhesive film, and SUS, copper, aluminum, etc. are more preferred.
• the temperature is at a temperature that is at least 15°C higher than the softening temperature of the adhesive layer, and specifically, for example, 185°C or higher.
• the present invention also includes a die-formed product obtained from the die-formed laminate.
• the adhesive layer and the resin film deform in accordance with the deformation of the die-formed substrate, so that the die-formed product is free from peeling or wrinkles of the resin film and has good design properties.
• a long-chain polymer polyol (a1) and a short-chain polymer polyol (a2) were copolymerized with a tri- or higher functional polycarboxylic acid component to produce a polyester resin (A) having carboxy groups in the side chains.
• the number average molecular weight (Mn), acid value, and glass transition temperature of the obtained long-chain polymer polyol (a1-1) and short-chain polymer polyol (a2-1) were measured using the following procedure. These physical property values are shown in Table 1.
• Acid Value 0.2 g of the obtained long-chain polymer polyol (a1-1) or short-chain polymer polyol (a2-1) was dissolved in 20 ml of chloroform and subjected to neutralization titration with a 0.1 N potassium hydroxide (KOH) ethanol solution using phenolphthalein as an indicator. From the titration amount, the number of mg of KOH consumed for neutralization was converted into the amount per 1 g of long-chain polymer polyol (a1-1) or short-chain polymer polyol (a2-1) to calculate the acid value (mg KOH/g).
• KOH potassium hydroxide
• (A) Polyester Resin Having Carboxy Groups in the Side Chains In a reactor equipped with a stirrer, thermometer, and reflux condenser, 80 parts by mass of long-chain polymer polyol (a1-1), 20 parts by mass of short-chain polymer polyol (a2-1), 2.6 parts by mass of pyromellitic anhydride as a trifunctional or higher polycarboxylic acid component, and 100 parts by mass of toluene were charged and dissolved in toluene while gradually heating to 80 ° C. After dissolution was complete, 0.05 parts by mass of triethylamine was added as a reaction catalyst, and the temperature was gradually raised to 105 ° C. and the reaction was allowed to proceed for 24 hours.
• an adhesive layer was produced using the obtained polyester resin (A-1), an epoxy-based crosslinking agent (B), and an ester exchange catalyst (D).
• Epoxy compound (B-1) 1,4-butanediol diglycidyl ether (hereinafter sometimes referred to as BDE) used was "Epogose (registered trademark) BD” manufactured by Yokkaichi Synthetic Co., Ltd. 1,4-butanediol diglycidyl ether has two epoxy groups in the molecule.
• Epoxy compound (B-3) As a novolac type epoxy resin, "YDCN-700-10” manufactured by Nippon Steel Chemical & Material Co., Ltd. "YDCN-700-10” is a multifunctional epoxy with an epoxy equivalent weight of 198 to 210.
• Transesterification catalyst (D) "Zinc acetate anhydride (Zn(OAc) 2 )" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. was used.
• Transesterification catalyst (D-2) 1,5,7-triazabicyclo[4.4.0]dec-5-ene (hereinafter sometimes referred to as TBD) manufactured by Tokyo Chemical Industry Co., Ltd. was used.
• Example 1 The amount (molar equivalent) of carboxy groups in the polyester resin (A-1) and the amount (molar equivalent) of epoxy groups in the epoxy compound (B-1) were dissolved in toluene to a specific ratio, and a solution 1 with a solids content of 25.5% by mass was prepared.
• the amount of epoxy compound (B-1) was 50 molar parts per 100 molar parts of carboxy groups in the polyester resin (A-1).
• the transesterification catalyst (D-1) was dissolved in N,N-dimethylformamide to prepare a solution 2 with a solids content of 8.3% by mass.
• Solution 1 and solution 2 were mixed so that the amount (molar equivalent) of carboxy groups in the polyester resin (A-1) and the amount (molar equivalent) of the transesterification catalyst (D-1) were a specific ratio, and a coating solution 1 with a solids content of 20% by mass was produced.
• the amount of transesterification catalyst (D-1) was 20 molar parts per 100 molar parts of carboxy groups in the polyester resin (A-1).
• the obtained coating liquid 1 was applied to a resin film and dried to produce adhesive film 1 consisting of a resin film and adhesive layer 1.
• a PET film (Toyobo G2000, thickness 38 ⁇ m) that had been subjected to plasma treatment and corona treatment as surface treatment was used as the resin film, and coating liquid 1 was applied to the surface of the PET film.
• Coating liquid 1 was applied using an applicator. The required amount of liquid was dropped onto the surface of the PET film, and then uniformly applied to the PET film surface using an applicator with a 200 ⁇ m gap.
• the PET film coated with coating liquid 1 was heat-treated at 100°C for 3 hours to produce adhesive film 1 consisting of a PET film and adhesive layer 1.
• the dry film thickness of adhesive layer 1 in the obtained adhesive film 1 was approximately 0.025 mm.
• the physical properties of the obtained adhesive layer 1 were evaluated.
• the PET film was peeled off from Adhesive Film 1, removing Adhesive Layer 1.
• a test piece measuring 250 mm in length and 10 mm in width was cut from Adhesive Layer 1 in the longitudinal direction.
• a tensile test was performed using a tensile testing machine (Tensilon Universal Testing Machine, manufactured by Orientec Co., Ltd.) by pulling the test piece longitudinally with an initial tensile chuck distance of 20 mm and a tensile speed of 20 mm/min. The tensile test was performed after placing the test piece in a thermostatic chamber set to 170°C or 250°C and preheating for 30 seconds.
• the load applied to the film when the test piece was elongated to 100% (i.e., when the chuck distance was 40 mm) and when the test piece was elongated to 200% (i.e., when the chuck distance was 60 mm) was read, and the load applied to the film when the test piece was elongated to 100% (i.e., when the chuck distance was 40 mm) and 200% (i.e., when the chuck distance was 60 mm) were read, and the values obtained by dividing the read load by the cross-sectional area of the test piece before the tensile test (film thickness x 10 mm) were used to calculate the stress at 100% elongation and the stress at 200% elongation, respectively.
• test specimen was not placed in a thermostatic chamber and a tensile test was performed at room temperature (25°C), and the stress at 100% elongation and 200% elongation were calculated.
• Table 3 shows the stress of adhesive layer 1 at 100% longitudinal elongation at 25°C, 170°C, or 250°C, the stress of adhesive layer 1 at 200% longitudinal elongation at 25°C, 170°C, or 250°C, and the elongation at break of adhesive layer 1 at 170°C or 250°C.
• a galvannealed steel sheet (hereinafter sometimes referred to as a GA steel sheet) was used as the drawing substrate.
• the GA steel sheet was placed on the heating stage of a laminating machine and preheated at 185°C for 5 minutes. The laminating machine was then operated, transporting the GA steel sheet at a speed of 9.0 m/min.
• Adhesive film 1 was supplied to the GA steel sheet so that the galvannealed layer of the GA steel sheet came into contact with adhesive layer 1 of adhesive film 1.
• the GA steel sheet was laminated at a laminating pressure of 3 bar. After passing through a laminating roll, the sheet was immersed in a water bath to cool, producing a drawing laminate 1.
• the laminating machine used was an original machine with a continuous structure of a steel plate heating stage and laminating roll.
• the laminate structure of the draw-forming laminate 1 is PET film/adhesive layer/GA steel plate.
• the adhesion between the PET film and the GA steel sheet was evaluated for the resulting draw-forming laminate 1.
• the adhesion was evaluated by a peel test in which one end of the PET film was pulled while being folded back 180° along the surface of the draw-forming laminate 1, and the load at which the PET film peeled off was measured.
• the width of the test piece was 20 mm, and the pulling speed of the PET film was 100 mm/min.
• the adhesion was evaluated based on the measured load and according to the following criteria. The evaluation results are shown in Table 3 below. (Evaluation criteria) When the load per 20 mm width of the PET film was more than 10 N, the adhesion was evaluated as being particularly excellent, and this was indicated as A in Table 3.
• Example 2 A draw-forming laminate 2 was produced under the same conditions as in Example 1, except that the temperature at which the GA steel sheet was preheated on the heating stage of the laminator was changed from 185°C to 200°C. The resulting draw-forming laminate 2 was evaluated for adhesion between the PET film and the GA steel sheet, and draw formability, under the same conditions as in Example 1. The evaluation results are shown in Table 3 below.
• Example 3 A draw-forming laminate 3 was produced under the same conditions as in Example 1, except that the temperature at which the GA steel sheet was preheated on the heating stage of the laminator was changed from 185°C to 230°C. The resulting draw-forming laminate 3 was evaluated for adhesion between the PET film and the GA steel sheet, and draw formability, under the same conditions as in Example 1. The evaluation results are shown in Table 3 below.
• Example 4 Coating solution 4 was produced under the same conditions as in Example 1, except that instead of using 20 mol parts of transesterification catalyst (D-1) per 100 mol parts of carboxy groups in polyester resin (A), 20 mol parts of transesterification catalyst (D-2) were used. Next, the resulting coating solution 4 was applied to a resin film under the same conditions as in Example 1 and dried to produce an adhesive film 4 consisting of a resin film and an adhesive layer 4. The dry film thickness of adhesive layer 4 in the resulting adhesive film 4 was approximately 0.353 mm. The physical properties of the resulting adhesive layer 4 were evaluated under the same conditions as in Example 1.
• a draw-forming laminate 4 was produced under the same conditions as in Example 1, except that the temperature at which the GA steel sheet was preheated on the heating stage of the laminator was changed from 185°C to 200°C.
• the resulting draw-forming laminate 4 was evaluated for adhesion between the PET film and the GA steel sheet, as well as for draw formability, under the same conditions as in Example 1. The evaluation results are shown in Table 3 below.
• Example 5 Coating solution 5 was produced under the same conditions as in Example 1, except that 50 mol parts of transesterification catalyst (D-1) were used instead of 20 mol parts per 100 mol parts of carboxy groups in polyester resin (A). Next, the resulting coating solution 5 was applied to a resin film under the same conditions as in Example 1 and dried to produce an adhesive film 5 consisting of a resin film and an adhesive layer 5. The dry thickness of adhesive layer 5 in the resulting adhesive film 5 was approximately 0.017 mm. The physical properties of the resulting adhesive layer 5 were evaluated under the same conditions as in Example 1.
• a draw-forming laminate 5 was produced under the same conditions as in Example 1, except that the temperature at which the GA steel sheet was preheated on the heating stage of the laminator was changed from 185°C to 200°C.
• the resulting draw-forming laminate 5 was evaluated for adhesion between the PET film and the GA steel sheet, and for draw-formability, under the same conditions as in Example 1. The evaluation results are shown in Table 3 below.
• Example 6 Coating liquid 6 was produced under the same conditions as in Example 1, except that instead of 50 mol parts of epoxy compound (B-1) per 100 mol parts of carboxy groups in the polyester resin (A), 33 mol parts of epoxy amine compound (B-2) were used. Next, the resulting coating liquid 6 was applied to a resin film under the same conditions as in Example 1 and dried to produce an adhesive film 6 consisting of a resin film and an adhesive layer 6. The dry film thickness of the adhesive layer 6 in the resulting adhesive film 6 was approximately 0.487 mm. The physical properties of the resulting adhesive layer 6 were evaluated under the same conditions as in Example 1.
• a draw-forming laminate 6 was produced under the same conditions as in Example 1, except that the temperature at which the GA steel sheet was preheated on the heating stage of the laminator was changed from 185°C to 200°C.
• the resulting draw-forming laminate 6 was evaluated for adhesion between the PET film and the GA steel sheet, and for draw-formability, under the same conditions as in Example 1. The evaluation results are shown in Table 3 below.
• Example 7 Coating liquid 7 was produced under the same conditions as in Example 1, except that, per 100 mol parts of carboxy groups in the polyester resin (A), 47 mol parts of epoxy compound (B-1) were used instead of 50 mol parts, and 2 mol parts of epoxyamine compound (B-2) were used, and 10 mol parts of transesterification catalyst (D-1) were used instead of 20 mol parts.
• the resulting coating liquid 7 was applied to a resin film under the same conditions as in Example 1 and dried to produce an adhesive film 7 consisting of a resin film and an adhesive layer 7. The physical properties of the resulting adhesive layer 7 were evaluated under the same conditions as in Example 1.
• a draw-forming laminate 7 was produced under the same conditions as in Example 1, except that the temperature at which the GA steel sheet was preheated on the heating stage of the laminator was changed from 185°C to 200°C.
• the resulting draw-forming laminate 7 was evaluated for adhesion between the PET film and the GA steel sheet, and for draw-formability, under the same conditions as in Example 1. The evaluation results are shown in Table 3 below.
• a draw-forming laminate 11 was produced under the same conditions as in Example 1, except that the temperature at which the GA steel plate was preheated on the heating stage of the laminator was changed from 185°C to 200°C.
• the obtained draw-forming laminate 11 was evaluated for adhesion between the PET film and the GA steel plate and draw formability under the same conditions as in Example 1. The evaluation results are shown in Table 3 below.
• a draw-forming laminate 12 was produced under the same conditions as in Example 1, except that the temperature at which the GA steel plate was preheated on the heating stage of the laminator was changed from 185°C to 200°C.
• the resulting draw-forming laminate 12 was evaluated for adhesion between the PET film and the GA steel plate and for draw-formability under the same conditions as in Example 1. The evaluation results are shown in Table 3 below.
• Examples 1 to 7 are examples using adhesive films that satisfy the requirements of the present invention.
• the adhesive layer contained in the adhesive film is easily stretched and not easily broken during drawing. Therefore, the laminate in which the GA steel sheet and PET film are bonded together via the adhesive layer exhibited good adhesion between the GA steel sheet and the PET film, and the PET film was not easily peeled off from the GA steel sheet during drawing.
• Comparative Examples 1 and 2 are examples using adhesive films that do not satisfy the requirements of the present invention.
• the adhesive layer contained in the adhesive film is easily stretched and not easily broken during drawing. Therefore, the laminate in which the GA steel sheet and PET film are bonded together via the adhesive layer exhibited poor adhesion between the GA steel sheet and the PET film, and the PET film peeled off from the GA steel sheet during drawing.

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