Classifications

• • 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
  • C09J7/38—Pressure-sensitive adhesives [PSA]
• • 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
• • 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
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
  • C08G63/181—Acids containing aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
• • 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
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
• • 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
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
  • C08K5/1515—Three-membered rings
• • 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
  • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
  • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
• • 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
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
  • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
• • 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
  • C09J2301/00—Additional features of adhesives in the form of films or foils
  • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
  • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
• • 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
  • C09J2467/00—Presence of polyester

Definitions

• the present invention relates to a polyester pressure-sensitive adhesive composition, a polyester pressure-sensitive adhesive, a pressure-sensitive adhesive sheet, a decorative film, a film for electronic components, and a decorated molded article, and more specifically relates to adhesive strength, heat resistance, moist heat resistance, and optical properties.
• the present invention relates to a polyester pressure-sensitive adhesive composition having excellent properties, a pressure-sensitive adhesive obtained by crosslinking such a pressure-sensitive adhesive composition, and a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer containing such a pressure-sensitive adhesive.
• the present invention also relates to a decorative film made of such a pressure-sensitive adhesive sheet and a decorated molded product formed by laminating such decorative films.
• polyester resins have excellent heat resistance, chemical resistance, durability, and mechanical strength, so they have been used in a wide range of applications such as films, PET bottles, fibers, toners, electrical parts, adhesives, and adhesives. ing.
• polyester resin has high polarity due to its polymer structure, it can exhibit excellent adhesion to polar polymers such as polyester, polyvinyl chloride, polyimide, and epoxy resin, as well as metal materials such as copper and aluminum. are known.
• decorative films are laminated to molded products such as automobile interior and exterior parts, home appliance parts, and building material parts as an alternative to conventional painting methods, with the aim of improving design and suppressing VOC (Volatile Organic Compounds) emissions. , or transfer is being performed.
• a molding method using a decorative film in-mold molding by injection molding, vacuum molding, vacuum-pressure molding, etc. are used.
• a decorative film to be attached to a molded product a decorative film provided with an adhesive layer is known.
• Patent Document 1 describes a thermoplastic polyester elastomer with excellent moldability, water resistance, and weather resistance, in which the acid component is mainly aromatic dicarboxylic acid, and the glycol component is 1 to 60 mol% based on the total glycol component.
• a thermoplastic polyester elastomer has been proposed, which is a copolymerized polyester containing a dimer diol having a reduced viscosity of 0.5 to 3.0.
• Patent Document 2 describes a polyester pressure-sensitive adhesive composition that exhibits little change over time, such as an increase in adhesive strength, even when used in high-temperature environments.
• a polyester pressure-sensitive adhesive composition has been proposed which is characterized by containing a polyester resin having a carboxy group derived from at least one of the above carboxylic acid and its acid anhydride.
• Patent Document 3 describes a polyester that has excellent solvent solubility, heat resistance, low tackiness, low dielectric constant and dielectric loss tangent, and excellent dielectric properties when the polycarboxylic acid component is 100 mol%.
• an adhesive composition containing 50 mol % or more of a naphthalene dicarboxylic acid component and at least one of a dimer diol component and tricyclodecane dimethanol as a polyhydric alcohol component has been proposed.
• Patent Document 4 describes an adhesive composition that has excellent long-term durability in a moist heat environment and also has high adhesive properties, with an ester bond concentration of 7 mmol/g or less, an acid value of 3 mgKOH/g or more, and a glass transition An adhesive composition containing a polyester resin that satisfies the requirement that the temperature is -5° C. or higher has been proposed.
• Patent Document 1 discloses a technology related to a polyester elastomer, and since the polyester resin has high crystallinity, the tackiness at room temperature (23° C.) is low, making it difficult to use in adhesive applications. Further, since the polyester resin is not given an acid value that becomes a reaction point with the polyepoxy compound, no consideration has been given to heat resistance.
• Patent Document 2 discloses a technique related to a polyester adhesive for masking, and although it has excellent heat resistance, the acid value of the polyester resin that serves as a crosslinking point with a polyepoxy compound is too high, so it has a high crosslinking density. However, the adhesion was extremely low and problems remained. Further, no consideration was given to heat and humidity resistance, and there was room for improvement in long-term durability in a heat and humidity environment.
• Patent Document 3 discloses a technology related to polyester with excellent dielectric properties, in which a large amount of polycyclic polycarboxylic acid with high crystal orientation is added to polycarboxylic acids for the purpose of reducing dielectric constant, dielectric loss tangent, and water absorption. As a result, the glass transition temperature becomes high, and problems remain with respect to tackiness and molding stability when used as a pressure-sensitive adhesive sheet.
• polyhydric alcohols contain large amounts of polyhydric alcohols with long-chain alkyl groups with low polarity, they have poor solubility in polar solvents, resulting in poor long-term stability of resin solutions and compatibility with polyepoxy compounds, etc. The problem was that the optical properties were low.
• Patent Document 4 is a technical disclosure regarding polyester adhesives, and the polyester resin has a high glass transition temperature to be tack-free and has low tackiness at room temperature (23°C), making it difficult to use in adhesive applications. It was something.
• the present invention provides polyester adhesive compositions with excellent adhesive strength, heat resistance, heat and humidity resistance, and optical properties, as well as adhesives, adhesive sheets, and processed adhesives crosslinked with such adhesive compositions.
• a decorative film, a film for electronic components, and a decorative molded article are provided.
• the gist of the present invention is the following [1] to [21].
• the polyester resin (A) has a structural unit derived from a polyhydric carboxylic acid (a) and a structural unit derived from a polyhydric alcohol (b).
• the content of the structural unit derived from the cyclic structure-containing polyvalent carboxylic acid (a1) is 30 mol% or more with respect to 100 mol% of the structural unit derived from the polyvalent carboxylic acid (a).
• the structural unit derived from the polyhydric alcohol (b) contains a structural unit derived from the aliphatic polyhydric alcohol (b1).
• the acid value of the polyester resin (A) is 1.5 to 30 mgKOH/g.
• the glass transition temperature of the polyester resin (A) is -75 to -20°C.
• the structural unit derived from the cyclic ester in the polyester resin (A) is less than 140 mol% with respect to 100 mol% of the structural unit derived from the polyhydric carboxylic acid (a).
• the structural unit derived from the aliphatic polyhydric alcohol (b1) contains a structural unit derived from a polyhydric alcohol having a hydrocarbon group in at least one of the side chains.
• the content of the structural unit derived from the aliphatic polyhydric alcohol (b1) is 5 to 80 mol% with respect to 100 mol% of the structural unit derived from the polyhydric alcohol (b) [1] to [4]
• the total content of structural units derived from dimer acid (a2) and structural units derived from dimer diol (b2) with respect to the entire polyester resin (A) is 20 to 90% by mass [1] to [ 6].
• the polyester pressure-sensitive adhesive composition according to any one of [6] [8] The polyester adhesive composition according to any one of [1] to [7], wherein the polyester resin (A) has an ester bond concentration of 1.5 to 8.0 mmol/g. [9] The polyester adhesive composition according to any one of [1] to [8], wherein the polyester resin (A) has a heat of crystal fusion of 3 J/g or less. [10] The polyester adhesive composition according to any one of [1] to [9], wherein the polyepoxy compound (B) contains a nitrogen atom-containing polyepoxy compound.
• a decorative film comprising the pressure-sensitive adhesive sheet according to [17].
• a film for electronic components comprising the pressure-sensitive adhesive sheet according to [17].
• a decorated molded article obtained by laminating the decorative film according to [18] on a molded article.
• a decorative film comprising an adhesive layer formed from a polyester adhesive composition containing a polyester resin (A) and a polyepoxy compound (B), A decorative film in which the polyester resin (A) satisfies all of the following (1) to (4).
• the polyester resin (A) has a structural unit derived from a polyhydric carboxylic acid (a) and a structural unit derived from a polyhydric alcohol (b).
• the content of the structural unit derived from the cyclic structure-containing polyvalent carboxylic acid (a1) is 30 mol% or more with respect to 100 mol% of the structural unit derived from the polyvalent carboxylic acid (a).
• the structural unit derived from the polyhydric alcohol (b) contains a structural unit derived from the aliphatic polyhydric alcohol (b1).
• the acid value of the polyester resin (A) is 1.5 to 30 mgKOH/g.
• the polyester pressure-sensitive adhesive composition of the present invention can form a pressure-sensitive adhesive with excellent adhesive strength, heat resistance, heat-and-moisture resistance, and optical properties. It is effective as an adhesive used in films.
• the glass transition temperature of the polyester resin is raised or a functional group is added to increase the number of crosslinking points.
• structural units derived from polycarboxylic acids having a specific acid value and glass transition temperature and derived from a cyclic structure we use structural units derived from aliphatic polyhydric alcohols that can reduce durability.
• the term "class” added after a compound name is a concept that includes not only the compound but also derivatives of the compound.
• carboxylic acids includes not only carboxylic acids but also carboxylic acid derivatives such as carboxylic acid salts, carboxylic acid anhydrides, carboxylic acid halides, and carboxylic esters.
• X and/or Y (X, Y are arbitrary configurations) means at least one of X and Y, and means three ways: X only, Y only, and X and Y. It is something to do.
• a polyester adhesive composition according to an embodiment of the present invention contains a polyester resin (A) and a polyepoxy compound (B). , the polyester resin (A) satisfies all of the following (1) to (6).
• the polyester resin (A) has a structural unit derived from a polyhydric carboxylic acid (a) and a structural unit derived from a polyhydric alcohol (b).
• the content of the structural unit derived from the cyclic structure-containing polyvalent carboxylic acid (a1) is 30 mol% or more with respect to 100 mol% of the structural unit derived from the polyvalent carboxylic acid (a).
• the structural unit derived from the polyhydric alcohol (b) contains a structural unit derived from the aliphatic polyhydric alcohol (b1).
• the acid value of the polyester resin (A) is 1.5 to 30 mgKOH/g.
• the glass transition temperature of the polyester resin (A) is -75 to -20°C.
• the structural unit derived from the cyclic ester in the polyester resin (A) is less than 140 mol% with respect to 100 mol% of the structural unit derived from the polyhydric carboxylic acid (a).
• the polyester resin (A) has a structural unit derived from a polyhydric carboxylic acid (a) and a structural unit derived from a polyhydric alcohol (b) in its molecule, and preferably contains a structural unit derived from a polyhydric carboxylic acid (a). ) and a polyhydric alcohol (b) through an ester bond.
• polyhydric carboxylic acids (a) examples include cyclic structure-containing polycarboxylic acids (a1) such as monocyclic polycarboxylic acids and polycyclic polycarboxylic acids; dimer acids (a2), and acid anhydrides. Examples include trivalent or higher polycarboxylic acids having 0 or 1 base; aliphatic polycarboxylic acids; and the like.
• the polyester resin (A) contains a structural unit derived from the cyclic structure-containing polycarboxylic acid (a1). Moreover, one type or two or more types of polyhydric carboxylic acids (a1) can be used.
• the content of the structural unit derived from the cyclic structure-containing polyvalent carboxylic acid (a1) relative to 100 mol% of the structural unit derived from the polyvalent carboxylic acid (a) is 30 mol% or more, preferably 40 to 99 mol%, and It is preferably 50 to 95 mol%, particularly preferably 55 to 90 mol%, particularly preferably 60 to 85 mol% or more.
• the upper limit is usually 100 mol%. If the content of the structural unit derived from the cyclic structure-containing polycarboxylic acid (a1) is too small, the heat resistance and moist heat resistance will be insufficient. In addition, if the content is too high, the compatibility with the polyepoxy compound (B) will decrease, resulting in insufficient optical properties, or the glass transition temperature will increase, resulting in insufficient tackiness, adhesive strength, and molding stability. Become.
• the content (molar ratio) of the structural unit derived from the cyclic structure-containing polyvalent carboxylic acid (a1) with respect to 100 mol % of the structural unit derived from the polyvalent carboxylic acid (a) is determined from the following formula.
• Content (mol%) of structural units derived from cyclic structure-containing polycarboxylic acids (a1) (content (mol) of structural units derived from cyclic structure-containing polycarboxylic acids (a1)/polycarboxylic acids (a ) content of structural units derived from (mol)) x 100
• the content of the structural unit derived from the cyclic structure-containing polycarboxylic acid (a1) based on the entire polyester resin (A) is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably is 7 to 35% by weight, particularly preferably 10 to 30% by weight, particularly preferably 15 to 25% by weight. If the content of the structural unit derived from the cyclic structure-containing polycarboxylic acid (a1) is too small, heat resistance and heat-and-moisture resistance tend to be insufficient, and if it is too large, the compatibility with the polyepoxy compound (B) will be poor. There is a tendency for the optical properties to decrease and the optical properties to become insufficient, or for the glass transition temperature to become high and to result in insufficient tackiness, adhesive strength, and molding stability.
• Examples of the cyclic structure-containing polycarboxylic acids (a1) include monocyclic polycarboxylic acids (a1-1) and polycyclic polycarboxylic acids (a1-2).
• the cyclic structure-containing polycarboxylic acids (a1) preferably contain monocyclic polycarboxylic acids (a1-1), particularly preferably from the viewpoint of excellent adhesive strength, molding stability, and optical properties.
• the cyclic structure-containing polyvalent carboxylic acid (a1) is a monocyclic polyvalent carboxylic acid (a1-1).
• Examples of the monocyclic polycarboxylic acids (a1-1) include aromatic monocyclic dicarboxylic acids such as terephthalic acids, isophthalic acids, and orthophthalic acids, 1,4-cyclohexanedicarboxylic acids, and 1,3-cyclohexane.
• Examples include dicarboxylic acids and alicyclic monocyclic dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acids.
• the monocyclic polycarboxylic acids (a-1) also include trifunctional or higher functional monocyclic polycarboxylic acids that are introduced for the purpose of imparting a branched skeleton or acid value to the polyester resin (A). included.
• the trifunctional or more functional monocyclic polycarboxylic acids include trimellitic acids, trimesic acids, pyromellitic acids, and the like.
• monocyclic polycarboxylic acids (a1-1) monocyclic aromatic dicarboxylic acids such as terephthalic acids, isophthalic acids, and orthophthalic acids are preferred, particularly preferred, because they have excellent heat resistance and moist heat resistance.
• terephthalic acids and isophthalic acids are more preferred because they lower the crystallinity of the polyester resin (A) and have excellent stability after dissolution in a solvent, and are also excellent in tackiness and adhesive strength.
• the monocyclic polyvalent carboxylic acids (a1-1) can also be classified into asymmetric monocyclic polyvalent carboxylic acids and symmetric monocyclic polyvalent carboxylic acids.
• the polycarboxylic acid (a) contains an asymmetric monocyclic polycarboxylic acid, and in terms of excellent solvent dissolution stability, It is preferable to contain asymmetric monocyclic polyvalent carboxylic acids and symmetric monocyclic polyvalent carboxylic acids.
• Examples of the asymmetric monocyclic polycarboxylic acids include isophthalic acids, orthophthalic acids, 1,3-cyclohexanedicarboxylic acids, 1,2-cyclohexanedicarboxylic acids, and the like. In this respect, isophthalic acids are particularly preferred.
• Examples of the symmetrical monocyclic polycarboxylic acids include terephthalic acids and 1,4-cyclohexanedicarboxylic acids.
• the polyester resin (A) contains a structural unit derived from the monocyclic polycarboxylic acid (a1-1), the monocyclic polycarboxylic acid based on 100 mol% of the structural unit derived from the polycarboxylic acid (a)
• the content of structural units derived from acids (a1-1) is preferably 30 mol% or more, more preferably 40 to 98 mol%, even more preferably 50 to 95 mol%, particularly preferably 55 to 90 mol%. %, particularly preferably 60 to 85 mol %.
• the cyclic structure-containing polycarboxylic acid (a1) may contain a polycyclic polycarboxylic acid (a1-2) from the viewpoint of heat resistance and heat-and-moisture resistance.
• the polycyclic polycarboxylic acids (a1-2) include polycyclic aromatic dicarboxylic acids such as biphenyl dicarboxylic acids, naphthalene dicarboxylic acids, and dimethyl naphthalene dicarboxylate.
• the polyester resin (A) contains a structural unit derived from the polycyclic polycarboxylic acid (a1-2), the polycyclic polycarboxylic acid based on 100 mol% of the structural unit derived from the polycarboxylic acid (a1)
• the content of structural units derived from acids (a1-2) is preferably 50 mol% or less, more preferably 40 mol% or less, even more preferably 30 mol% or less, particularly preferably 20 mol% or less, especially It is preferably 10 mol% or less, most preferably 5 mol% or less.
• the structural unit derived from the polyhydric carboxylic acid (a) preferably contains a structural unit derived from the dimer acid (a2) from the viewpoints of heat-and-moisture resistance and adhesive strength.
• dimer acids (a2) include dimer acids (mainly those having 36 to 44 carbon atoms) derived by dimerizing unsaturated aliphatic acids such as oleic acid, linoleic acid, linolenic acid, and erucic acid. ), and hydrogenated products thereof.
• hydrogenated substances are preferred from the viewpoint of suppressing gelation during the production of polyester resins.
• the content of structural units derived from dimer acids (a2) with respect to 100 mol% of structural units derived from polyhydric carboxylic acids (a) is preferably 70 mol% or less, more preferably 3 to 60 mol%, still more preferably 5 to 50 mol%, particularly preferably 10 to 45 mol%, particularly preferably 15 to 40 mol%. If the content of structural units derived from dimer acids (a2) is too small, adhesive strength and heat and humidity resistance tend to be insufficient, while if it is too large, compatibility with the polyepoxy compound (B) decreases and optical properties deteriorate. There is a tendency for the solvent dissolution stability to become insufficient.
• the polyester resin (A) contains structural units derived from dimer acids (a2)
• the content of structural units derived from dimer acids (a2) with respect to the entire polyester resin (A) is 3 to 80% by mass. It is preferable that %. If the content of structural units derived from dimer acids (a2) is too small, adhesive strength and heat and humidity resistance tend to be insufficient, while if it is too large, compatibility with the polyepoxy compound (B) decreases and optical properties deteriorate. There is a tendency for the solvent dissolution stability to become insufficient.
• the structural unit derived from polyvalent carboxylic acids (a) may contain a structural unit derived from aliphatic polyvalent carboxylic acids from the viewpoint of adhesive strength and molding stability.
• the aliphatic polycarboxylic acids include malonic acids, dimethylmalonic acids, succinic acids, glutaric acids, adipic acids, trimethyladipic acids, pimelic acids, 2,2-dimethylglutaric acids, azelaic acids, sebacic acids, and fumaric acids.
• Acids include maleic acids, itaconic acids, thiodipropionic acids, diglycolic acids, 1,9-nonanedicarboxylic acids, and the like. These may be used alone or in combination of two or more.
• adipic acids, sebacic acids, and azelaic acids are particularly preferred because they lower the glass transition temperature and have excellent adhesive strength and molding stability, as well as excellent optical properties of the resin.
• the polyester resin (A) contains a structural unit derived from an aliphatic polycarboxylic acid
• the amount is preferably 70 mol% or less, more preferably 3 to 60 mol%, even more preferably 5 to 50 mol%, particularly preferably 10 to 45 mol%, particularly preferably 15 to 40 mol%. . If the content of structural units derived from aliphatic polyhydric carboxylic acids is too small, adhesive strength and molding stability tend to be insufficient, and if it is too large, heat resistance and moist heat resistance tend to be insufficient.
• the structural unit derived from the polyvalent carboxylic acid (a) is a structure derived from a trivalent or higher polyvalent carboxylic acid having an acid anhydride group of 0 or 1. It is preferable to contain units from the viewpoint of adhesive strength.
• the valence of the carboxy group in the trivalent or higher polyvalent carboxylic acid in which the acid anhydride group is 0 or 1 is preferably 3 to 6 valences, more preferably 3 to 4 valences.
• trivalent or higher polyhydric carboxylic acids in which the acid anhydride group is 0 or 1 include trimellitic acid, trimesic acid, ethylene glycol bis(anhydrotrimellitate), glycerol tris(anhydrotrimellitate), etc.
• trimellitic anhydride trimellitic anhydride, pyromellitic dianhydride, oxydiphthalic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenyl Tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride, 2,2'-bis[ (dicarboxyphenoxy)phenyl]propane dianhydride, etc., which have 0 or 1 acid anhydride group; trivalent or higher aromatic polycarboxylic acids, etc.; hydrogenated trimellitic anhydride, etc., which has 0 acid anhydride group; or trivalent or higher aliphatic polycarboxylic acids which are monovalent.
• trivalent or higher aromatic polycarboxylic acids having 0 or 1 acid anhydride group are preferred, and more preferably trivalent or higher aromatic polycarboxylic acids having 1 acid anhydride group.
• trimellitic anhydride is particularly preferred.
• the polyester resin (A) may be a sulfone such as sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, or 5(4-sulfophenoxy)isophthalic acid.
• sulfone such as sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, or 5(4-sulfophenoxy)isophthalic acid.
• polyester resin (A ) the content thereof is preferably 10 mol% or less, more preferably 5 mol% or less, and particularly preferably It is 3 mol% or less, more preferably 1 mol% or less, and most preferably 0 mol%.
• polyhydric alcohol (b) examples include aliphatic polyhydric alcohols (b1), dimer diols (b2), alicyclic polyhydric alcohols, aromatic polyhydric alcohols, and bisphenol skeleton-containing polyhydric alcohols. Examples include alcohols. One type or two or more types of polyhydric alcohols (b) can be used.
• the polyester resin (A) contains a structural unit derived from an aliphatic polyhydric alcohol (b1) as a structural unit derived from a polyhydric alcohol (b).
• Examples of the aliphatic polyhydric alcohols (b1) include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 1,10-decanediol, 2-ethyl-2-butyl
• Examples include propanediol, 2,4-diethyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.
• 1,2-propylene glycol, 2-methyl-1,3-propanediol, neopentyl glycol, 3-methyl-1 Aliphatic polyhydric compounds having a hydrocarbon group in at least one side chain, such as 5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, etc. Alcohols are preferred, with 2-methyl-1,3-propanediol and 3-methyl-1,5-pentanediol being particularly preferred, and 3-methyl-1, 5-pentanediol. Note that the aliphatic polyhydric alcohols having a hydrocarbon group in at least one side chain exclude dimer diols (b2) described below.
• the content of the structural unit derived from the aliphatic polyhydric alcohol (b1) relative to 100 mol% of the structural unit derived from the polyhydric alcohol (b) is preferably 5 to 95 mol%, more preferably 15 to 90 mol%.
• the mole % is particularly preferably 25 to 85 mole %, more preferably 35 to 80 mole %, particularly preferably 45 to 75 mole %. If the content of the structural unit derived from the aliphatic polyhydric alcohol (b1) is too small, the compatibility with the polyepoxy compound (B) will decrease, resulting in insufficient optical properties or insufficient solvent dissolution stability. If the amount is too high, heat resistance, heat and humidity resistance, and adhesive strength tend to be insufficient.
• the polyester resin (A) preferably contains a structural unit derived from dimer diols (b2) as a structural unit derived from polyhydric alcohol (b).
• dimer diols (b2) examples include dimer acids (mainly those having 36 to 44 carbon atoms) derived by dimerizing unsaturated aliphatic acids such as oleic acid, linoleic acid, linolenic acid, and erucic acid.
• dimer diols which are reduced forms of (2), and hydrogenated products thereof.
• hydrogenated substances are preferred from the viewpoint of suppressing gelation during production of the polyester resin (A).
• the proportion of structural units derived from dimer diols (b2) relative to 100 mol% of structural units derived from polyhydric alcohols (b) is The content is preferably 3 to 95 mol%, more preferably 5 to 90 mol%, particularly preferably 4 to 80 mol%, even more preferably 5 to 70 mol%, particularly preferably 10 to 90 mol%. 50 mol%, most preferably 25-40 mol%.
• the polyester resin (A) contains structural units derived from dimer diols (b2)
• the content of structural units derived from dimer diols (b2) with respect to the entire polyester resin (A) is 3 to 3. It is preferably 80% by weight, more preferably 5 to 70% by weight, even more preferably 10 to 60% by weight, particularly preferably 15 to 50% by weight, particularly preferably 18 to 40% by weight, most preferably 30% by weight. ⁇ 45% by mass. If the content of the structural unit derived from dimer diols (b2) is too small, heat resistance, heat and humidity resistance, and adhesive strength tend to be insufficient, and if it is too large, the compatibility with the polyepoxy compound (B) will be poor. There is a tendency for the optical properties to deteriorate and the solvent dissolution stability to become insufficient.
• alicyclic polyhydric alcohols examples include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, tricyclodecanediol, tricyclodecane dimethanol, spiroglycol, and the like.
• aromatic polyhydric alcohols examples include paraxylene glycol, meta-xylene glycol, orthoxylene glycol, 1,4-phenylene glycol, and ethylene oxide adducts of 1,4-phenylene glycol. .
• Examples of the bisphenol skeleton-containing polyhydric alcohols include bisphenol A, bisphenol B, bisphenol E, bisphenol F, bisphenol AP, bisphenol BP, bisphenol P, bisphenol PH, bisphenol S, bisphenol Z, and 4,4'-dihydroxybenzophenone. , bisphenol fluorene and their hydrogenated products, and glycols such as ethylene oxide adducts and propylene oxide adducts obtained by adding one to several moles of ethylene oxide or propylene oxide to the hydroxyl group of bisphenols.
• the polyester resin (A) may be prepared using polyhydric alcohols (b) such as polyester diol, polyether diol, polycaprolactone diol, polycarbonate diol, and polybutadiene diol. , polyisoprene diol, etc. may also be used. Further, these may be used alone or in combination of two or more.
• polyhydric alcohols (b) such as polyester diol, polyether diol, polycaprolactone diol, polycarbonate diol, and polybutadiene diol.
• polyisoprene diol, etc. may also be used. Further, these may be used alone or in combination of two or more.
• the polyester resin (A) preferably contains a structural unit derived from dimer acids (a2) and/or a structural unit derived from dimer diols (b2) from the viewpoints of heat-and-moisture resistance and adhesive strength.
• the polyester resin (A) contains structural units derived from dimer acids (a2) and/or structural units derived from dimer diols (b2)
• the amount derived from dimer acids (a2) relative to the entire polyester resin (A) is preferably 20 to 90% by mass, more preferably 30 to 85% by mass, particularly preferably 35 to 80% by mass, even more preferably is from 40 to 75% by weight, particularly preferably from 45 to 70% by weight, most preferably from 50 to 65% by weight.
• the adhesive strength and heat-and-moisture resistance tend to be insufficient; if it is too large, the polyepoxy-based There is a tendency for the compatibility with compound (B) to decrease, resulting in insufficient optical properties or insufficient solvent dissolution stability.
• the polyester resin (A) preferably contains, as a branched skeleton, a structural unit derived from a trifunctional or higher functional polycarboxylic acid and/or a structural unit derived from a trifunctional or higher functional polyhydric alcohol.
• a crosslinking agent when reacting with a crosslinking agent to form a crosslinked structure, the presence of a branched skeleton in the polyester resin (A) increases the number of crosslinking points in the polyester resin (A), resulting in efficient aggregation with a small amount of crosslinking agent. A strong adhesive can be obtained.
• the trifunctional or higher-functional polycarboxylic acids used to introduce a branched skeleton into the polyester resin (A) are different from the polycarboxylic acids used in the depolymerization reaction described below.
• trifunctional or higher-functional polycarboxylic acids examples include trimellitic acid, trimesic acid, ethylene glycol bis(anhydrotrimellitate), glycerol tris(anhydrotrimellitate), trimellitic anhydride, and pyromellitate.
• Compounds such as substances and the like can be mentioned.
• trifunctional or higher-functional polyhydric alcohols examples include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and the like. These trifunctional or more functional polycarboxylic acids and trifunctional or more functional polyhydric alcohols can each be used singly or in combination of two or more.
• the polyester resin (A) contains a structural unit derived from a trifunctional or more functional polyhydric carboxylic acid and/or a structural unit derived from a trifunctional or more functional polyhydric alcohol as a branched skeleton
• the polyhydric carboxylic acid (a ) The content of trifunctional or higher-functional polycarboxylic acids relative to 100 mol% of structural units derived from ) is preferably 0.1 to 5 mol%, more preferably 0.3 to 4 mol%, and still more preferably 0.5 to 5 mol%. 3 mol%, particularly preferably 1 to 2.5 mol%.
• the content of the trifunctional or higher functional polyhydric alcohol relative to 100 mol% of the structural unit derived from the polyhydric alcohol (b) is preferably 0.1 to 5 mol%, more preferably 0.3 to 4 mol%. , more preferably 0.5 to 3 mol %, particularly preferably 1 to 2.5 mol %. If the content of both or either one is too large, the mechanical properties such as elongation at break of the coating film formed by applying the adhesive tend to decrease, and the adhesive strength tends to decrease. It also has a tendency to gel.
• the polyester resin (A) has a structural unit derived from a polyhydric carboxylic acid (a) and a structural unit derived from a polyhydric alcohol (b), but further contains a structural unit derived from a cyclic ester. It's okay.
• cyclic ester examples include lactide, ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -butyrolactone, ⁇ -hexanolactone, ⁇ -octanolactone, ⁇ -valerolactone, ⁇ -hexalanolactone, ⁇ -octa
• These cyclic ester monomers can be used alone or in combination of two or more.
• the structural unit derived from the cyclic ester in the polyester resin (A) is preferably less than 140 mol%, more preferably 100 mol%, based on 100 mol% of the structural unit derived from the polyhydric carboxylic acid (a). particularly preferably less than 60 mol %, more preferably less than 30 mol %, particularly preferably less than 15 mol % and most preferably 0 mol %. If the content of structural units derived from cyclic esters is too large, heat resistance, moist heat resistance, and solvent dissolution stability tend to be insufficient.
• the polyester resin (A) can be produced by a known method. For example, polyhydric carboxylic acids (a) and polyhydric alcohols (b) are subjected to an esterification reaction in the presence of a catalyst if necessary to obtain a prepolymer, and then polycondensation is performed to form a polyester. It can be manufactured by obtaining a resin and further introducing an acid value as necessary.
• the temperature in the esterification reaction of polyhydric carboxylic acids (a) and polyhydric alcohols (b) is usually 180 to 280°C, and the reaction time is usually 60 minutes to 8 hours.
• the temperature in polycondensation is usually 220 to 280°C, and the reaction time is usually 20 minutes to 4 hours. Moreover, it is preferable to perform polycondensation under reduced pressure.
• Examples of the method for introducing an acid value into the polyester resin include a method of introducing a carboxyl group into the polyester resin by an acid addition method or a depolymerization method after an esterification reaction or reduced pressure polycondensation.
• a carboxyl group into the polyester resin by an acid addition method or a depolymerization method after an esterification reaction or reduced pressure polycondensation.
• the carboxy group is efficiently introduced, increasing the molecular weight between crosslinking points with the polyepoxy compound (B), improving adhesive strength, heat resistance.
• the depolymerization method is particularly preferred since it has excellent molding stability.
• an acid addition method is preferred.
• polyhydric carboxylic acids (a) and polyhydric alcohols (b) are mixed in the presence of a catalyst as necessary. After obtaining a prepolymer by subjecting it to an esterification reaction, it may be subjected to polycondensation and further depolymerization.
• trivalent or higher polyhydric carboxylic acids having 0 or 1 acid anhydride group from the viewpoint of adhesive strength.
• trivalent or higher polyhydric carboxylic acids having 0 or 1 acid anhydride group include compounds such as trimellitic acid, trimellitic anhydride, hydrogenated trimellitic anhydride, and trimesic acid.
• the temperature during depolymerization is usually 200 to 260°C, and the reaction time is usually 10 minutes to 3 hours.
• a trivalent or higher polyvalent carboxylic acid having an acid anhydride group number of 0 or 1 is added to 100 mol% of the structural unit derived from the polyvalent carboxylic acid (a).
• the content of acid-derived structural units exceeds 20 mol%, the molecular weight of the resin tends to decrease significantly. Therefore, the content of structural units derived from trivalent or higher carboxylic acids having an acid anhydride group of 0 or 1 with respect to 100 mol% of structural units derived from polyvalent carboxylic acids (a) shall be 20 mol% or less. It is preferably 1 to 15 mol%, particularly preferably 2 to 10 mol%, and even more preferably 3 to 8 mol%.
• an esterification reaction is performed between polycarboxylic acids (a) excluding polycarboxylic acid anhydrides and polyhydric alcohols (b).
• the resulting hydroxyl group-containing prepolymer may be subjected to acid addition by reacting with a polyhydric carboxylic acid anhydride.
• a monocarboxylic acid, dicarboxylic acid, or polyfunctional carboxylic acid compound is used, a decrease in molecular weight may occur due to transesterification, so a compound containing at least one carboxylic acid anhydride should be used. is preferred.
• examples of the acid addition and depolymerization methods include a method of directly adding in a bulk state and a method of adding after converting the polyester resin into a solution.
• the reaction in the bulk state is fast, but gelation may occur if a large amount is added, and the reaction takes place at high temperatures, so care must be taken to prevent oxidation by blocking oxygen gas.
• addition in a solution state allows a large amount of carboxy groups to be stably introduced, although the reaction is slow.
• carboxylic anhydride examples include succinic anhydride, maleic anhydride, orthophthalic anhydride, 2,5-norbornenedicarboxylic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, and pyromellitic dianhydride.
• oxydiphthalic dianhydride 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, 3,3',4, Compounds such as 4'-diphenylsulfonetetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride, 2,2'-bis[(dicarboxyphenoxy)phenyl]propane dianhydride, etc. etc.
• polyester resin (A) When producing polyester resin (A) by an acid addition method, gelation may occur if acid addition is performed in an amount of 15 mol% or more based on 100 mol% of structural units derived from polyhydric carboxylic acids (a). Therefore, it is preferable to carry out acid addition at less than 15 mol%.
• composition ratio of polyester resin (A) the ratio (composition ratio) of structural sites derived from each component of the polyester resin (A) is determined by a known method using NMR, for example, 1 H-NMR measurement at a resonance frequency of 400 MHz (proton type nuclear magnetism). It can be determined by resonance spectroscopy), 13 C-NMR measurement (carbon type nuclear magnetic resonance spectroscopy), etc.
• the glass transition temperature of the polyester resin (A) used in the present invention is -75 to -20°C, preferably -70 to -22°C, more preferably -65 to -24°C, particularly preferably -60 to -24°C. -26°C, more preferably -55 to -28°C, particularly preferably -50 to -30°C, and most preferably -45 to -35°C. If the glass transition temperature is too high, the tackiness and adhesion will be insufficient, and the tensile properties will decrease, resulting in insufficient processing suitability and molding stability. If the glass transition temperature is too low, the heat resistance will be insufficient. , moisture and heat resistance tends to be insufficient.
• the method for measuring glass transition temperature is as follows.
• the glass transition temperature can be determined by measuring using a differential scanning calorimeter.
• the measurement conditions were a measurement temperature range of -90 to 100°C and a temperature increase rate of 10°C/min.
• the polyester resin (A) is crosslinked with a polyepoxy compound (B) and has a carboxyl group as a crosslinking point.
• the acid value of the polyester resin (A) is 1.5 to 30 mgKOH/g, preferably 2 to 20 mgKOH/g, particularly preferably 2.5 to 15, and even more preferably 3 to 12 mgKOH/g. g, particularly preferably from 3.5 to 10 mgKOH/g, most preferably from 4 to 8 mgKOH/g. If the acid value is too low, the number of crosslinking points tends to decrease, resulting in insufficient heat resistance; if the acid value is too high, the number of crosslinking points increases, resulting in insufficient adhesion and molding stability. In addition, the amount of polyepoxy compound (B) required for crosslinking tends to increase, resulting in insufficient optical properties.
• the definition and measurement method of acid value are as follows.
• the hydroxyl value of the polyester resin (A) is preferably 10 mgKOH/g or less, particularly 5 mgKOH/g or less, further 3 mgKOH/g or less, more preferably 2 mgKOH/g or less, particularly preferably 1 mgKOH/g. /g or less, most preferably 0.5 mgKOH/g or less. If the hydroxyl value is too high, the number of crosslinking points with the polyepoxy compound (B) will decrease, and the heat resistance and moist heat resistance will tend to be insufficient.
• the hydroxyl value of the polyester resin (A) is determined by neutralization titration based on JIS K 0070.
• the ester bond concentration of the polyester resin (A) used in the present invention is preferably 1.5 to 8 mmol/g, more preferably 2 to 7.5 mmol/g, even more preferably 2.5 to 7 mmol/g. mmol/g, particularly preferably 3 to 6.5 mmol/g, particularly preferably 3.5 to 6 mmol/g, most preferably 4 to 5.5 mmol/g. If the ester bond concentration is too high, heat resistance and heat-moisture resistance tend to be insufficient, and if the ester bond concentration is too low, the compatibility with the polyepoxy compound (B) decreases, resulting in insufficient optical properties. There is a tendency to
• ester bond concentration refers to the number of moles of ester bonds in 1 g of the polyester resin (A), and is obtained, for example, from a calculated value from the amount charged.
• This calculation method is a value obtained by dividing the smaller number of moles of each of the charged amounts of polyhydric carboxylic acids (a) and polyhydric alcohols (b) by the mass of the entire polyester resin (A), An example of the calculation formula is shown below.
• the amounts of the polyhydric carboxylic acids (a) and the polyhydric alcohols (b) are the same molar amount, either of the following calculation formulas may be used.
• the calculation method when using a monomer having both a carboxyl group and a hydroxyl group, or when producing polyester from caprolactone or the like, the calculation method must be changed as appropriate.
• Ester group concentration (mmol/g) [(A1/a1 ⁇ m1+A2/a2 ⁇ m2+A3/a3 ⁇ m3...)/Z] ⁇ 1000
• the ester bond concentration can be determined by a known method using NMR or the like, such as 1 H-NMR measurement (proton type nuclear magnetic resonance spectroscopy) or 13 C-NMR measurement (carbon type nuclear magnetic resonance spectroscopy) at a resonance frequency of 400 MHz. It can also be measured by
• the peak top molecular weight (Mp) of the polyester resin (A) is preferably 5,000 to 150,000, more preferably 10,000 to 120,000, particularly preferably 20,000 to 100,000, still more preferably 30,000 to 90,000, particularly preferably 40,000 to 80,000. It is. If the peak top molecular weight (Mp) is too low, the cohesive force tends to be insufficient, and the heat resistance and moist heat durability tend to be insufficient. Furthermore, if the peak top molecular weight (Mp) is too high, the adhesive strength tends to be insufficient, the compatibility with the polyepoxy compound (B) decreases, and the optical properties tend to become insufficient.
• the weight average molecular weight (Mw) of the polyester resin (A) is preferably 5,000 to 500,000, more preferably 10,000 to 300,000, particularly preferably 20,000 to 200,000, still more preferably 30,000 to 150,000, particularly preferably 50,000 to 130,000. It is. If the weight average molecular weight (Mw) is too low, the cohesive force tends to be insufficient, and the heat resistance and moist heat durability tend to be insufficient. Furthermore, if the weight average molecular weight (Mw) is too high, the adhesive strength tends to be insufficient, the compatibility with the polyepoxy compound (B) decreases, and the optical properties tend to become insufficient.
• the method for measuring the peak top molecular weight (Mp) and weight average molecular weight (Mw) is as follows.
• the peak top molecular weight (Mp) and weight average molecular weight (Mw) were measured using a column (TSKgel SuperMultipore HZ-M (exclusion limit molecular weight: 2 ⁇ 10 6
• the polyester resin (A) is preferably an amorphous polyester resin in terms of solvent solubility, solution stability, tackiness, optical properties, etc.
• the polyester resin (A) is crystalline, it tends to have insufficient solvent solubility, solution stability, tackiness, molding stability, optical properties, etc.
• the amorphousness can be confirmed by a differential scanning calorimeter, for example, if no endothermic peak due to crystal melting is observed when measured at a temperature range of -90 to 400°C and a temperature increase rate of 10°C/min. say. Note that the measurement temperature range and temperature increase rate can be changed as appropriate depending on the sample.
• the heat of crystal fusion of the polyester resin (A), when crystallized, is 35 J/g or less, preferably 20 J/g or less, particularly preferably 10 J/g or less, particularly preferably 5 J/g or less. It is preferable that it is more preferably 3 J/g or less, most preferably 1 J/g or less.
• the polyester resin (A) is amorphous, which is preferable in terms of solvent solubility, solution stability, tackiness, optical properties, etc.
• the polyester resin (A) is preferably made of plant-derived raw materials and has a biomass content in order to reduce the burden on the global environment.
• the biomass degree of the polyester resin (A) is preferably 10% or more, more preferably 20% or more, particularly preferably 30% or more, still more preferably 40% or more, and particularly preferably 50%. or more, most preferably 60% or more. Note that the upper limit is 100%. If the degree of biomass is low, there is a tendency for the reduction of the burden on the global environment to be insufficient.
• the biomass degree of the polyester resin (A) refers to the amount of plant-derived raw materials used in producing the polyester resin (A) that are incorporated into the resin, relative to the total mass of the polyester resin (A). It is the mass percentage of the part that has been removed, and its calculation method is as follows.
• the biomass degree of polyhydric carboxylic acids (a) and polyhydric alcohol (b) shall be determined from the weighted average of the respective biomass degrees. Furthermore, it is sufficient that the value obtained by any one of the following calculation methods is within the above range.
• Biomass degree (%) [(Number of moles of carbon in the plant-derived monomer calculated from the molar ratio of polycarboxylic acids (a) and polyhydric alcohols (b) in polyester resin (A)) / (Polyester resin Number of moles of carbon in all constituent monomers in resin (A)] x 100
• the degree of biomass can also be determined by analyzing the composition ratio using NMR and calculating the number of carbon atoms in the plant-derived monomer/the number of carbon atoms in total.
• the degree of biomass can also be measured by the method described in "Biofuel Origin Determination Technology Using Natural Radioactive Carbon C-14", Tokyo Metropolitan Industrial Technology Research Center Research Report, No. 4, 2009. .
• the polyester resin (A) is soluble in a non-petroleum organic solvent and a non-aldehyde organic solvent. If the solubility in such organic solvents is insufficient, the burden on the human body and the global environment will be large, the preparation of the adhesive composition will be difficult, and the solution stability after dissolution will tend to be insufficient. be.
• the non-petroleum organic solvents and non-aldehyde organic solvents include, for example, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, alcohol solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and isobutyl alcohol, and ethyl acetate. , ester solvents such as n-butyl acetate, acetate solvents such as cellosolve acetate and methoxy acetate, or a mixture of two or more of these solvents.
• ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone
• alcohol solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and isobutyl alcohol, and ethyl acetate.
• ester solvents such as n-butyl
• ketone solvents and ester solvents are preferred, particularly methyl ethyl ketone, cyclohexanone, and ethyl acetate, and more preferred are methyl ethyl ketone and ethyl acetate because of their low boiling points and excellent drying efficiency.
• the adhesive composition further contains a polyepoxy compound (B) as a crosslinking agent. Since the present adhesive composition contains the polyepoxy compound (B), the epoxy group in the polyepoxy compound (B) and the carboxyl group in the polyester resin (A) react, resulting in crosslinking (curing). ), it is possible to obtain an adhesive with excellent not only adhesive strength but also heat resistance.
• the polyepoxy compound (B) refers to a compound having at least two or more epoxy groups in the molecule.
• polyepoxy compound (B) examples include glycidyls such as tetraglycidyldiaminodiphenylmethane, triglycidylpara-aminophenol, tetraglycidylbisaminomethylcyclohexane, and N,N,N',N'-tetraglycidyl-m-xylene diamine.
• glycidyls such as tetraglycidyldiaminodiphenylmethane, triglycidylpara-aminophenol, tetraglycidylbisaminomethylcyclohexane, and N,N,N',N'-tetraglycidyl-m-xylene diamine.
• Bifunctional glycidyl ether types such as bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, and brominated bisphenol A diglycidyl ether; Multifunctional glycidyl ether types such as phenol novolac glycidyl ether and cresol novolac glycidyl ether; Hexahydrophthal Glycidyl ester types such as acid glycidyl ester and dimer acid glycidyl ester; examples include alicyclic or aliphatic epoxides such as triglycidyl isocyanurate, 3,4-epoxycyclohexylmethyl carboxylate, epoxidized polybutadiene, and epoxidized soybean oil. .
• One type or two or more types of polyepoxy compounds (B) can be used.
• This pressure-sensitive adhesive composition uses a nitrogen atom-containing polyepoxy compound (nitrogen-containing polyepoxy It is preferable to contain a type compound).
• a type compound Particularly preferred are aromatic glycidylamine type polyepoxy compounds such as tetraglycidyldiaminodiphenylmethane, triglycidyl para-aminophenol, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N', It is an aliphatic glycidylamine-type polyepoxy compound such as N'-tetraglycidyl-m-xylene diamine, and has excellent low-temperature curability, and is commonly used in 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N, Preferably, it is an aliphatic glycidylamine type polyepoxy compound such as N,N',N'-tetragly
• the equivalent weight of the epoxy group of the polyepoxy compound (B) to the carboxyl group of the polyester resin (A) is preferably 0.3 to 5 equivalents, more preferably 0.5 to 4 equivalents, even more preferably 0.7 to 3.5 equivalents, more preferably 0.9 to 3.0 equivalents, particularly preferably 1.0 to 2.8 equivalents, particularly preferably 1.2 to 2.6 equivalents, particularly preferably 1.4 to 2.4 equivalents, most preferably 1.6 to 2.2 equivalents. If the amount is too large, the polyepoxy compound (B) that is not incorporated into the crosslinking will remain, and the optical properties and heat resistance will tend to be insufficient. On the other hand, if it is too small, the crosslinking density tends to be low, resulting in insufficient heat resistance, moist heat resistance, and adhesive strength.
• the equivalent weight of the epoxy group to the carboxyl group (COOH) is determined by the following formula from the acid value of the polyester resin (A) and the epoxy equivalent (g/eq) of the blended polyepoxy compound (B).
• Equivalent weight of epoxy group to COOH (e ⁇ WPE)/(AV ⁇ 56.1 ⁇ 1000 ⁇ P) e: Mass (g) of polyepoxy compound (B) used for blending
• WPE Epoxy equivalent (g/eq) of polyepoxy compound (B)
• AV Acid value of polyester resin (A) (mgKOH/g)
• P Mass (g) of polyester resin (A) used for blending
• the epoxy equivalent (WPE) of the polyepoxy compound (B) is preferably 500 g/eq or less, more preferably 350 g/eq or less, even more preferably 250 g/eq or less, particularly preferably 200 g/eq or less, Particularly preferably 150 g/eq or less. If the epoxy equivalent of the polyepoxy compound (B) is too large, the crosslink density after curing may decrease, resulting in insufficient heat resistance, or it may be necessary to add a large amount of the polyepoxy compound (B) to increase the crosslink density. Therefore, the optical properties tend to be insufficient. Note that the lower limit of the epoxy equivalent (WPE) of the polyepoxy compound (B) is usually 50 g/eq or more. In the present invention, "epoxy equivalent (WPE)" is defined as "the mass of an epoxy resin containing 1 equivalent of epoxy group” and can be measured according to JIS K 7236.
• the blending amount of the epoxy compound (B) is preferably 0.1 to 15 parts by mass, more preferably 0.2 to 10 parts by mass, even more preferably is 0.3 to 5 parts by weight, particularly preferably 0.5 to 4.5 parts by weight, particularly preferably 0.7 to 4 parts by weight, most preferably 1 to 3.5 parts by weight. If the amount of the polyepoxy compound (B) is too large, the polyepoxy compound (B) that is not incorporated into the crosslinking will remain, and the optical properties and heat resistance will tend to be insufficient. On the other hand, if the amount is too small, the crosslinking density tends to be low, resulting in insufficient heat resistance, wet heat resistance, and adhesive strength.
• the present adhesive composition may contain a polyisocyanate compound (C) as a crosslinking agent from the viewpoint of heat and humidity resistance.
• a polyisocyanate compound (C) refers to a compound having at least two or more isocyanate groups in the molecule.
• polyisocyanate compound (C) examples include tolylene diisocyanate compounds such as 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, and xylylene diisocyanate compounds such as 1,3-xylylene diisocyanate.
• diphenylmethane compounds such as diphenylmethane-4,4-diisocyanate
• aromatic diisocyanate compounds such as naphthalene diisocyanate crosslinking agents such as 1,5-naphthalene diisocyanate
• isophorone diisocyanate 1,4-cyclohexane diisocyanate
• 4,4' -Alicyclic diisocyanate compounds such as dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, isopropylidene dicyclohexyl-4,4'-diisocyanate, 1,3-diisocyanatomethylcyclohexane, norbornane diisocyanate
• hexamethylene diisocyanate trimethylhexamethylene diisocyanate aliphatic diisocyanate compounds such as the above-mentioned aromatic diisocyanate compounds, alicyclic diisocyanate
• the polyisocyanate compound (C) may also be one in which the isocyanate moiety is blocked with phenol, lactam, or the like. These polyisocyanate compounds (C) may be used alone or in combination of two or more. Among these, from the viewpoint of optical properties and heat resistance, alicyclic diisocyanate compounds and aliphatic diisocyanate compounds are preferable, and aliphatic diisocyanate compounds are particularly preferable, and isocyanurates of hexamethylene diisocyanate are more preferable. preferable.
• the equivalent of the isocyanate group of the polyisocyanate compound (C) to the hydroxyl group of the polyester resin (A) is preferably 3 equivalents or less, more preferably 2 equivalents or less, still more preferably 1.5 equivalents or less, particularly preferably 1 equivalent.
• the amount below is particularly preferably 0.5 equivalent or less. If the amount is too large, the polyisocyanate compound (C) that is not incorporated into the crosslinking tends to remain, resulting in insufficient optical properties or a high urethane bond concentration, resulting in insufficient heat resistance.
• the content thereof is preferably 5 parts by mass or less, more preferably The amount is 4 parts by weight or less, more preferably 3 parts by weight or less, particularly preferably 2 parts by weight or less, particularly preferably 1.5 parts by weight or less, most preferably 1 part by weight or less. If the amount of the polyisocyanate compound added is too large, the polyisocyanate compound (C) that is not incorporated into the crosslinking will remain, resulting in insufficient optical properties or a decrease in heat resistance due to an increase in the urethane bond concentration. Tend.
• the present adhesive composition may contain a carbodiimide compound from the viewpoint of heat and humidity resistance.
• the number of carbodiimide groups in the molecule is usually 50 or less, and if there are too many carbodiimide groups, the molecular structure becomes too large, which tends to reduce compatibility and result in insufficient optical properties.
• a high molecular weight polycarbodiimide produced by subjecting a diisocyanate to a decarboxylation condensation reaction in the presence of a carbodiimidation catalyst may be used.
• Examples of such high molecular weight polycarbodiimides include those obtained by subjecting the following diisocyanates to a decarboxylation condensation reaction.
• Examples of such diisocyanates include 4,4'-diphenylmethane diisocyanate, 3,3'-dimethoxy-4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 4,4'- Diphenyl ether diisocyanate, 3,3'-dimethyl-4,4'-diphenyl ether diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, isophorone diisocyanate, 4, Examples include 4'-dicyclohexylmethane diisocyanate and tetramethylxylylene diisocyanate, and these may be used alone or in
• the content thereof is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, based on 100 parts by mass of the polyester resin (A). , more preferably 3 parts by weight or less, particularly preferably 2 parts by weight or less, particularly preferably 1 part by weight or less, and most preferably 0.5 parts by weight or less. If the amount of the carbodiimide compound added is too large, an excessive amount of the carbodiimide compound that is not incorporated into the crosslinking may remain, resulting in insufficient optical properties, or the polyester resin (A) and polyepoxy compound (B) may have insufficient optical properties. This tends to inhibit crosslinking with other materials, resulting in insufficient heat resistance.
• the present adhesive composition may contain a metal chelate compound as a crosslinking agent from the viewpoint of heat and humidity resistance.
• metal chelate compounds include metal alkoxides such as tetraethyl titanate, tetraethyl zirconate, and aluminum isopropionate, and aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium.
• metal chelate compounds include acetylacetone and acetoacetate of polyvalent metals, metal chelate compounds of ethylenediaminetetraacetic acid coordination compounds, acetic acid-ammonium complex salts, ammonium-carbonate complex salts, and the like. These metal chelate compounds may be used alone or in combination of two or more.
• the content thereof is preferably 5 parts by mass or less, more preferably 4 parts by mass, based on 100 parts by mass of the polyester resin (A).
• the amount is more preferably 3 parts by weight or less, particularly preferably 2 parts by weight or less, particularly preferably 1 part by weight or less, and most preferably 0.5 parts by weight or less. If the amount of the metal chelate compound added is too large, the metal chelate compound that is not incorporated into the crosslinking may remain, resulting in insufficient optical properties, or the relationship between the polyester resin (A) and the polyepoxy compound (B) may become insufficient. This tends to inhibit cross-linking of the resin, resulting in insufficient heat resistance.
• the present adhesive composition may contain a tackifier resin in order to improve adhesive properties.
• the tackifier resin is not particularly limited, and conventionally known ones can be used.
• the tackifying resin include hydrocarbon resins, terpene resins, phenol resins, rosin resins, xylene resins, epoxy resins, polyamide resins, ketone resins, and elastomer resins. These may be used alone or in combination of two or more. Among these, hydrocarbon-based tackifying resins and terpene-based resins are preferred from the viewpoint of their compatibility with the polyester resin (A) and excellent heat resistance.
• hydrocarbon tackifying resin examples include aliphatic hydrocarbon resins, aromatic hydrocarbon resins, aliphatic cyclic hydrocarbon resins, aliphatic/aromatic petroleum resins (styrene-olefin copolymers, etc.), aliphatic/alicyclic petroleum resins, hydrogenated hydrocarbon resins, coumaron-based resins, coumaron-indene-based resins, and various other hydrocarbon-based resins.
• terpene resin examples include terpene resin, terpene phenol resin, aromatic modified terpene resin, etc. Specifically, ⁇ -pinene polymer, ⁇ -pinene polymer, dipentene polymer, etc. Phenol-modified, aromatic-modified, hydrogenated-modified, and hydrocarbon-modified terpene resins can be used. Further, terpene phenol resin is preferred because it has excellent compatibility with the polyester resin (A) and excellent heat resistance.
• phenolic resin for example, condensates of various phenols such as phenol, m-cresol, 3,5-xylenol, p-alkylphenol, and resorcinol, and formaldehyde can be used. Furthermore, resols obtained by addition reaction of the above-mentioned phenols and formaldehyde under an alkali catalyst, novolacs obtained by a condensation reaction of the above-mentioned phenols and formaldehyde under an acid catalyst, unmodified or modified rosin, and these. A rosin-modified phenol resin obtained by adding phenol to a rosin such as a derivative thereof under an acid catalyst and thermally polymerizing it can be used.
• rosin resin examples include rosin resin, polymerized rosin resin, hydrogenated rosin resin, rosin ester resin, hydrogenated rosin ester resin, rosin phenol resin, and polymerized rosin ester.
• gum rosin Unmodified rosins (raw rosins) such as wood rosin and tall oil rosin, modified rosins obtained by hydrogenating, disproportionating, polymerizing, or other chemical modifications of these rosins, and derivatives thereof can be used.
• the tackifying resin preferably has an acid value of 30 mgKOH/g or less, particularly 15 mgKOH/g or less, further 10 mgKOH/g or less, particularly 6 mgKOH/g or less, and most preferably 3 mgKOH/g from the viewpoint of heat and humidity resistance. /g is preferable. When multiple types of tackifying resins are used together, it is preferable that the average thereof is within the above range.
• the softening point of the tackifying resin is preferably 60 to 170°C, particularly 80 to 160°C, and more preferably 100 to 150°C. It is preferable that the softening point is within the above range because tackiness and adhesive strength can be improved.
• the tackifier resin is preferably derived from plants in order to preserve the global environment.
• plant-derived tackifying resins include terpene resins and rosin resins.
• the content thereof is preferably 50 parts by mass or less, more preferably 30 parts by mass, based on 100 parts by mass of the polyester resin (A).
• the amount is more preferably 15 parts by weight or less, particularly preferably 10 parts by weight or less, particularly preferably 5 parts by weight or less. If the content is within the above range, tackiness and adhesive strength can be improved, and if the content is too large, the glass transition temperature of the adhesive will increase, resulting in poor tackiness, adhesive strength, and molding stability. It tends to be inadequate.
• the adhesive composition may contain a catalyst in order to allow crosslinking (curing) by the polyepoxy compound (B) to proceed at a low temperature.
• catalysts examples include 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, and the like.
• imidazole-based compounds triethylamine, triethylenediamine, N'-methyl-N-(2-dimethylaminoethyl)piperazine, 1,8-diazabicyclo(5,4,0)-undecene-7, 1,5-diazabicyclo(4 , 3,0)-nonene-5,6-dibutylamino-1,8-diazabicyclo(5,4,0)-undecene-7; , compounds made into amine salts with quaternized tetraphenylborate salts, etc.; cationic catalysts such as triallylsulfonium hexafluoroantimonate and diallyliodonium hexafluoroantimonate; triphenylphosphine, and the like.
• the amount thereof is preferably 0.01 to 1 part by mass based on 100 parts by mass of the polyester resin (A).
• the content is within the above range, an adhesive with a high degree of crosslinking can be obtained by reacting the polyester resin (A) and the polyepoxy compound (B) at a low temperature and in a short time.
• the present adhesive composition contains an antioxidant (D) from the viewpoint of increasing the heat resistance of the polyester resin (A).
• antioxidant (D) examples include hindered phenol antioxidants, amine antioxidants, sulfur antioxidants, phosphoric acid antioxidants, and the like. Among these, at least one selected from hindered phenol-based antioxidants, amine-based antioxidants, and phosphoric acid-based antioxidants is preferable, and antioxidant (D) consisting of hindered phenol-based compounds is particularly preferable.
• the hindered phenolic antioxidant is, for example, a hinderer in which a group with a large steric hindrance such as a tertiary butyl group is bonded to at least one of the adjacent carbon atoms of the carbon atom on the aromatic ring to which the hydroxyl group of phenol is bonded. Examples include antioxidants having a dophenol structure.
• the amount thereof is preferably 0.001 to 5 parts by mass, more preferably 0.001 to 5 parts by mass, based on 100 parts by mass of the polyester resin (A). is 0.01 to 3 parts by weight, more preferably 0.02 to 2 parts by weight, particularly preferably 0.03 to 1 part by weight, particularly preferably 0.05 to 0.5 parts by weight. If the content is too small, the heat resistance tends to be insufficient, and if the content is too large, the optical properties tend to be insufficient.
• This adhesive composition contains the above-mentioned polyester resin (A), polyepoxy compound (B), polyisocyanate compound (C), carbodiimide compound, metal chelate compound, catalyst, tackifier resin, and antioxidant.
• agent (D) other ingredients may be used as long as they do not impair the effects of the present invention, such as plasticizers, ultraviolet absorbers, stabilizers, antistatic agents, silane coupling agents, fluxes, flame retardants, and dispersants.
• Powder and particulate additives such as emulsifiers, emulsifiers, antifoaming agents, leveling agents, ion trapping agents, inorganic or organic fillers, metal powders, pigments, etc. can be blended. These can be used alone or in combination of two or more. Further, the present adhesive composition may contain a small amount of impurities contained in the manufacturing raw materials of the constituent components of the present adhesive composition.
• the content thereof is preferably 70% by mass or less, more preferably 0.001 to 50% by mass, particularly preferably 0. 0.005 to 30% by weight, more preferably 0.01 to 10% by weight.
• the content of the polyester resin (A) in the present pressure-sensitive adhesive composition is usually 70% by mass or more, more preferably 80-99.5% by mass, particularly preferably 85-99% by mass, still more preferably 90-98% by mass. 5% by weight, particularly preferably 95-98% by weight.
• Such an adhesive composition of the present invention can be prepared, for example, by preparing the polyester resin (A), the polyepoxy compound (B), and any necessary optional components, and mixing and dispersing them during the production of the polyester resin (A). Alternatively, it can be obtained by adding it to a solution of the polyester resin (A) dissolved in an organic solvent and dispersing it using a mixing roller or the like.
• a solvent may be added to the present adhesive composition in order to appropriately adjust the viscosity of the present adhesive composition and to facilitate handling when forming a coating film.
• the solvent is used to ensure ease of handling and workability in molding the pressure-sensitive adhesive composition, and there is no particular restriction on the amount used.
• the solvent examples include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate; ethers such as ethylene glycol monomethyl ether; N,N-dimethylformamide, N,N-dimethylacetamide. Alcohols such as methanol and ethanol; Alkanes such as hexane and cyclohexane; Aromatics such as toluene and xylene.
• ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone
• esters such as ethyl acetate
• ethers such as ethylene glycol monomethyl ether
• N,N-dimethylformamide N,N-dimethylacetamide.
• Alcohols such as methanol and ethanol
• Alkanes such as hexane and
• ketone solvents and ester solvents are preferred from the viewpoint of VOC emission regulation, particularly methyl ethyl ketone, cyclohexanone, and ethyl acetate, and even more preferred are methyl ethyl ketone and ethyl acetate because of their low boiling point and excellent drying efficiency.
• the above-mentioned solvents may be used alone or in a mixture of two or more in any combination and ratio.
• the polyester adhesive according to one embodiment of the present invention (hereinafter sometimes referred to as “the present adhesive") is obtained by crosslinking the present adhesive composition, and has excellent adhesive strength, heat resistance, and moist heat resistance. Also, it has excellent optical properties.
• Crosslinking in the present invention means intentionally crosslinking the pressure-sensitive adhesive composition by heat and/or light, and the degree of crosslinking can be controlled depending on the desired physical properties and use.
• the degree of crosslinking can be confirmed by the gel fraction of the pressure-sensitive adhesive, and preferably the gel fraction is 20 to 100%, more preferably 30 to 98%, even more preferably 40 to 95%, particularly preferably 50 to 100%. 90%, particularly preferably 55-85%, most preferably 60-80%. If the gel fraction is too low, heat resistance, holding power, adhesive strength, and wet heat durability tend to be insufficient, and if it is too high, tackiness and adhesive strength tend to be insufficient. Note that the gel fraction serves as a measure of the degree of crosslinking, and is calculated, for example, by the following method.
• an adhesive sheet (without a release sheet) consisting of a polymer sheet (such as PET film) as a base material and an adhesive layer formed thereon is wrapped in a 200-mesh SUS wire mesh and placed in toluene.
• the wire gauze is immersed at 23° C. for 24 hours, and the mass percentage of the undissolved adhesive component remaining in the wire gauze after immersion with respect to the mass of the adhesive component before immersion is defined as the gel fraction.
• the mass of the base material should be subtracted.
• a pressure-sensitive adhesive layer is then formed from the present pressure-sensitive adhesive, and a pressure-sensitive adhesive sheet having such a pressure-sensitive adhesive layer can be obtained.
• sheet includes “film” and “tape.”
• the pressure-sensitive adhesive sheet according to one embodiment of the present invention (hereinafter sometimes referred to as "the present pressure-sensitive adhesive sheet”) can be produced, for example, as follows.
• Such a pressure-sensitive adhesive sheet can be produced according to a known general pressure-sensitive adhesive sheet production method.
• the present pressure-sensitive adhesive composition is coated on a base material, dried, and crosslinked, and then By pasting a release sheet on the side of the adhesive layer and curing if necessary, the present adhesive sheet having an adhesive layer containing an adhesive on the base material can be obtained.
• Such an adhesive layer is preferably formed on one or both sides of the base material.
• the adhesive composition of the present invention can be coated on a release sheet, dried, and crosslinked, a base material is attached to the side of the adhesive layer opposite to the release sheet, and the adhesive composition is cured if necessary. can get.
• a base material-less double-sided pressure-sensitive adhesive sheet can be produced by forming a pressure-sensitive adhesive layer on a release sheet and laminating the release sheet to the opposite side of the pressure-sensitive adhesive layer.
• the release sheet is peeled off from the pressure-sensitive adhesive layer and the pressure-sensitive adhesive layer and the adherend are bonded together.
• the base material examples include polyester resins such as polyethylene naphthalate, polyethylene terephthalate, polybutylene terephthalate, and polyethylene terephthalate/isophthalate copolymers; polyolefin resins such as polyethylene, polypropylene, and polymethylpentene; polyvinyl fluoride; Polyfluorinated ethylene resins such as polyvinylidene fluoride and polyethylene fluoride; polyamides such as nylon 6 and nylon 6,6; polyvinyl chloride, polyvinyl chloride/vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl Vinyl polymers such as alcohol copolymers, polyvinyl alcohol, and vinylon; Cellulose resins such as cellulose triacetate and cellophane; Acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, and polybutyl acrylate.
• polyester resins
• Fluorine resin Polystyrene; Polycarbonate; Acrylonitrile-butadiene-styrene copolymer; Acrylonitrile-styrene-acrylic acid ester copolymer; Polyarylate; Polyimide; Cycloolefin polymer: Urethane acrylate resin, etc.
• Examples include sheets made of at least one synthetic resin; metal foils of aluminum, copper, and iron; papers such as high-quality paper and glassine paper; and woven and nonwoven fabrics made of glass fibers, natural fibers, synthetic fibers, and the like. These base materials can be used as a single layer body or as a multilayer body in which two or more types are laminated.
• base materials made of polyethylene terephthalate, acrylic resin, polycarbonate, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene-acrylic acid ester copolymer, polyimide, and urethane acrylate resin are particularly preferred, and particularly heat-resistant Acrylic resins, fluorine resins, and urethane acrylate resins are preferred because they have excellent properties and moldability.
• a foam base material for example, a foam sheet made of a synthetic resin foam such as polyurethane foam, polyethylene foam, or polyacrylate foam, can be used.
• polyurethane foam and polyacrylate foam are preferred because they have excellent balance of heat resistance, followability to adherends, and adhesive strength.
• the thickness of the base material is, for example, preferably 1 to 1000 ⁇ m, particularly preferably 10 to 800 ⁇ m, even more preferably 25 to 600 ⁇ m, particularly preferably 50 to 400 ⁇ m.
• release sheet for example, a sheet made of the various synthetic resins exemplified as the base material, paper, cloth, nonwoven fabric, etc. that has been subjected to release treatment can be used.
• release sheet it is preferable to use a silicone release sheet.
• a gravure roll coater for example, a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, a spray coater, a comma coater, etc. may be used.
• the conditions for the curing treatment include a temperature of 0 to 80°C and a duration of usually 1 to 30 days, specifically, for example, 23°C for 1 to 20 days, preferably 23°C for 2 to 14 days, particularly Preferably, the treatment is carried out at 23°C for 3 to 7 days, and at 40°C for 1 to 10 days. If the temperature of the curing treatment is higher than 80° C., the optical properties of the pressure-sensitive adhesive sheet tend to become insufficient due to thermal history, and production efficiency tends to decrease.
• the drying temperature is preferably 60 to 140°C, particularly preferably 80 to 120°C, and the drying time is preferably 0.5 to 30 minutes, particularly preferably 1 to 5 minutes.
• the thickness of the adhesive layer of the present adhesive sheet and the base material-less double-sided adhesive sheet is preferably 1 to 500 ⁇ m, particularly preferably 3 to 200 ⁇ m, even more preferably 5 to 100 ⁇ m, particularly preferably 10 to 50 ⁇ m. be. If the thickness of the adhesive layer is too thin, the adhesive strength tends to decrease, while if it is too thick, the uniformity of the coating film will decrease, resulting in poor appearance, or bubbles will form in the coating film, resulting in insufficient optical properties. Tend.
• the thickness of the adhesive layer is determined by subtracting the measured thickness of the constituent members other than the adhesive layer from the measured thickness of the entire adhesive sheet using "ID-C112B" manufactured by Mitutoyo. .
• the present pressure-sensitive adhesive sheet preferably has a haze of 3% or less, more preferably 2.5% or less, particularly preferably 2% or less. When the haze is less than or equal to the above value, optical properties tend to be excellent.
• the above-mentioned Hayes applied the present adhesive sheet to a polyethylene terephthalate (PET) film and alkali-free glass to prepare a test piece consisting of a PET film/adhesive layer/alkali-free glass plate. It can be determined by measuring using HAZE MATER NDH2000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.) in an environment of °C and 50% RH.
• the molding stability of the adhesive sheet can be confirmed by the elongation of the adhesive sheet.
• Such elongation is preferably 100 to 2000%, more preferably 200 to 1500%, even more preferably 300 to 1400%, particularly preferably 400 to 1300%, particularly preferably 500 to 1200%. If the elongation is too low, the adhesive layer will not be able to follow the molded product, and the molding stability will tend to be insufficient; if the elongation is too high, the holding power and wet heat durability will tend to be insufficient.
• the elongation can be determined by subjecting the adhesive sheet to a tensile test in accordance with JIS K 7127.
• a substrate-less adhesive sheet with an adhesive layer thickness of 200 ⁇ m is cut out to a size of 15 mm in width and 75 mm in length, and the release film on both sides is peeled off to create a test piece.
• Autograph AG-X manufactured by Shimadzu Corporation
• such a pressure-sensitive adhesive sheet may be protected by providing a release sheet on the outside of the pressure-sensitive adhesive layer, if necessary.
• the pressure-sensitive adhesive layer is formed on one side of the base material, by applying a peeling treatment to the surface of the base material opposite to the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer can be layered using the peel-treated surface. It is also possible to protect
• This adhesive can be used for laminating various parts, and has excellent adhesive strength, heat resistance, heat and humidity resistance, and optical properties, so it is especially suitable for single-sided or double-sided adhesive sheets used for laminating decorative films and molding. , used as a film for electronic components.
• a decorative film according to an embodiment of the present invention includes the present adhesive sheet.
• a decorative film according to another embodiment of the present invention contains a polyester resin (A) and a polyepoxy compound (B).
• a decorative film comprising an adhesive layer formed from a polyester adhesive composition The polyester resin (A) satisfies all of the following (1) to (4).
• the polyester resin (A) has a structural unit derived from a polyhydric carboxylic acid (a) and a structural unit derived from a polyhydric alcohol (b).
• the content of the structural unit derived from the cyclic structure-containing polyvalent carboxylic acid (a1) is 30 mol% or more with respect to 100 mol% of the structural unit derived from the polyvalent carboxylic acid (a).
• the structural unit derived from the polyhydric alcohol (b) contains a structural unit derived from the aliphatic polyhydric alcohol (b1).
• the acid value of the polyester resin (A) is 1.5 to 30 mgKOH/g.
• the polyester resin (A) and polyepoxy compound (B) used in the present decorative film 2 are as explained in the above-mentioned present pressure-sensitive adhesive composition.
• the polyester adhesive composition used in the present decorative film 2 includes the polyisocyanate compound (C), the carbodiimide compound, the metal chelate compound, the tackifying resin, which were explained in the above-mentioned present adhesive composition, An antioxidant (D) and additives may be included.
• the main decorative films 1 and 2 (hereinafter sometimes simply referred to as “main decorative films”) will be explained.
• the above-mentioned decorative film imparts design to a resin layer or metal formed from a thermoplastic resin, and the decorative film includes at least a base material and an adhesive layer.
• Examples of the base material in the present decorative film include a resin layer formed from a thermoplastic resin.
• examples of the thermoplastic resin include polyethylene terephthalate, acrylic resin, polycarbonate, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene-acrylic acid ester copolymer, polyimide acrylic resin, fluorine resin, and urethane acrylate resin.
• resin may be used alone or in combination of two or more.
• acrylic resins, fluororesins, and urethane acrylate resins are preferred because they have excellent spreadability, bendability, and shape followability during molding.
• the base material in this decorative film may be colorless or colored.
• a known coloring agent may be added to the resin.
• the base material in this decorative film may be transparent, translucent, or opaque.
• the thickness of the base material is preferably 1 to 1000 ⁇ m, particularly preferably 10 to 800 ⁇ m, even more preferably 25 to 600 ⁇ m, particularly preferably 50 to 400 ⁇ m. If the thickness of the base material is within the above range, processability, shape followability, and handling properties tend to be good when producing a decorative molded product.
• the present decorative film may have a decorative layer on the base material and/or between the base material and the adhesive layer.
• the decorative layer is a layer provided to impart design to the decorative film, and is a pattern layer that expresses patterns, letters, patterned pictures, and the like.
• the decorative layer can be provided, for example, by known printing methods such as inkjet printing, screen printing, and gravure printing, or by vapor deposition of metals or metal oxides such as aluminum, chromium, nickel, gold, tin, indium, and copper. .
• the base material in this decorative film is located at the outermost layer of the decorative molded product after the molded product described below is decorated with this decorative film, and serves as a protective layer for the decorative molded product.
• a decorative molded article with excellent durability such as abrasion resistance, chemical resistance, and weather resistance can be obtained.
• a decorated molded article according to an embodiment of the present invention (hereinafter sometimes referred to as "this decorative molded article") is produced by a vacuum forming method, a pressure forming method (preferably a vacuum forming method), etc. It is formed by laminating the main decorative film on top. That is, the present decorative molded product is obtained by laminating the present decorative film on the molded product, and more specifically, the molded product is laminated with an adhesive layer, an optional decorative layer, and a base material. are laminated.
• the molded body examples include a resin layer formed from a thermoplastic resin.
• the thermoplastic resin include polyethylene terephthalate, acrylic resin, polycarbonate, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene-acrylic ester copolymer, and the like.
• the film for electronic components according to one embodiment of the present invention usually consists of the present pressure-sensitive adhesive sheet and a base material.
• the film for electronic components is used in the manufacturing process of electronic components, for example, in the semiconductor manufacturing process, for masking, fixing, protecting, and transporting electronic components.
• Examples of the base material in the film for electronic components include polyethylene terephthalate resin, polyimide resin, polyphenylene sulfide resin, polyethylene naphthalate resin, polyether ether ketone resin, polyether sulfone resin, polycyclohexane dimethylene terephthalate resin, and polyethylene terephthalate resin.
• Examples include etherimide resin, aromatic polyamide resin, liquid crystal polymer resin, and the like. These may be used alone or in combination of two or more.
• polyethylene terephthalate resin, polyimide resin, and polyphenylene sulfide are preferable because they have excellent heat resistance and processability.
• the thickness of the base material is preferably 1 to 1000 ⁇ m, particularly preferably 3 to 500 ⁇ m, even more preferably 5 to 300 ⁇ m, particularly preferably 10 to 100 ⁇ m.
• the film tends to have good heat resistance and processability as a film for electromagnetic members.
• polyester resin (A-1) In a reaction vessel equipped with a thermometer, stirrer, rectification column, and nitrogen inlet tube, 124 parts of isophthalic acid (IPA), 104.3 parts of terephthalic acid (TPA), and trimellitic anhydride were added as polycarboxylic acids (a).
• TMAn 4 parts of TMAn, 39 parts of ethylene glycol (EG) as a polyhydric alcohol, 664.2 parts of dimer diol "Pripol 2033" (P2033) (manufactured by Croda), 2-methyl-1,3 propanediol (2MPG) ), 0.1 part of tetrabutyl titanate as a catalyst was charged, the temperature was raised over 2.5 hours until the internal temperature reached 260°C, and the esterification reaction was carried out at 260°C for 1.5 hours. . Next, 0.1 part of tetrabutyl titanate was added as a catalyst, the pressure inside the system was reduced to 2.5 hPa, and a polymerization reaction was carried out over 2 hours. Further, the temperature was lowered until the internal temperature reached 235°C, 8 parts of trimellitic acid anhydride (TMAn) was charged, and a depolymerization reaction was carried out over 1 hour to obtain a polyester resin (A-1).
• EG ethylene glycol
• Polyester resins (A-2 to A-5, A'-2) were obtained in the same manner as A-1 except that the resin composition was changed as shown in Table 1.
• polyester resin (A'-1) In a reaction vessel equipped with a thermometer, a stirrer, a rectification column, and a nitrogen inlet tube, 225.5 parts of terephthalic acid (TPA) was added as a polyhydric carboxylic acid (a), and ethylene glycol (EG) was added as a polyhydric alcohol (b). ), 126.4 parts of dimer diol "Pripol 2033" (P2033) (manufactured by Croda), 1.8 parts of trimethylolpropane (TMP), and 0.1 part of tetrabutyl titanate as a catalyst.
• TPA terephthalic acid
• P2033 dimer diol "Pripol 2033"
• TMP trimethylolpropane
• TMP trimethylolpropane
• PET resin sheet with one-sided release film> After applying each of the obtained polyester resins (A) and (A') to a polyethylene terephthalate (PET) film (manufactured by Toray Industries, Ltd., Lumirror T60, thickness 38 ⁇ m) so that the thickness after drying is about 25 ⁇ m, It was dried at 100° C. for 3 minutes to form an adhesive layer. After that, a release-treated PET film (release film) (manufactured by Mitsui Chemicals Tohcello, SP-PET-01-BU, thickness 38 ⁇ m) was attached to the adhesive layer to protect its surface. A PET resin sheet with a release film was obtained.
• PET polyethylene terephthalate
• a polyester pressure-sensitive adhesive composition was produced as described below using each of the polyester resins (A) and (A') obtained above and a crosslinking agent.
• Example 1 The polyester resin (A-1) obtained above was diluted with ethyl acetate to a solid concentration of 50%, and a polyepoxy compound was added to this polyester resin (A-1) solution (100 parts as solid content).
• a polyester pressure-sensitive adhesive composition was obtained by adding 1.3 parts of (B-1) (solid content) and stirring and mixing.
• Examples 2 to 5 Comparative Examples 1 to 3
• a polyester pressure-sensitive adhesive composition was obtained in the same manner as in Example 1, except that the components shown in Table 3 were blended.
• PET adhesive sheet with one-sided release film Each of the obtained polyester adhesive compositions was applied to a polyethylene terephthalate (PET) film (manufactured by Toray Industries, Inc., Lumirror T60, thickness 38 ⁇ m) so that the thickness after drying was approximately 25 ⁇ m, and then heated at 100° C. for 3 minutes. It was dried to form an adhesive layer. After that, a release-treated PET film (release film) (manufactured by Mitsui Chemicals Tohcello, SP-PET-01-BU, thickness 38 ⁇ m) was attached to the adhesive layer to protect its surface, and the temperature It was cured for 4 days in an atmosphere of 40°C to obtain a PET adhesive sheet with a release film on one side.
• PET polyethylene terephthalate
• a SUS-BA plate was prepared as an adherend.
• the PET adhesive sheet with a single-sided release film obtained above was cut into 25 mm x 200 mm in an environment of 23°C and 50% RH, the release film was peeled off, and the adhesive layer side was placed on a SUS-BA plate using a 2 kg roller. It was pasted under pressure by moving back and forth twice. Then, after standing for 30 minutes under the same atmosphere, the 180 degree peel strength (N/25 mm) was measured using an Autograph (manufactured by Shimadzu Corporation, Autograph AG-X 50N) at a peeling speed of 300 mm/min. .
• ABS board was prepared as an adherend.
• the PET adhesive sheet with a single-sided release film obtained above was cut into 25 mm x 200 mm in an environment of 23°C and 50% RH, the release film was peeled off, and the adhesive layer side was placed on a SUS-BA plate using a 2 kg roller. It was pasted under pressure by moving back and forth twice. Then, after standing for 30 minutes under the same atmosphere, the 180 degree peel strength (N/25 mm) was measured using an Autograph (manufactured by Shimadzu Corporation, Autograph AG-X 50N) at a peeling speed of 300 mm/min. .
• Optical properties (H1: resin sheet haze)
• the PET resin sheet with a single-sided release film obtained above was cut into a size of 30 mm x 50 mm in an environment of 23°C and 50% RH, the release film was peeled off, and the adhesive layer side was cut into a size of 30 mm x 50 mm.
• a 2 kg roller was applied to glass (Eagle The haze (H1) of the test piece was measured in an environment of 23° C. and 50% RH using HAZE MATER NDH2000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.).
• Optical properties (H2: adhesive sheet haze)
• the PET adhesive sheet with a single-sided release film obtained above was cut into a size of 30 mm x 50 mm in an environment of 23°C and 50% RH, the release film was peeled off, and the adhesive layer side was cut into a size of 30 mm x 50 mm.
• a 2 kg roller was applied to glass (Eagle The haze (H2) of the test piece was measured in an environment of 23° C. and 50% RH using HAZE MATER NDH2000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.).
• PI adhesive sheet with one-sided release film Each of the obtained polyester pressure-sensitive adhesive compositions was applied to a polyimide (PI) film (manufactured by DuPont-Toray, Kapton 200H, thickness 50 ⁇ m) so that the thickness after drying was approximately 25 ⁇ m, and then heated at 100°C for 30 minutes. It was dried for a minute to form an adhesive layer. After that, a release-treated PET film (release film) (manufactured by Mitsui Chemicals Tohcello, SP-PET-01-BU, thickness 38 ⁇ m) was attached to the adhesive layer to protect its surface, and the temperature After curing for 4 days in an atmosphere of 40° C., a PI adhesive sheet with a release film on one side was obtained.
• PI polyimide
• the obtained PI adhesive sheet with a single-sided release film was evaluated as follows. The evaluation results are shown in Table 3 below.
• the release film of the PI adhesive sheet with a single-sided release film obtained above was peeled off, and it was pasted on copper foil in an environment of 23°C and 50% RH, and cut into a size of 2.0 x 2.0 cm. Thereafter, heat treatment was performed in an environment of 130° C. for 1 hour to prepare a test piece having a configuration of copper foil/adhesive layer/PI.
• the heat resistance of the test piece was measured by floating it in a solder bath at a predetermined temperature (300° C., 320° C.) for 60 seconds with the PI film side facing up. (Evaluation criteria) ⁇ (excellent)...No change in appearance ⁇ (poor)...There are changes in appearance such as lifting and peeling
• a SUS-BA plate was prepared as an adherend.
• the PET adhesive sheet with a single-sided release film obtained above was cut into 25 mm x 200 mm in an environment of 23°C and 50% RH, the release film was peeled off, and the adhesive layer side was placed on a SUS-BA plate using a 2 kg roller. It was pasted under pressure by moving back and forth twice. Then, after leaving it for 500 hours in an environment of 85°C and 85% RH, and for 1 hour in an environment of 23°C and 50% RH, an Autograph (manufactured by Shimadzu Corporation, Autograph AG-X 50N) was used. The 180 degree peel strength (N/25 mm) was measured using a peel speed of 300 mm/min.
• the polyester adhesive compositions and adhesive layers of the adhesive sheets of Examples 1 to 5 have excellent adhesive strength, heat resistance, and moist heat resistance, and also have excellent optical properties. there were.
• the adhesive compositions and adhesive layers of the adhesive sheets of Comparative Examples 1 to 3 have excellent optical properties, they are inferior in at least one of adhesive strength, heat resistance, and heat-and-moisture resistance. It did not satisfy the purpose.
• the polyester pressure-sensitive adhesive composition of the present invention has excellent adhesive strength, heat resistance, heat-and-moisture resistance, and optical properties when used as a pressure-sensitive adhesive. It is effective as an adhesive used in films for parts.

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• 2023
  • 2023-03-22 EP EP23774920.5A patent/EP4497797A4/en active Pending
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