WO2023017835A1 - ポリイソシアネート組成物、硬化膜、粘着性樹脂組成物、粘着性樹脂シート、及び積層フィルム - Google Patents

ポリイソシアネート組成物、硬化膜、粘着性樹脂組成物、粘着性樹脂シート、及び積層フィルム Download PDF

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WO2023017835A1
WO2023017835A1 PCT/JP2022/030544 JP2022030544W WO2023017835A1 WO 2023017835 A1 WO2023017835 A1 WO 2023017835A1 JP 2022030544 W JP2022030544 W JP 2022030544W WO 2023017835 A1 WO2023017835 A1 WO 2023017835A1
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mass
polyisocyanate composition
less
adhesive resin
parts
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PCT/JP2022/030544
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English (en)
French (fr)
Japanese (ja)
Inventor
昌嗣 東
麗 武井
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旭化成株式会社
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Priority to KR1020247003829A priority Critical patent/KR20240028493A/ko
Priority to CN202280055540.2A priority patent/CN117794973A/zh
Priority to JP2023541457A priority patent/JPWO2023017835A1/ja
Publication of WO2023017835A1 publication Critical patent/WO2023017835A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • 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
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners

Definitions

  • the present invention relates to polyisocyanate compositions, cured films, adhesive resin compositions, adhesive resin sheets, and laminated films.
  • plastic films and adhesives have been used in various fields due to their wide range of functions. Under such circumstances, applications are increasing not only for flat parts, but also for applications such as curved parts and parts with bending motion, which were rarely used before. For example, there are flexible displays, foldable displays, and lamination of automobile members, etc., and the demand has increased rapidly in recent years. Along with this, there is a demand for highly flexible films and pressure-sensitive adhesives that are tough and have good conformability, stretchability and bending resistance to curved surfaces and bends. For optical applications, high transparency, specifically haze value of 3.0% or less is also required at the same time.
  • an extensible polyurethane paint prepolymer comprising reacting an aliphatic diisocyanate or an alicyclic diisocyanate with a polycaprolactone diol and/or triol having a number average molecular weight of 500 or more and 1500 or less is disclosed.
  • Patent Document 2 a prepolymer obtained by reacting an aliphatic diisocyanate or an alicyclic diisocyanate with a polytetramethylene glycol having a number average molecular weight of 700 or more and 1500 or less, an aliphatic diisocyanate or an alicyclic diisocyanate and a number and a prepolymer obtained by reacting a polycaprolactone polyol having an average molecular weight of 500 or more and 1500 or less.
  • the present invention has been made in view of the above circumstances, and the cured film obtained by curing the polyisocyanate composition alone has good flexibility and transparency, and has excellent elongation and tensile breaking stress.
  • a polyisocyanate composition from which a film, a pressure-sensitive adhesive resin composition and a pressure-sensitive adhesive resin sheet having excellent adhesive strength, curability and transparency are obtained.
  • the present invention also provides a laminated film comprising the adhesive resin sheet.
  • the present invention includes the following aspects. (1) at least one diisocyanate selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates; at least one polyester polyol selected from the group consisting of a bifunctional polyester polyol (A) having a number average molecular weight Mn of 500 or more and a trifunctional or higher polyester polyol (B) having a number average molecular weight Mn of 500 or more; A polyisocyanate composition derived from The molar ratio of the isocyanate groups of the diisocyanate to the hydroxyl groups of the polyester polyol is 1.5 or more and 30.0 or less, A polyisocyanate composition, wherein the weight average molecular weight of the polyisocyanate composition is 1400 or more and 800000 or less.
  • the content of the polyester polyol (A) is 0.1 parts by mass or more and 900 parts by mass or less with respect to 100 parts by mass of the diisocyanate;
  • a cured film having a thickness of 40 ⁇ m formed by coating on glass and storing it for 168 hours in an environment of 23° C. and 65% humidity has a Konig hardness of 60 times or less in an environment of 23° C.
  • the haze value measured with a haze meter is 3.0% or less when the cured film having a thickness of 40 ⁇ m is attached on a glass having a haze value of 0.1%.
  • the elongation in a tensile test measured at a speed of 20 mm / min is 140% or more
  • the stress at elongation of 140% is 25.0 MPa or less
  • the cured film according to (8), wherein the content of the polyisocyanate composition is 0.01 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the polyol.
  • An adhesive resin composition comprising the polyisocyanate composition according to any one of (1) to (7) and a crosslinkable functional group-containing polymer having a glass transition temperature of 0.0° C. or less. .
  • the crosslinkable functional group-containing polymer comprises a polymerizable (meth)acrylic monomer having a crosslinkable functional group and a (meth)acrylic acid ester monomer having 1 or more and 18 or less carbon atoms at the end of the ester group.
  • Tg glass transition temperature
  • the crosslinkable functional group-containing polymer has a weight average molecular weight of 1.0 ⁇ 10 5 or more and 5.0 ⁇ 10 6 or less.
  • the crosslinkable functional group is one or more selected from the group consisting of a hydroxyl group, an epoxy group, an oxetane group, a carboxy group, a vinyl group, and an amino group.
  • the film substrate is a polyester-based resin, an acetate-based resin, a polyethersulfone-based resin, a polycarbonate-based resin, a polyamide-based resin, a polyimide-based resin, a polyolefin-based resin, a (meth)acrylic-based resin, or a polyvinyl chloride-based resin.
  • (23) The laminated film according to (21) or (22), which is used for optical purposes.
  • the cured film obtained by curing the polyisocyanate composition alone has good flexibility and transparency, and has excellent elongation and tensile breaking stress. It is possible to provide a polyisocyanate composition from which a pressure-sensitive adhesive resin composition and a pressure-sensitive adhesive resin sheet having excellent strength, curability and transparency can be obtained. Further, the present invention can provide a laminated film comprising the adhesive resin sheet.
  • polyol means a compound having two or more hydroxy groups (--OH) in one molecule.
  • polyisocyanate means a reaction product in which a plurality of monomeric compounds having two or more isocyanate groups (--NCO) are combined.
  • (meth)acryl includes methacryl and acryl
  • (meth)acrylate includes methacrylate and acrylate.
  • the polyisocyanate composition of the present embodiment comprises a diisocyanate, a bifunctional polyester polyol (A) having a number average molecular weight of 500 or more (hereinafter simply referred to as “polyester polyol (A)”), and a number average molecular weight Mn of 500 or more. and at least one polyester polyol selected from the group consisting of trifunctional or higher polyester polyols (B) (hereinafter simply referred to as “polyester polyols (B)").
  • the polyisocyanate composition of the present embodiment is a reaction product of a diisocyanate and one or more of the above polyester polyols, and contains a polyisocyanate modified with one or more of the above polyester polyols.
  • Diisocyanate is at least one selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates.
  • the molar ratio of the isocyanate groups of the diisocyanate to the hydroxyl groups of the polyester polyol (A) and/or the polyester polyol (B) is 1.5 or more and 30.0.
  • 2.0 or more and 25.0 or less are preferable, 2.1 or more and 23.0 or less are more preferable, 2.2 or more and 20.0 or less are more preferable, and 2.3 or more and 20.0 or less are more preferable.
  • the isocyanate group/hydroxyl molar ratio is, for example, the molar amount of hydroxyl groups in the polyester polyol (A) and/or polyester polyol (B) used in the production of the polyisocyanate composition, and the molar amount of the isocyanate groups in the diisocyanate. can be calculated.
  • the weight average molecular weight of the polyisocyanate composition of the present embodiment is 1400 or more, preferably 1500 or more, more preferably 2000 or more, further preferably 2500 or more, and 3000 or more. is particularly preferred. Although the upper limit of the weight average molecular weight of the polyisocyanate composition of the present embodiment is not particularly limited, it can be 800,000. The weight average molecular weight of the polyisocyanate composition of the present embodiment can be measured, for example, by gel permeation chromatography (hereinafter sometimes abbreviated as "GPC").
  • GPC gel permeation chromatography
  • the polyisocyanate composition of the present embodiment has a lower hardness than conventional cured films obtained by curing the polyisocyanate composition alone, and has good flexibility and transparency. Further, by using the polyisocyanate composition of the present embodiment, the stress at 140% elongation is lower than before, the elongation is higher than before, and the tensile breaking stress is higher than before. A cured film can be obtained. . Furthermore, by using the polyisocyanate composition of the present embodiment, an adhesive resin sheet having excellent adhesive strength, curability and transparency can be obtained.
  • a polyisocyanate has structural units derived from a diisocyanate and one or more of the polyester polyols in one molecule.
  • the polyisocyanate composition of the present embodiment is derived from diisocyanate, polyester polyol (A) and polyester polyol (B), diisocyanate, polyester polyol (A) and polyester polyol (A) in one molecule It may be a polyisocyanate having all structural units derived from B), a polyisocyanate having structural units derived from diisocyanate and polyester polyol (A) in one molecule, and a polyisocyanate derived from diisocyanate and polyester polyol (B) It may be a mixture with a polyisocyanate having structural units.
  • the polyisocyanate can have at least one structure selected from the group consisting of allophanate structure, uretdione structure, iminooxadiazinedione structure, isocyanurate structure, urea structure, urethane structure, and biuret structure. Among them, it is preferable to have at least one structure selected from the group consisting of a urethane structure, an allophanate structure, a biuret structure, a urea structure, a uretdione structure, and an isocyanurate structure.
  • a uretdione structure it more preferably has at least one structure selected from the group consisting of a uretdione structure, more preferably has at least one structure selected from the group consisting of a urethane structure, an allophanate structure, a urea structure, and a uretdione structure, and a urethane structure.
  • an allophanate structure, and a uretdione structure more preferably having at least one structure selected from the group consisting of a urethane structure and an allophanate structure, and having a urethane structure is particularly preferred.
  • Diisocyanate is at least one selected from the group consisting of aliphatic diisocyanates and alicyclic diisocyanates.
  • Aliphatic diisocyanates include, but are not limited to, 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, ethyl (2,6-diisocyanato)hexanoate, 1,6-diisocyanate natohexane (hereinafter sometimes abbreviated as "HDI"), 1,9-diisocyanatononane, 1,12-diisocyanatododecane, 2,2,4- or 2,4,4-trimethyl-1 , 6-diisocyanatohexane, and the like. These aliphatic diisocyanates may be used alone or in combination of two or more.
  • Alicyclic diisocyanates include, but are not limited to, 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane (hereinafter sometimes abbreviated as “hydrogenated XDI”), 1 , 3- or 1,4-diisocyanatocyclohexane, 3,5,5-trimethyl 1-isocyanato-3-(isocyanatomethyl)cyclohexane (hereinafter sometimes abbreviated as "IPDI”), 4-4' -diisocyanato-dicyclohexylmethane (hereinafter sometimes abbreviated as "hydrogenated MDI”), 2,5- or 2,6-diisocyanatomethylnorbornane, and the like. These alicyclic diisocyanates may be used singly or in combination of two or more.
  • any of these aliphatic diisocyanates and alicyclic diisocyanates may be used alone, or two or more of these aliphatic diisocyanates and alicyclic diisocyanates may be used in combination.
  • the mass ratio of the alicyclic polyisocyanate to the aliphatic diisocyanate is preferably 0/100 or more and 30/70 or less.
  • diisocyanates include 1,4-diisocyanatobutane, HDI, 1,5-pentamethylene diisocyanate (PDI), 1,7-diisocyanatoheptane, 1,8-diisocyanatooctane, IPDI, hydrogenated XDI or hydrogenated MDI is preferred, HDI, PDI or IPDI is more preferred, HDI or PDI is even more preferred, and HDI is particularly preferred.
  • isocyanate monomers may be used for the production of polyisocyanates.
  • Aromatics such as diphenylmethane-4,4'-diisocyanate (MDI), 1,5-naphthalene diisocyanate, tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), m-tetramethylxylylene diisocyanate (TMXDI) Diisocyanate.
  • NTI 4-isocyanatomethyl-1,8-octamethylene diisocyanate
  • HTI 1,3,6-hexamethylene triisocyanate
  • GTI bis(2-isocyanatoethyl) 2-isocyanatoglutarate
  • LTI lysine triisocyanate
  • polyester polyol (A) and polyester polyol (B) are bifunctional polyester polyol (diol) having a number average molecular weight of 500 or more.
  • the polyester polyol (B) is a polyester polyol having a number average molecular weight of 500 or more and a functionality of 3 or more.
  • the number average molecular weight of the polyester polyol (A) is 500 or more, preferably 800 or more, more preferably 1500 or more, even more preferably 1800 or more.
  • the number average molecular weight of the polyester polyol (A) is at least the above lower limit, the cured film obtained by curing the polyisocyanate composition alone has low hardness and good flexibility.
  • the upper limit of the number average molecular weight of the polyester polyol (A) is not particularly limited. 6000 is preferable, 5000 is more preferable, and 4500 is even more preferable.
  • the number average molecular weight Mn of the polyester polyol (A) is, for example, a polystyrene-based number average molecular weight measured by GPC. When two or more polyester polyols (A) are mixed and used, the number average molecular weight of the mixture is calculated and used.
  • the polyester polyol (B) has a number average molecular weight of 500 or more, preferably 800 or more.
  • the number average molecular weight of the polyester polyol (B) is at least the above lower limit, the cured film obtained by curing the polyisocyanate composition alone has low hardness and good flexibility.
  • the upper limit of the number average molecular weight of the polyester polyol (B) is not particularly limited. It can be 4000, preferably 3500, more preferably 3000, even more preferably 2500.
  • the number average molecular weight Mn of the polyester polyol (B) is, for example, a polystyrene-based number average molecular weight measured by GPC. When two or more polyester polyols (B) are mixed and used, the number average molecular weight of the mixture is calculated and used.
  • the polyester polyol (A) includes, for example, the following polyester polyols (1) or (2).
  • the dibasic acid include carboxylic acids such as succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, and 1,4-cyclohexanedicarboxylic acid.
  • dihydric alcohol examples include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, trimethylpentanediol, cyclohexanediol and the like.
  • bifunctional polycaprolactone polyol is preferable as the polyester polyol (A).
  • bifunctional polycaprolactone polyols include, for example, Daicel's product name "PLAXEL 210" (number average molecular weight: 1000, hydroxyl value: 112.8 mgKOH/g, acid value: 0.09 mgKOH/g), "PLAXEL 210CP” (number average molecular weight 1000, hydroxyl value 112.8 mgKOH/g, acid value 0.16 mgKOH/g), trade name “PLAXEL 212” (number average molecular weight 1250, hydroxyl value 90.8 mgKOH/g, acid value 0.09 mgKOH / g), trade name “Plaxel 212CP” (number average molecular weight 1250, hydroxyl value 90.2 mgKOH / g, acid value 0.14 mgKOH / g), “Plaxel 220” (number average molecular weight 2000, hydroxyl value 56.7 mgKOH / g , acid value 0.06 mgKOH / g), "Plaxel 220” (
  • the polyester polyol (B) may be a tri- or more functional polyester polyol, preferably a tri- to 10-functional polyester polyol, more preferably a tri- to 7-functional polyester polyol, and tri- to penta-functional. is more preferred, tri- to tetra-functional polyester polyols are particularly preferred, and tri-functional polyester polyols (triols) are most preferred.
  • Examples of the trifunctional polyester polyol (B) include the following polyester polyols (1) or (2).
  • the dibasic acid include carboxylic acids such as succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, and 1,4-cyclohexanedicarboxylic acid.
  • the trihydric alcohol include trimethylolpropane, glycerin, pentaerythritol, 2-methylolpropanediol, and ethoxylated trimethylolpropane.
  • trifunctional polycaprolactone polyol is preferable as the trifunctional polyester polyol (B).
  • trifunctional polycaprolactone polyols include, for example, Daicel's product name "PLAXEL 305" (number average molecular weight: 550, hydroxyl value: 305.6 mgKOH/g, acid value: 0.50 mgKOH/g), "PLAXEL 308” (number average molecular weight 850, hydroxyl value 195.3 mgKOH/g, acid value 0.38 mgKOH/g), “Placcel 309” (number average molecular weight 900, hydroxyl value 187.3 mgKOH/g, acid value 0.20 mgKOH/g ), “Plaxel 312” (number average molecular weight 1250, hydroxyl value 136.1 mgKOH / g, acid value 0.38 mgKOH / g), “Plaxel 320” (number average molecular weight 2000, hydroxyl value 85.4 mgKOH / g, acid value 0 .29 mg KOH/g).
  • the content (preparation amount) of the polyester polyol (A) is preferably 0.1 parts by mass or more and 900 parts by mass or less with respect to 100 parts by mass of the diisocyanate. It is more preferably from 5 parts by mass to 800 parts by mass, even more preferably from 1 part by mass to 700 parts by mass, and even more preferably from 1 part by mass to 600 parts by mass.
  • the content of the polyester polyol (A) is at least the above lower limit, the cured film obtained by curing the polyisocyanate composition alone has low hardness and good flexibility.
  • an adhesive resin sheet having excellent adhesive strength and curability can be obtained.
  • the content of the polyester polyol (A) is equal to or less than the above upper limit, the liquid state can be maintained without gelation during the production of the polyisocyanate composition, the elongation rate and breaking strength are high, and the adhesiveness The flexibility of the flexible resin sheet becomes better.
  • the content of polyester polyol (A) can be calculated, for example, from the blending amounts of diisocyanate and polyester polyol (A) during production of the polyisocyanate composition and the yield of the obtained polyisocyanate composition.
  • the content (charge amount) of the polyester polyol (B) is preferably 0.1 parts by mass or more and 900 parts by mass or less with respect to 100 parts by mass of the diisocyanate. It is more preferably from 5 parts by mass to 800 parts by mass, even more preferably from 1 part by mass to 700 parts by mass, and even more preferably from 1 part by mass to 600 parts by mass.
  • the content of the polyester polyol (B) is at least the above lower limit, the cured film obtained by curing the polyisocyanate composition alone has low hardness and good flexibility.
  • an adhesive resin sheet having excellent adhesive strength and curability can be obtained.
  • the content of the polyester polyol (B) is the above upper limit or less, the liquid state can be maintained without gelation during the production of the polyisocyanate composition, and the flexibility when made into an adhesive resin sheet It will have better properties.
  • the content of the polyester polyol (B) can be calculated, for example, from the blending amounts of the diisocyanate and the polyester polyol (B) during production of the polyisocyanate composition and the yield of the resulting polyisocyanate composition.
  • polyester polyol (A) and polyester polyol (B) may be collectively referred to simply as polyester polyol.
  • polyester polyol (A) and polyester polyol (B) are used in combination
  • polyester polyol (A) and polyester polyol (B) can be used individually or as a mixture. When used as a mixture, they may be mixed before reacting with diisocyanate, or each polyester polyol may be reacted with diisocyanate alone to form polyisocyanate and then mixed.
  • a method for producing a polyisocyanate composition for example, a method of simultaneously reacting a diisocyanate, a polyester polyol (A), and a polyester polyol (B) to obtain a polyisocyanate composition; ), a diisocyanate, and a polyester polyol (B) are reacted to obtain a polyisocyanate composition; a diisocyanate and a polyester polyol (A) or a polyester polyol (B) and then further reacting the remaining polyester polyol to obtain a polyisocyanate composition.
  • the molar ratio of the isocyanate groups of the diisocyanate to the hydroxyl groups of the polyester polyol (A) and the polyester polyol (B) is 1.5 or more and 30 or less, and 2.0 or more and 25 or less. preferably 2.1 or more and 23 or less, more preferably 2.2 or more and 20 or less, further preferably 2.3 or more and 20.0 or less, further preferably 2.4 or more and 20.0 or less, and 2.5 or more It is more preferably 20.0 or less, and most preferably 2.52 or more and 20.0 or less.
  • the reaction between the polyester polyol and the diisocyanate is carried out as follows.
  • the reaction temperature is generally room temperature (approximately 23° C.) or higher and 200° C. or lower, preferably 60° C. or higher and 180° C. or lower, and preferably 60° C. or higher and 170° C. or lower. If the reaction temperature is at least the above lower limit, the reaction time will be shorter. On the other hand, if it is at most the above upper limit, viscosity increase and gelation of the polyisocyanate due to undesirable side reactions can be further avoided, and the resulting polyisocyanate coloring can also be avoided.
  • the reaction may be carried out without a solvent, or may be carried out using any solvent inert to isocyanate groups. Also, if necessary, a known catalyst may be used to accelerate the reaction between the isocyanate group and the hydroxyl group.
  • the isocyanate group content (NCO group content) of the polyisocyanate composition of the present embodiment is 1.0% by mass or more with respect to the total mass of the polyisocyanate composition in a state where it does not substantially contain a solvent or diisocyanate. It is preferably 8.7% by mass or less, more preferably 1.5% by mass or more and 8.6% by mass or less, further preferably 2.0% by mass or more and 8.5% by mass or less, It is more preferably 2.5% by mass or more and 8.5% by mass or less, further preferably 2.7% by mass or more and 8.5% by mass or less, and 2.9% by mass or more and 8.5% by mass or less. is particularly preferred.
  • the NCO group content can be determined, for example, by reacting the isocyanate groups of the polyisocyanate composition with excess amine (such as dibutylamine) and back titrating the remaining amine with an acid such as hydrochloric acid.
  • excess amine such as dibutylamine
  • the average isocyanate functional group number of the polyisocyanate composition of the present embodiment is preferably 2.0 or more and 6.0 or less, and 2.1 or more and 5.9 or less, in terms of improving the curability and flexibility of the adhesive resin composition. is more preferred.
  • the average number of isocyanate functional groups of the polyisocyanate composition of the present embodiment can be measured using the method described in Examples below.
  • the polyisocyanate composition of the present embodiment is preferably liquid at 23°C from the viewpoint of handling such as blending.
  • the cured film 1 of the present embodiment is obtained by curing the above-described polyisocyanate composition alone.
  • the cured film 1 of this embodiment has low hardness and good flexibility and transparency.
  • the cured film 1 of the present embodiment is obtained by, for example, diluting or dissolving the above-described polyisocyanate composition with a solvent as necessary, using a coater or the like, coating it on the adherend, and optionally It can be produced by drying and curing with heat.
  • the cured film 1 of the present embodiment is obtained by coating only the above-described polyisocyanate composition on glass and storing it for 168 hours in an environment of 23 ° C. and 65% humidity, and the moisture in the air and the polyisocyanate composition
  • the Konig hardness of the cured film at 23 ° C. is 60 times or less, preferably 59 times or less, and 58 times or less. is more preferable.
  • the Konig hardness is equal to or less than the above upper limit value, the hardness is low and the flexibility is excellent.
  • the lower limit of the Konig hardness of the cured film is not particularly limited, but can be, for example, 3 times, 4 times, or 5 times.
  • the cured film 1 of the present embodiment is obtained by coating only the above-described polyisocyanate composition on glass and storing it for 168 hours in an environment of 23 ° C. and 65% humidity, and the moisture in the air and the polyisocyanate composition
  • the haze value measured with a haze meter is 3.0 ⁇ m when the cured film is adhered to glass having a haze value of 0.1%. It is preferably 0% or less, more preferably 2.9% or less, even more preferably 2.8% or less.
  • the haze value of the cured film is equal to or less than the above upper limit value, the transparency is more excellent.
  • the lower limit of the haze value of the cured film is not particularly limited, and is preferably as close to 0.0% as possible.
  • the polyisocyanate composition described above can also be used as a curing agent component of the resin composition. That is, the cured film 2 of the present embodiment is obtained by curing a resin composition containing the above-described polyisocyanate composition and polyol (preferably acrylic polyol).
  • the cured film 2 can function, for example, as an adhesive layer.
  • the content of the above-described polyisocyanate composition is preferably 0.01 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the polyol, and 0.05 parts by mass or more and 190 parts by mass or less. and more preferably 0.10 parts by mass or more and 180 parts by mass or less.
  • the molar ratio NCO/OH of the isocyanate groups of the polyisocyanate composition to the hydroxyl groups of the polyol is determined according to the required physical properties of the resin film, but is usually 0.01 or more and 50 or less.
  • the cured film 2 of the present embodiment is the above-described polyisocyanate composition, a glass transition temperature of 0 ° C. or higher and 100 ° C. or lower, a hydroxyl value of 10 mg KOH / g or higher and 400 mg KOH / g or lower, and a weight average molecular weight of and a polyol of 5.0 ⁇ 10 3 or more ⁇ 2.0 ⁇ 10 5 or less so that the molar ratio NCO/OH of the isocyanate groups of the polyisocyanate composition to the hydroxyl groups of the polyol is 1.
  • the cured film is cut into a width of 10 mm and a length of 100 mm.
  • a test piece consisting of the following is set in a tensile tester so that the gripper distance is 20 mm, and the elongation in the tensile test measured at a speed of 20 mm / min is 140% or more, and the stress at the elongation of 140% is It is preferably 25.0 MPa or less, and the tensile breaking stress is preferably 1.2 times or more the stress at elongation of 140%.
  • the elongation rate is preferably 140% or higher, more preferably 145% or higher, even more preferably 150% or higher, particularly preferably 155% or higher, and most preferably 160% or higher.
  • the upper limit of the elongation rate can be, for example, 5000%.
  • the stress at the elongation rate of 140% is preferably 25.0 MPa or less, more preferably 24.0 MPa or less, and even more preferably 23.0 MPa or less.
  • the lower limit of the stress at the elongation rate of 140% can be set to 0.01 MPa, for example.
  • the tensile breaking stress is preferably 1.2 times or more, more preferably 1.3 times or more, and even more preferably 1.4 times or more the stress at 140% elongation. , more preferably 1.5 times or more, even more preferably 1.6 times, and particularly preferably 1.7 times.
  • the upper limit of the ratio of the tensile breaking stress to the stress at the elongation of 140% can be, for example, 30 times.
  • the elongation is the lower limit or more
  • the stress at the elongation of 140% is the upper limit or less
  • the ratio of the tensile breaking stress to the stress at the elongation of 140% is the lower limit or more.
  • the adhesive resin composition of this embodiment contains the polyisocyanate composition described above and a crosslinkable functional group-containing polymer having a glass transition temperature of 0.0° C. or less.
  • the adhesive resin composition of the present embodiment can form an adhesive layer having higher flexibility than before, and has adhesive strength, holding power, curability, and transparency. It is possible to obtain a pressure-sensitive adhesive resin sheet having excellent properties, bending resistance, step conformability, impact resistance, and durability.
  • the glass transition temperature of the crosslinkable functional group-containing polymer is 0.0° C. or less, preferably ⁇ 75.0° C. or more and 0.0° C. or less, more preferably ⁇ 75.0° C. or more and ⁇ 5.0° C. or less, and— 75.0°C or higher and -7.0°C or lower is more preferable, and -75.0°C or higher and -10.0°C or lower is particularly preferable.
  • Tg of the crosslinkable functional group-containing polymer is within the above range, the adhesive strength of the cured product of the adhesive resin composition tends to be more excellent.
  • the glass transition temperature of the crosslinkable functional group-containing polymer is determined, for example, by removing the organic solvent and water in the solution in which the crosslinkable functional group-containing polymer is dissolved or dispersed, under reduced pressure, and then vacuum drying. A value measured using a DSC) measuring device at a heating rate of 5° C./min can be used as the glass transition temperature.
  • the weight average molecular weight Mw of the crosslinkable functional group-containing polymer is preferably 1.0 ⁇ 10 5 or more and 5.0 ⁇ 10 6 or less, and is 1.5 ⁇ 10 5 or more and 4.0 ⁇ 10 6 or less. is more preferably 2.0 ⁇ 10 5 or more and 3.0 ⁇ 10 6 or less, and particularly preferably 2.5 ⁇ 10 5 or more and 2.5 ⁇ 10 6 or less.
  • the weight-average molecular weight of the crosslinkable functional group-containing polymer is within the above range, the cured product of the adhesive resin composition has adhesive strength, holding power, flexibility, bending resistance, step conformability, impact resistance, and It tends to be more durable.
  • the weight-average molecular weight Mw of the polyol can be measured, for example, using the method described in Examples below.
  • the crosslinkable functional group-containing polymer may be a polymer containing a crosslinkable functional group capable of reacting with the isocyanate group of the polyisocyanate composition.
  • the crosslinkable functional group include hydroxyl group, thiol group, amino group, epoxy group, oxetane group, carboxy group, vinyl group, amino group, etc. Among them, hydroxyl group, epoxy group, carboxy group, vinyl group, Or an amino group is preferable, a hydroxyl group, an epoxy group, an oxetane group, a carboxy group, or an amino group is more preferable, a hydroxyl group, a carboxy group, or an amino group is more preferable, and a hydroxyl group is particularly preferable.
  • polyol is preferable as the crosslinkable functional group-containing polymer.
  • crosslinkable functional group-containing polymers include aliphatic hydrocarbon polyols, polyether polyols, polyester polyols, epoxy resins, fluorine-containing polyols, acrylic polymers, and urethane polymers.
  • the crosslinkable functional group-containing polymer is preferably an acrylic polymer or a urethane polymer.
  • aliphatic hydrocarbon polyol examples include hydroxyl-terminated polybutadiene and hydrogenated products thereof.
  • polyether polyol examples include those obtained by using any one of the following methods (1) to (3).
  • the polyhydric alcohol examples include glycerin and propylene glycol.
  • Examples of the alkylene oxide include ethylene oxide and propylene oxide.
  • Examples of the polyfunctional compound include ethylenediamine and ethanolamine.
  • polyester polyols examples include the following polyester polyols (1) or (2).
  • a polyester polyol resin obtained by a condensation reaction between a dibasic acid alone or a mixture of two or more kinds and a polyhydric alcohol alone or a mixture of two or more kinds.
  • a polycaprolactone polyol obtained by ring-opening polymerization of ⁇ -caprolactone with a polyhydric alcohol.
  • the dibasic acid include carboxylic acids such as succinic acid, adipic acid, dimer acid, maleic anhydride, phthalic anhydride, isophthalic acid, terephthalic acid, and 1,4-cyclohexanedicarboxylic acid.
  • polyhydric alcohol examples include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, trimethylpentanediol, cyclohexanediol, trimethylolpropane, glycerin, and pentaerythritol. , 2-methylolpropanediol, ethoxylated trimethylolpropane, and the like.
  • epoxy resins examples include novolac type epoxy resins, ⁇ -methylepichloro type epoxy resins, cyclic oxirane type epoxy resins, glycidyl ether type epoxy resins, glycol ether type epoxy resins, epoxy type aliphatic unsaturated compounds, and epoxidized fatty acid esters. , ester-type polycarboxylic acids, aminoglycidyl-type epoxy resins, halogenated-type epoxy resins, resorcinol-type epoxy resins, and resins obtained by modifying these epoxy resins with amino compounds, polyamide compounds, and the like.
  • fluorine-containing polyol examples include fluoroolefins, cyclohexyl vinyl ethers, hydroxyalkyls, and the like disclosed in Reference Document 1 (JP-A-57-34107) and Reference Document 2 (JP-A-61-275311). Copolymers such as vinyl ethers and monocarboxylic acid vinyl esters are included.
  • the acrylic polymer contains one or more polymerizable (meth)acrylic monomer units having a crosslinkable functional group.
  • the crosslinkable functional group preferably contains a hydroxyl group, a carboxyl group, an epoxy group, or a vinyl group, more preferably a hydroxyl group or a carboxyl group, and still more preferably a hydroxyl group.
  • the acrylic polymer may contain a single crosslinkable functional group, or may contain a combination of two or more different types of crosslinkable functional groups.
  • the acrylic polymer may be obtained by polymerizing a polymerizable (meth)acrylic monomer having a crosslinkable functional group alone, or a polymerizable (meth)acrylic monomer having different types of crosslinkable functional groups. may be obtained by combining two or more of the above and copolymerizing them.
  • the acrylic polymer can contain one or more polymerizable acrylic monomer units having no crosslinkable functional group in addition to polymerizable (meth)acrylic monomer units having a crosslinkable functional group.
  • the acrylic polymer polymerizes a polymerizable (meth)acrylic monomer having one or more crosslinkable functional groups, or polymerizes a polymerizable (meth)acrylic monomer having one or more crosslinkable functional groups and one It can be obtained by copolymerizing a polymerizable (meth)acrylic monomer having no crosslinkable functional group.
  • the acrylic polymer contains, in addition to a polymerizable (meth)acrylic monomer unit having a crosslinkable functional group, one or more (meth)acrylic acid ester monomer units having 1 to 18 carbon atoms at the end of the ester group. is preferred. That is, the acrylic polymer comprises at least one polymerizable (meth)acrylic monomer having a crosslinkable functional group and at least one (meth)acrylic acid ester monomer having at least 1 to 18 carbon atoms at the end of the ester group. It may be one that does not copolymerize with.
  • the (meth)acrylate monomer may or may not have a crosslinkable functional group, but preferably not.
  • the number of carbon atoms at the end of the ester group of the (meth)acrylate monomer is preferably 1 or more and 18 or less.
  • Examples of the polymerizable (meth)acrylic monomer having a crosslinkable functional group include the following (i) to (v). These may be used individually by 1 type, and may be used in combination of 2 or more type.
  • (iii) (meth)acrylic acid esters having a polyvalent hydroxy group such as glycerol monoacrylate or methacrylic acid monoester, trimethylolpropane acrylic acid monoester or methacrylic acid monoester; (iv) unsaturated carboxylic acids such as acrylic acid and methacrylic acid; (v) (meth)acrylic acid esters having an epoxy group such as glycidyl methacrylate;
  • Examples of the (meth)acrylic acid ester monomer having 1 to 18 carbon atoms at the end of the ester group include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (meth)acryl isopropyl acid, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, (meth)acrylate isopentyl acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth) acrylate, decyl (meth) acrylate,
  • the acrylic polymer can further contain monomer units other than the (meth)acrylic acid ester monomer. That is, the acrylic polymer polymerizes a polymerizable (meth)acrylic monomer having one or more crosslinkable functional groups, or polymerizes a polymerizable (meth)acrylic monomer having one or more crosslinkable functional groups. It is obtained by copolymerizing with one or more other monomers. Other monomers may or may not have a crosslinkable functional group, but preferably not.
  • Other monomers include, for example, the following (i) to (ii). These may be used individually by 1 type, and may be used in combination of 2 or more type.
  • unsaturated amides such as (meth)acrylamide, N-methylolacrylamide, diacetoneacrylamide, dimethylaminopropylacrylamide;
  • styrene vinyl toluene, vinyl acetate, (meth)acrylonitrile, N-vinylpyrrolidone, N-vinylcaprolactam, acryloylmorpholine, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate.
  • JP-A-1-261409 Reference 3
  • JP-A-3-006273 A polymerizable UV-stable monomer disclosed in Reference 4) or the like may also be used.
  • polymerizable UV-stable monomer examples include 4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(meth)acryloylamino-2,2,6 , 6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 2-hydroxy-4-(3-methacryloxy-2-hydroxypropoxy)benzophenone and the like. be done.
  • an acrylic polymer can be obtained by solution-polymerizing the monomer components described above in the presence of a radical polymerization initiator such as a known peroxide or an azo compound, and diluting with an organic solvent or the like as necessary. can.
  • a radical polymerization initiator such as a known peroxide or an azo compound
  • a water-based acrylic polymer When obtaining a water-based acrylic polymer, it can be produced by a known method such as a method of solution-polymerizing an olefinic unsaturated compound and converting it into a water layer, or emulsion polymerization. In that case, water-solubility or water-dispersibility can be imparted by neutralizing acidic moieties such as carboxylic acid-containing monomers such as acrylic acid and methacrylic acid and sulfonic acid-containing monomers with amines or ammonia.
  • a known method such as a method of solution-polymerizing an olefinic unsaturated compound and converting it into a water layer, or emulsion polymerization.
  • water-solubility or water-dispersibility can be imparted by neutralizing acidic moieties such as carboxylic acid-containing monomers such as acrylic acid and methacrylic acid and sulfonic acid-containing monomers with amines or ammonia.
  • the content of the above-described polyisocyanate composition is 0.01 parts by mass or more and 20.00 parts by mass or less with respect to 100 parts by mass of the crosslinkable functional group-containing polymer. It is preferably 0.03 parts by mass or more and 15.00 parts by mass or less, and further preferably 0.05 parts by mass or more and 13.0 parts by mass or less.
  • the adhesive resin composition of this embodiment may further contain other additives.
  • Other additives include, for example, curing agents other than polyisocyanate compositions that can react with the crosslinkable functional group-containing polymer, curing catalysts, solvents, pigments (extender pigments, coloring pigments, metallic pigments, etc.), tackifying resins, Photopolymerization initiators, UV absorbers, light stabilizers, radical stabilizers, anti-yellowing agents that suppress coloring during the baking process, coating surface conditioners, flow control agents, pigment dispersants, antifoaming agents, thickeners, Examples include film-forming aids.
  • curing agent examples include melamine resins, urea resins, epoxy group-containing compounds or resins, carboxy group-containing compounds or resins, acid anhydrides, alkoxysilane group-containing compounds or resins, and hydrazide compounds.
  • the curing catalyst may be a basic compound or a Lewis acidic compound.
  • the basic compound include metal hydroxides, metal alkoxides, metal carboxylates, metal acetylacetinates, hydroxides of onium salts, onium carboxylates, halides of onium salts, metal salts of active methylene compounds, Examples include onium salts of active methylene compounds, aminosilanes, amines, phosphines, and the like.
  • the onium salt an ammonium salt, a phosphonium salt or a sulfonium salt is suitable.
  • the Lewis acidic compound include organic tin compounds, organic zinc compounds, organic titanium compounds, organic zirconium compounds, and the like.
  • the solvent examples include 1-methylpyrrolidone, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-3-methyl -1-butanol, ethylene glycol diethyl ether, diethylene glycol diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether (DPDM), propylene glycol dimethyl ether, methyl ethyl ketone, acetone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethanol, methanol , iso-propanol, 1-propanol, iso-butanol, 1-butanol, tert-butanol, 2-ethylhexanol, cyclohex
  • pigments extendender pigments, color pigments, metallic pigments, etc.
  • ultraviolet absorbers light stabilizers, radical stabilizers, anti-yellowing agents that suppress coloring during the baking process, coating surface conditioners, flow control agents, pigments
  • coating surface conditioners coating surface conditioners, flow control agents, pigments
  • pigments As the dispersant, antifoaming agent, thickener and film-forming aid, known ones can be appropriately selected and used.
  • the adhesive resin composition can be produced by a conventionally known method.
  • a Banbury mixer a single-screw extruder, a twin-screw extruder, a co-kneader, a melt-kneading method using a general kneader such as a multi-screw extruder, after dissolving or dispersing and mixing each component, using a coater or the like
  • a method such as removing the solvent by heating after coating on the scratched film is used.
  • the adhesive resin composition of this embodiment may be foamed in order to reduce weight, increase flexibility, and improve adhesion.
  • Foaming methods include chemical methods, physical methods, and the use of thermally expandable microballoons. Bubbles can be distributed inside the material by adding a chemical foaming agent such as an inorganic foaming agent or an organic foaming agent, or a physical foaming agent, or by adding thermally expandable microballoons.
  • hollow fillers (already inflated balloons) may be added to reduce weight, increase flexibility, and improve adhesion.
  • a tackifying resin may be added to the adhesive resin composition of the present embodiment to adjust adhesive strength.
  • tackifying resins include rosin-based tackifying resins, terpene-based tackifying resins, petroleum-based tackifying resins, and styrene-based tackifying resins. These tackifying resins may be used singly or in combination of two or more. Also, the softening point of the tackifier resin is preferably 90° C. or higher and 160° C. or lower.
  • the adhesive resin sheet of this embodiment is obtained by curing the adhesive resin composition described above with heat or light.
  • the adhesive resin sheet of the present embodiment is excellent in adhesiveness, bending resistance, holding power, curability, conformability to unevenness, impact resistance, durability, and transparency.
  • the thickness of the adhesive resin sheet (adhesive layer) of the present embodiment can be appropriately determined depending on the application, but is preferably 1 ⁇ m or more and 1000 ⁇ m or less, and 2 ⁇ m or more and 900 ⁇ m or less. is more preferably 3 ⁇ m or more and 800 ⁇ m or less, and particularly preferably 5 ⁇ m or more and 700 ⁇ m or less.
  • the adhesive resin sheet of the present embodiment can be produced, for example, by applying an adhesive resin composition onto a substrate, drying it if necessary, and then curing it.
  • Examples of the method of applying the adhesive resin composition onto the substrate include a method of applying using an applicator, roll coater, knife coater, gravure coater, and the like.
  • drying is performed after the coating, for example, the obtained laminate is placed in a dryer or the like, for example, at a temperature of 50 ° C. or more and 150 ° C. or less, a heat drying method of drying for 1 minute or more and 30 minutes or less.
  • other drying methods include, for example, natural drying, hot air drying, infrared drying, and the like.
  • the substrate is not particularly limited, but for example, paper such as woodfree paper, coated paper, cast coated paper, thermal paper, inkjet paper; cloth such as woven fabric and nonwoven fabric; polyvinyl chloride, synthetic paper, polyethylene terephthalate (PET ), polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, polystyrene, polycarbonate, nylon, polyvinyl alcohol, ethylene-vinyl acetate copolymer, resin films such as polyimide; porous resin films such as porous polypropylene film; PET, polyolefin A metal foil is exemplified.
  • the base material may be one whose surface has been subjected to release treatment.
  • the heating temperature during curing can be from 70°C to 160°C, from 75°C to 155°C, and from 80°C to 150°C.
  • the adhesive resin sheet of the present embodiment is obtained by coating the adhesive resin composition on a polyethylene terephthalate film having a thickness of 38 ⁇ m and having undergone release treatment, drying at 135° C. for 3 minutes and curing, followed by curing at 23° C. and 50° C. % RH environment for 7 days, the adhesive resin sheet obtained by peeling off the release-treated polyethylene terephthalate film from a laminate having a 50 ⁇ m thick adhesive resin sheet was stored in a 23° C., 50% RH environment.
  • the gel fraction calculated by drying at 120°C for 2 hours is 20.0% by mass. It is preferably at least 99.9% by mass, more preferably at least 25.0% by mass and at most 99.9% by mass, further preferably at least 30.0% by mass and not more than 99.9% by mass. , 32.0% by mass or more and 99.9% by mass or less, and most preferably 35.0% by mass or more and 99.9% by mass or less.
  • the gel fraction referred to here is the percentage of the mass of the adhesive resin sheet dried after being immersed in ethyl acetate with respect to the mass of the adhesive resin sheet before being immersed in ethyl acetate.
  • the adhesive resin sheet of the present embodiment is obtained by coating the adhesive resin composition on a polyethylene terephthalate film having a thickness of 25 ⁇ m, drying it at 135° C. for 3 minutes and curing it, and then under an environment of 23° C. and 50% RH.
  • a laminate comprising an adhesive resin sheet with a thickness of 50 ⁇ m, a width of 20 mm, and a length of 100 mm stored for 7 days is attached to the SUS304BA plate that is the adherend, and is pressed back and forth with a 2 kg roller and cured at 23 ° C. for 30 minutes. After that, the 180 degree peel adhesive strength measured at 23 ° C.
  • a speed of 300 mm / min is preferably 0.05 N / 20 mm or more and 65.00 N / 20 mm or less, and 0.05 N / 20 mm or more and 64.50 N / 20 mm or less More preferably, 0.05 N/20 mm or more and 64.00 N/20 mm or less is more preferable, and 0.05 N/20 mm or more and 63.50 N/20 mm or less is particularly preferable, and 0.05 N/20 mm It is most preferable to be above 63.00 N/20 mm or below. When the 180-degree peel adhesive strength is equal to or higher than the above lower limit, the adhesive strength is excellent.
  • the adhesive resin sheet of the present embodiment is obtained by coating the adhesive resin composition on a polyethylene terephthalate film having a thickness of 38 ⁇ m and having undergone release treatment, drying at 135° C. for 3 minutes and curing, followed by curing at 23° C. and 50° C. % RH environment for 7 days, and an adhesive resin sheet having a thickness of 50 ⁇ m obtained by peeling from the polyethylene terephthalate film subjected to the peeling treatment was laminated on glass having a haze value of 0.1%,
  • the haze value measured with a haze meter is preferably 2.0% or less, more preferably 1.8% or less, even more preferably 1.6% or less, and 1.3% or less.
  • the content is 1.0% or less, most preferably 1.0% or less. It is excellent by transparency because a haze value is below the said upper limit.
  • the lower limit of the haze value of the adhesive resin sheet is not particularly limited, and is preferably as close to 0.0% as possible. .
  • the laminated film of this embodiment is obtained by laminating a film substrate on at least one side of the adhesive resin sheet described above.
  • the laminated film of the present embodiment is suitable for application to optical members, and is particularly preferably used for attachment to metal thin films and metal electrodes in optical applications.
  • metal thin films include thin films made of metals, metal oxides, and mixtures thereof, and are not particularly limited. Examples include thin films of ITO (indium tin oxide), ZnO, SnO, and CTO (cadmium tin oxide). be done. Although the thickness of the metal thin film is not particularly limited, it is about 10 to 200 nm.
  • a metal thin film such as ITO is usually provided on a transparent plastic film substrate such as a polyethylene terephthalate film (PET film) and used as a transparent conductive film.
  • PET film polyethylene terephthalate film
  • the metal electrode is not particularly limited as long as it is an electrode made of metal, metal oxide, or a mixture thereof. Examples include electrodes of ITO, silver, copper, and CNT (carbon nanotube).
  • a touch panel can be given as an example of a specific application of the laminated film of the present embodiment.
  • the pressure-sensitive adhesive sheet for a touch panel includes a transparent conductive film provided with a metal thin film such as ITO, a polymethyl methacrylate resin (PMMA) plate, a hard coat film, a glass lens, and the like. It is used for pasting together.
  • the touch panel is not particularly limited, but is used for, for example, mobile phones, tablet computers, personal digital assistants, and the like.
  • an optical member can be used as the film substrate of the laminated film of the present embodiment.
  • the adhesive resin composition is directly applied to the optical member, and the polymerization solvent and the like are removed by drying to obtain an adhesive optical member in which the adhesive resin sheet is formed on the optical member.
  • the adhesive resin sheet formed on the release-treated separator can be appropriately transferred to the optical member to obtain the adhesive optical member.
  • release-treated sheet used in the production of the adhesive optical member can be used as it is as a separator for the adhesive optical member, and the process can be simplified.
  • the adhesive layer is formed after forming an anchor layer on the surface of the optical member, or subjecting the surface of the optical member to various easy-adhesion treatments such as corona treatment and plasma treatment. can do. Further, the surface of the pressure-sensitive adhesive layer may be subjected to an easy-adhesion treatment.
  • the adhesive optical member can be used as a transparent conductive film with an adhesive layer by using a transparent conductive film as the optical member.
  • the transparent conductive film has a transparent conductive thin film, which is a metal thin film such as the above ITO, on one side of a transparent plastic film substrate.
  • the other surface of the transparent plastic film substrate has the laminated film of the present embodiment.
  • a transparent conductive thin film can be provided on the transparent plastic film substrate via an undercoat layer.
  • a plurality of undercoat layers can be provided.
  • An oligomer migration prevention layer can be provided between the transparent plastic film substrate and the adhesive resin sheet.
  • the transparent plastic film substrate is not particularly limited, but various transparent plastic films are used.
  • the plastic film is formed of one layer of film.
  • the materials include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, and (meth)acrylic resins.
  • polyvinyl chloride-based resins polyvinylidene chloride-based resins, polystyrene-based resins, polyvinyl alcohol-based resins, polyarylate-based resins, polyphenylene sulfide-based resins, triacetyl cellulose-based resins, and the like.
  • polyester-based resins polyimide-based resins and polyethersulfone-based resins.
  • the thickness of the film substrate is preferably 15 to 200 ⁇ m.
  • the surface of the film substrate is preliminarily subjected to sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical conversion, etching treatment such as oxidation, or undercoating treatment, and a transparent conductive thin film or undercoat is provided thereon. Adhesion of the layer to the film substrate may be improved. In addition, before providing the transparent conductive thin film or the undercoat layer, dust removal and cleaning may be performed by solvent cleaning, ultrasonic cleaning, or the like, if necessary.
  • the constituent material and thickness of the transparent conductive thin film are not particularly limited, and are as exemplified for the metal thin film above.
  • the undercoat layer can be formed of an inorganic material, an organic material, or a mixture of an inorganic material and an organic material.
  • inorganic substances include NaF (1.3), Na 3 AlF 6 (1.35), LiF (1.36), MgF 2 (1.38), CaF 2 (1.4), BaF 2 (1.4). 3) Inorganic substances such as SiO 2 (1.46), LaF 3 (1.55), CeF 3 (1.63), Al 2 O 3 (1.63) , which is the refractive index of light].
  • SiO 2 , MgF 2 , A1 2 O 3 and the like are preferred, and SiO 2 is particularly preferred.
  • a composite oxide containing about 10 to 40 parts by weight of cerium oxide and about 0 to 20 parts by weight of tin oxide can be used with respect to indium oxide.
  • organic substances include acrylic resins, urethane resins, melamine resins, alkyd resins, siloxane-based polymers, and organic silane condensates. At least one of these organic substances is used. In particular, it is desirable to use a thermosetting resin composed of a mixture of a melamine resin, an alkyd resin and an organic silane condensate as the organic substance.
  • the thickness of the undercoat layer is not particularly limited, it is usually about 1 to 300 nm, preferably 5 to 300 nm, from the viewpoint of optical design and the effect of preventing oligomer generation from the film substrate. .
  • the adhesive layer-attached transparent conductive film is used in the formation of various devices such as touch panels, liquid crystal displays, and organic EL displays.
  • it can be preferably used as an electrode plate for a touch panel.
  • a touch panel is suitably used for various detection methods (for example, a resistive film method, a capacitive method, etc.).
  • a capacitive touch panel normally has a transparent conductive film with a transparent conductive thin film having a predetermined pattern formed over the entire display area.
  • the pressure-sensitive adhesive layer-attached transparent conductive film is appropriately laminated so that the pressure-sensitive adhesive layer and the patterned transparent conductive thin film face each other.
  • the adhesive optical member can be used as an optical film with an adhesive layer by using an optical film for an image display device as the optical member.
  • the optical film those used for forming image display devices such as liquid crystal display devices and organic EL display devices are used, and the type thereof is not particularly limited.
  • the optical film includes a polarizing plate.
  • a polarizing plate having a transparent protective film on one or both sides of a polarizer is generally used.
  • the titration value obtained without the polyisocyanate sample was then taken as V1 ml. Then, the isocyanate group content (NCO %) (% by mass) of the polyisocyanate composition was calculated from the following formula. For the NCO%, a value calculated in a solvent-free state was adopted.
  • the number average molecular weight and weight average molecular weight are polystyrene-based number average molecular weight and weight average molecular weight measured by gel permeation chromatography (GPC) using the following equipment.
  • the average isocyanate functional group number (average NCO number) of the polyisocyanate composition was determined by the following formula.
  • Mn means number average molecular weight
  • NCO% the value calculated in “Physical Properties 1” was used.
  • Glass transition temperature Tg The glass transition temperature of the polyol for preparing the resin composition and the crosslinkable functional group-containing polymer is obtained by removing the organic solvent and moisture in the acrylic polyol solution or the crosslinkable functional group-containing polymer solution under reduced pressure, and then vacuum drying. A value measured using a differential scanning calorimeter (DSC) measuring apparatus at a heating rate of 5° C./min was used as the glass transition temperature.
  • DSC differential scanning calorimeter
  • the stress, elongation and ratio of tensile breaking stress to stress at 140% elongation were evaluated as good.
  • those having a large elongation rate, a low stress at an elongation rate of 140%, and a tensile breaking stress of 1.2 times or more of the stress at an elongation rate of 140% are evaluated to have better flex resistance. bottom.
  • adhesive resin composition X 1.0 parts by mass (solid content) of each polyisocyanate composition and ethyl acetate are added to 100 parts by mass of the solid content of the crosslinkable functional group-containing polymer (acrylic polymer) OH1 to give a solid content of 25 mass. % adhesive resin composition X was prepared.
  • adhesive resin composition Y 2.0 parts by mass (solid content) of each polyisocyanate composition and ethyl acetate are added to 100 parts by mass of the solid content of the crosslinkable functional group-containing polymer (acrylic polymer) OH2 to give a solid content of 25 mass. % adhesive resin composition Y was prepared.
  • Adhesive resin composition X or adhesive resin composition Y was applied on a polyethylene terephthalate (PET) film having a thickness of 25 ⁇ m using an applicator so that the thickness after drying was 50 ⁇ m, and dried at 135° C. for 3 minutes. After that, it was stored for 7 days under an environment of 23° C. and 50% RH to obtain an adhesive resin sheet for 180° peel adhesion measurement.
  • PET polyethylene terephthalate
  • Adhesive resin composition X or adhesive resin composition Y was coated on a peel-treated PET film having a thickness of 38 ⁇ m with an applicator so that the thickness after drying was 50 ⁇ m, and dried at 135 ° C. for 3 minutes. . After that, it was stored in an environment of 23° C. and 50% RH for 7 days to obtain an adhesive resin sheet for gel fraction measurement.
  • Adhesive resin composition X or adhesive resin composition Y is coated on a polyethylene terephthalate film having a thickness of 38 ⁇ m and has been subjected to release treatment, dried at 135° C. for 3 minutes and cured, and then cured in an environment of 23° C. and 50% RH.
  • a 50 ⁇ m-thick adhesive resin sheet obtained by peeling from the polyethylene terephthalate film subjected to the peeling treatment was stored for 7 days under a low temperature, and the haze value was 0.1%.
  • a laminate provided with the adhesive resin sheet for measurement was obtained.
  • the polyol for resin composition preparation had a glass transition temperature Tg of 29.5° C., a hydroxyl value of 139 mgKOH/g based on the resin solid content, and a weight average molecular weight Mw of 2.75 ⁇ 10 4 .
  • the reaction mixture was cooled to obtain an acrylic polymer OH2 having a solid content concentration of 42.2% by mass.
  • the acrylic polymer OH2 had a glass transition temperature of ⁇ 69.0° C. and a weight average molecular weight of 8.7 ⁇ 10 5 , which were measured without the solvent.
  • Example 1 Production of polyisocyanate composition PA-a1
  • the detection of the structure by NMR analysis is based on the total molar amount of allophanate groups, uretdione groups, iminooxadiazinedione groups, isocyanurate groups, urea groups, urethane groups, and biuret groups detected for individual bonds.
  • a ratio (mol %) of 1% or more was counted as the presence of the bond.
  • binding was counted by adopting the same method in the following examples.
  • Example 2 (Production of polyisocyanate composition PA-a2) A four-necked flask equipped with a thermometer, a stirring blade, and a reflux condenser was charged with 100 parts by mass of HDI under a nitrogen stream, and polyester polyol A1: 135 parts by mass (the ratio of the isocyanate group of HDI to the hydroxyl group of polyester polyol A1 was The temperature in the reactor was maintained at 100° C. while stirring the amount that would give a molar ratio of 8.7. The reaction was terminated when the yield reached 58.0% by mass. After filtering the reaction solution, unreacted HDI was removed by a thin film distillation apparatus to obtain a polyisocyanate composition PA-a2.
  • the resulting polyisocyanate composition PA-a2 was analyzed by H-NMR and C-NMR to confirm the presence of urethane groups and allophanate groups, and the molar ratio of urethane groups was the largest among these groups. Then, butyl acetate was added to the obtained polyisocyanate composition to dilute it to a solid content of 70% by mass, and the resulting composition was liquid at 23°C.
  • Example 3 (Production of polyisocyanate composition PA-a3) A four-necked flask equipped with a thermometer, stirring blades, and a reflux condenser was charged with 100 parts by mass of HDI under a nitrogen stream, 0.5 parts by mass of 1,3-butanediol, and 125 parts by mass of polyester polyol A1. The temperature in the reactor was maintained at 160°C for 20 minutes and then lowered to 100°C while stirring the part (an amount that gives a molar ratio of the isocyanate groups of HDI to the hydroxyl groups of polyester polyol A1 of 9.4). The reaction was terminated when the yield reached 56.0% by mass.
  • a polyisocyanate composition PA-a3 After filtering the reaction solution, unreacted HDI was removed with a thin film distillation apparatus to obtain a polyisocyanate composition PA-a3.
  • the resulting polyisocyanate composition PA-a3 was analyzed by H-NMR and C-NMR to confirm the presence of urethane groups, allophanate groups, uretdione groups, and urea groups. ratio was the highest.
  • butyl acetate was added to the obtained polyisocyanate composition to dilute it to a solid content of 70% by mass, and the resulting composition was liquid at 23°C.
  • Example 4 (Production of polyisocyanate composition PA-a4) A four-necked flask equipped with a thermometer, a stirring blade, and a reflux condenser was charged with 100 parts by mass of HDI under a nitrogen stream, and bifunctional polycaprolactone diol (hereinafter sometimes referred to as "polyester polyol A2" ) (manufactured by Daicel Corporation, trade name “PLAXEL 230”, number average molecular weight 3000, hydroxyl value 37.6 mgKOH/g, acid value 0.07 mgKOH/g): 150 parts by mass (the ratio of the isocyanate group of HDI to the hydroxyl group of polyester polyol A2 The temperature in the reactor was maintained at 100° C.
  • Example 5 (Production of polyisocyanate composition PA-a5) A four-necked flask equipped with a thermometer, a stirring blade, and a reflux condenser was charged with 100 parts by mass of HDI under a nitrogen stream, and bifunctional polycaprolactone diol (hereinafter sometimes referred to as "polyester polyol A3" ) (manufactured by Daicel Corporation, trade name “PLAXEL 240”, number average molecular weight 4000, hydroxyl value 28.5 mgKOH/g, acid value 0.07 mgKOH/g): 200 parts by mass (the ratio of the isocyanate group of HDI to the hydroxyl group of polyester polyol A3 The temperature in the reactor was maintained at 100° C.
  • Example 6 (Production of polyisocyanate composition PA-a6) A four-necked flask equipped with a thermometer, stirring blades, and a reflux condenser was charged with 100 parts by mass of HDI under a nitrogen stream, 0.8 parts by mass of 2-ethylhexanol, and 125 parts by mass of polyester polyol A1 ( The temperature in the reactor was kept at 100° C. while stirring the amount of the isocyanate groups of HDI to give a molar ratio of 9.4 for the isocyanate groups of the polyester polyol A1 to the hydroxyl groups. The reaction was terminated when the yield reached 56.0% by mass.
  • a polyisocyanate composition PA-a6 After filtering the reaction solution, unreacted HDI was removed by a thin film distillation apparatus to obtain a polyisocyanate composition PA-a6.
  • the resulting polyisocyanate composition PA-a6 was analyzed by H-NMR and C-NMR to confirm the presence of urethane groups and allophanate groups, and the molar ratio of urethane groups was the largest among these bonds. Then, butyl acetate was added to the obtained polyisocyanate composition to dilute it to a solid content of 70% by mass, and the resulting composition was liquid at 23°C.
  • Example 7 (Production of polyisocyanate composition PA-a7) A four-necked flask equipped with a thermometer, stirring blades, and a reflux condenser was charged with 100 parts by mass of HDI under a nitrogen stream, 0.5 parts by mass of 1,3-butanediol, and 118 parts by mass of polyester polyol A1. The temperature in the reactor was kept at 100° C. while stirring the part (the amount that the molar ratio of the isocyanate group of HDI to the hydroxyl group of polyester polyol A1 is 10.0). The reaction was stopped when the yield reached 54.7% by mass.
  • Example 8 (Production of polyisocyanate composition PA-a8) A four-necked flask equipped with a thermometer, a stirring blade, and a reflux condenser was charged with 100 parts by mass of HDI under a nitrogen stream, and trifunctional polycaprolactone polyol (hereinafter sometimes referred to as "polyester polyol B1"). ) (manufactured by Daicel Corporation, trade name “PLAXEL 308”, number average molecular weight 850, hydroxyl value 195.3 mgKOH/g, acid value 0.38 mgKOH/g): 37.5 parts by mass (HDI isocyanate for the hydroxyl group of polyester polyol B1 The temperature in the reactor was maintained at 100° C.
  • Example 9 to 12 (Production of polyisocyanate compositions PA-a9 to PA-a12) Each polyisocyanate composition was produced using the same method as in Example 8 except that the formulation shown in Table 2 was used. The resulting polyisocyanate composition was analyzed by H-NMR and C-NMR to confirm the presence of urethane groups and allophanate groups, with the urethane groups having the highest molar proportion of these bonds. Then, butyl acetate was added to the obtained polyisocyanate composition to dilute it to a solid content of 70% by mass, and the resulting composition was liquid at 23°C.
  • Example 13 (Production of polyisocyanate composition PA-a13) A four-necked flask equipped with a thermometer, stirring blades, and a reflux condenser was charged with 100 parts by mass of HDI under a nitrogen stream, 1,3-butanediol: 1.0 parts by mass, and polyester polyol A1: 115 parts by mass. The temperature in the reactor was maintained at 100° C. while stirring the part (the amount that the molar ratio of the isocyanate group of HDI to the hydroxyl group of polyester polyol A1 was 10.2). The reaction was terminated when the yield reached 53.0% by mass.
  • a polyisocyanate composition PA-a13 After filtering the reaction solution, unreacted HDI was removed by a thin film distillation apparatus to obtain a polyisocyanate composition PA-a13.
  • the resulting polyisocyanate composition PA-a13 was analyzed by H-NMR and C-NMR to confirm the presence of urethane bonds and allophanate bonds, and the molar ratio of urethane bonds was the largest among these bonds.
  • ethyl acetate was added to the obtained polyisocyanate composition to dilute it to a solid content of 70% by mass, and it was liquid at 23°C.
  • Example 14 (Production of polyisocyanate composition PA-a14) A four-necked flask equipped with a thermometer, stirring blades, and a reflux condenser was charged with 100 parts by mass of HDI under a nitrogen stream, 1.5 parts by mass of 1,3-butanediol, and 112 parts by mass of polyester polyol A1. The temperature in the reactor was maintained at 100° C. while stirring the part (the amount that the molar ratio of the isocyanate group of HDI to the hydroxyl group of polyester polyol A1 was 10.5). The reaction was terminated when the yield reached 51.5% by mass.
  • polyisocyanate component PA-a14 a polyisocyanate component.
  • the resulting polyisocyanate composition PA-a14 was analyzed by H-NMR and C-NMR to confirm the presence of urethane groups and allophanate groups. Among these bonds, the molar ratio of urethane groups was the largest. After that, ethyl acetate was added to the obtained polyisocyanate composition to dilute it to a solid content of 70% by mass, and it was liquid at 23°C.
  • Example 15 (Production of polyisocyanate composition PA-a15) A four-necked flask equipped with a thermometer, stirring blades, and a reflux condenser was charged with 100 parts by mass of HDI under a nitrogen stream, 2.0 parts by mass of 1,3-butanediol, and 130 parts by mass of polyester polyol A1. The temperature in the reactor was kept at 160°C for 20 minutes and then lowered to 100°C while stirring the part (an amount that gives a molar ratio of 9.1 for the isocyanate group of HDI to the hydroxyl group of polyester polyol A1). The reaction was terminated when the yield reached 56.3% by mass.
  • polyisocyanate component PA-a15 a polyisocyanate component PA-a15.
  • the resulting polyisocyanate composition PA-a15 was analyzed by H-NMR and C-NMR to confirm the presence of urethane groups, allophanate groups, uretdione groups, and urea groups. ratio was the highest. After that, ethyl acetate was added to the obtained polyisocyanate composition to dilute it to a solid content of 70% by mass, and it was liquid at 23°C.
  • Example 16 (Production of polyisocyanate composition PA-a16) A four-necked flask equipped with a thermometer, stirring blades, and a reflux condenser was charged with 100 parts by mass of HDI under a nitrogen stream, 2.5 parts by mass of 1,3-butanediol, and 135 parts by mass of polyester polyol A1. The temperature in the reactor was maintained at 160° C. for 20 minutes and then lowered to 100° C. while stirring the part (an amount that gives a molar ratio of the isocyanate groups of HDI to the hydroxyl groups of polyester polyol A1 of 8.7). The reaction was terminated when the yield reached 58.7% by mass.
  • polyisocyanate component PA-a16 for 120 minutes to obtain a polyisocyanate component PA-a16.
  • the resulting polyisocyanate composition PA-a16 was analyzed by H-NMR and C-NMR to confirm the presence of urethane groups, allophanate groups, uretdione groups, and urea groups. ratio was the highest.
  • ethyl acetate was added to the obtained polyisocyanate composition to dilute it to a solid content of 70% by mass, and it was liquid at 23°C.
  • Example 17 (Production of polyisocyanate composition PA-a17) A four-necked flask equipped with a thermometer, a stirring blade, and a reflux condenser was charged with 100 parts by mass of HDI under a nitrogen stream, and bifunctional polycaprolactone diol (hereinafter sometimes referred to as "polyester polyol A3" ) (manufactured by Daicel Corporation, trade name “PLAXEL 240”, number average molecular weight 4000, hydroxyl value 28.5 mgKOH/g, acid value 0.07 mgKOH/g): 215 parts by mass (the ratio of isocyanate groups of HDI to the hydroxyl groups of polyester polyol A3 The temperature in the reactor was maintained at 100° C.
  • Example 18 (Production of polyisocyanate composition PA-a18) A four-necked flask equipped with a thermometer, stirring blades, and a reflux condenser was charged with 100 parts by mass of HDI under a nitrogen stream, and polyester polyol A1: 115 parts by mass (the ratio of the isocyanate group of HDI to the hydroxyl group of polyester polyol A1 was The temperature in the reactor was maintained at 100° C. while stirring the amount that gives a molar ratio of 10.2. The reaction was terminated when the yield reached 52.2% by mass. After filtering the reaction liquid, unreacted HDI was removed by a thin film distillation apparatus to obtain an intermediate of a polyisocyanate composition.
  • the obtained intermediate of the polyisocyanate composition was placed in a four-necked flask equipped with a thermometer, a stirring blade, and a reflux condenser under a nitrogen stream, and 100 parts by mass of 1,3-butanediol: 1.0 Parts by mass were added, and the temperature inside the reactor was maintained at 160° C. for 1 hour to obtain polyisocyanate component PA-a18.
  • the resulting polyisocyanate composition PA-a18 was analyzed by H-NMR and C-NMR to confirm the presence of urethane groups, allophanate groups, uretdione groups, and urea groups. ratio was the highest. After that, ethyl acetate was added to the obtained polyisocyanate composition to dilute it to a solid content of 70% by mass, and it was liquid at 23°C.
  • Example 19 (Production of polyisocyanate composition PA-a19) A four-necked flask equipped with a thermometer, a stirring blade, and a reflux condenser was charged with 100 parts by mass of HDI under a nitrogen stream, and trifunctional polycaprolactone polyol (hereinafter sometimes referred to as "polyester polyol B1"). ) (manufactured by Daicel Corporation, trade name “PLAXEL 308”, number average molecular weight 850, hydroxyl value 195.3 mgKOH/g, acid value 0.38 mgKOH/g): 35.0 parts by mass (HDI isocyanate for the hydroxyl group of polyester polyol B1 The temperature in the reactor was maintained at 100° C.
  • polyester polyol B1 was added to 100 parts by mass of the obtained intermediate of the polyisocyanate composition in a four-necked flask equipped with a thermometer, a stirring blade, and a reflux condenser under a nitrogen stream.
  • 2-ethylhexyl acid phosphate (manufactured by Johoku Kagaku Kogyo Co., Ltd., trade name “JP508T”) was added at 90 mass ppm with respect to the resin content, and the temperature in the reactor was maintained at 95 ° C. for 120 minutes to obtain a polyisocyanate component PA. -a19 was obtained.
  • the resulting polyisocyanate composition PA-a19 was analyzed by H-NMR and C-NMR to confirm the presence of urethane groups and allophanate groups, and the molar ratio of urethane groups was the largest among these groups.
  • ethyl acetate was added to the obtained polyisocyanate composition to dilute it to a solid content of 70% by mass, and it was liquid at 23°C.
  • Example 20 (Production of polyisocyanate composition PA-a20) A four-necked flask equipped with a thermometer, a stirring blade, and a reflux condenser was charged with 100 parts by mass of HDI under a nitrogen stream, and trifunctional polycaprolactone polyol (hereinafter sometimes referred to as "polyester polyol B1").
  • the polyisocyanate was obtained by removing the unreacted HDI monomer with a thin-film distillation apparatus.
  • the resulting polyisocyanate had an isocyanate group content of 23.1% by mass and an average isocyanate functional group number of 3.4.
  • the resulting polyisocyanate composition PA-b4 was analyzed by H-NMR and C-NMR to confirm the presence of isocyanurate groups, and among these groups, the isocyanurate groups had the highest molar ratio.
  • the resulting polyisocyanate had an isocyanate group content of 23.4% by mass and an average isocyanate functional group number of 3.4.
  • the resulting polyisocyanate composition PA-b5 was analyzed by H-NMR and C-NMR to confirm the presence of biuret.
  • Tables 1 to 3 below show the physical properties of the polyisocyanate compositions obtained in Examples and Comparative Examples, and the results of evaluation by the methods described above.
  • Comparative Example 1 when the stress at the elongation rate of 140% was measured, the elongation rate was not elongated until the elongation rate was 140%, the breaking point stress was 73 MPa, and the measurement was impossible. bottom.
  • the comparative examples 4 and 5 are also the same.
  • each abbreviation means the following compounds.
  • A'1 Polytetramethylene ether glycol, manufactured by Mitsubishi Chemical Corporation, trade name "PTMG1000", number average molecular weight 1000
  • A'2 Polyether polyol, manufactured by Asahi Glass Co., Ltd., trade name "Excenol 2020”, number average molecular weight 2000
  • B3 trifunctional polycaprolactone polyol, manufactured by Daicel Corporation, trade name “PLAXEL 305”, number average molecular weight 550
  • B'1 trimethylolpropane (TMP)
  • the polyisocyanate compositions PA-b1 to PA-b5 (Comparative Examples 1 to 5) derived from a diisocyanate and a polyol that does not have the above physical properties, the polyisocyanate composition
  • the hardness and transparency of the cured film 1 obtained by curing the product alone, the stress, elongation rate, and tensile breaking stress at 140% elongation when used as the cured film 2, and when used as an adhesive resin sheet A product excellent in all of adhesiveness, curability and transparency was not obtained.
  • the cured film obtained by curing the polyisocyanate composition alone has good flexibility and transparency, and has excellent elongation and tensile breaking stress. It is possible to provide a polyisocyanate composition from which an adhesive resin composition and an adhesive resin sheet having excellent adhesive strength, curability and transparency can be obtained. Further, the present invention can provide a laminated film comprising the adhesive resin sheet.

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