WO2024150783A1 - Adhesive composition, adhesive layer, optical film with adhesive layer, and display device - Google Patents

Adhesive composition, adhesive layer, optical film with adhesive layer, and display device Download PDF

Info

Publication number
WO2024150783A1
WO2024150783A1 PCT/JP2024/000362 JP2024000362W WO2024150783A1 WO 2024150783 A1 WO2024150783 A1 WO 2024150783A1 JP 2024000362 W JP2024000362 W JP 2024000362W WO 2024150783 A1 WO2024150783 A1 WO 2024150783A1
Authority
WO
WIPO (PCT)
Prior art keywords
meth
group
mass
acrylate
adhesive layer
Prior art date
Application number
PCT/JP2024/000362
Other languages
French (fr)
Japanese (ja)
Inventor
由紀 西上
光敬 佐▲瀬▼
昂大 久保
大一 近藤
Original Assignee
住友化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Publication of WO2024150783A1 publication Critical patent/WO2024150783A1/en

Links

Images

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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • 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
    • 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
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • 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]

Definitions

  • the present invention relates to a pressure-sensitive adhesive composition, and further to a pressure-sensitive adhesive layer containing the pressure-sensitive adhesive composition, and an optical film with a pressure-sensitive adhesive layer.
  • Optical films such as polarizing plates used in image display devices such as liquid crystal display devices and organic electroluminescence (organic EL) display devices are often attached to other components (for example, image display elements such as liquid crystal cells in liquid crystal display devices) via an adhesive layer.
  • Image display devices are being deployed in touch input display device applications such as smartphones and tablet terminals.
  • an adhesive layer may be disposed on a metal layer composed of metal wiring.
  • the metal layer may corrode in high temperature and high humidity environments.
  • Patent Document 1 proposes an adhesive composition that contains a (meth)acrylic resin, a specific silane compound, and an ionic compound as an adhesive composition that can inhibit corrosion of a metal layer.
  • the object of the present invention is to provide an adhesive that exhibits excellent heat resistance and durability and metal corrosion resistance.
  • the present invention provides the following pressure-sensitive adhesive composition, pressure-sensitive adhesive layer, pressure-sensitive adhesive layer-attached optical film, and display device.
  • a composition comprising a (meth)acrylic resin (A), a crosslinking agent (B), a silane compound (C), and an ionic compound (D),
  • the (meth)acrylic resin (A) contains a structural unit derived from an alkyl methacrylate (a) having a homopolymer glass transition temperature of 30° C. or higher, a structural unit derived from a hydroxyl group-containing (meth)acrylate (b), and a structural unit derived from a carboxyl group-containing monomer (c),
  • the silane compound (C) is represented by the following formula (I):
  • L represents an alkanediyl group having 1 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and —CH 2 — constituting the alkanediyl group or the alicyclic hydrocarbon group may be replaced by —O— or —C( ⁇ O)—;
  • a 1 represents an alkyl group having 1 to 5 carbon atoms;
  • a 2 , A 3 , A 4 , A 5 and A 6 each independently represent an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.
  • a pressure-sensitive adhesive composition comprising a compound represented by the formula: [2] The pressure-sensitive adhesive composition according to [1], containing 0.01 parts by mass or more and 2.0 parts by mass or less of the silane compound (C) per 100 parts by mass of the (meth)acrylic resin (A). [3] The pressure-sensitive adhesive composition according to [1] or [2], containing, relative to 100 parts by mass of all structural units constituting the (meth)acrylic resin (A), 1 part by mass or more and 15 parts by mass or less of a structural unit derived from an alkyl methacrylate (a) having a homopolymer glass transition temperature of 30° C.
  • the (meth)acrylic resin (A) has a weight average molecular weight of 1,000,000 or more and 3,200,000 or less.
  • the pressure-sensitive adhesive composition according to any one of [1] to [9], comprising 0.1 parts by mass or more and 10.0 parts by mass or less of the ionic compound (D) per 100 parts by mass of the (meth)acrylic resin (A).
  • the ionic compound (D) is represented by the following formula:
  • the present invention provides an adhesive that exhibits excellent heat resistance and durability and metal corrosion resistance.
  • FIG. 1 is a schematic cross-sectional view showing an example of a pressure-sensitive adhesive layer-attached optical film according to the present invention.
  • FIG. 2 is a schematic cross-sectional view showing another example of a pressure-sensitive adhesive layer-attached optical film according to the present invention.
  • FIG. 1 is a schematic cross-sectional view showing an example of an optical laminate according to the present invention.
  • FIG. 2 is a schematic cross-sectional view showing another example of the optical laminate according to the present invention.
  • 1 is a schematic cross-sectional view showing an example of an image display device according to the present invention.
  • (Meth)acrylic resin (A) contained in the pressure-sensitive adhesive composition according to the present invention contains a structural unit derived from an alkyl methacrylate (a) [hereinafter also referred to as alkyl methacrylate (a)] having a homopolymer glass transition temperature of 30° C. or higher, a structural unit derived from a hydroxyl group-containing (meth)acrylate (b), and a structural unit derived from a carboxyl group-containing monomer (c).
  • alkyl methacrylate (a) having a homopolymer glass transition temperature of 30° C. or higher
  • a structural unit derived from a hydroxyl group-containing (meth)acrylate (b) a structural unit derived from a carboxyl group-containing monomer (c).
  • (meth)acrylic means that it may be either acrylic or methacrylic.
  • (Meth)acrylate means that it may be either acrylate or methacrylate.
  • the alkyl methacrylate (a) is an alkyl methacrylate having a homopolymer glass transition temperature (Tg) of 30°C or higher.
  • Tg homopolymer glass transition temperature
  • a literature value such as that in the POLYMER HANDBOOK (Wiley-Interscience) can be used.
  • the Tg of the alkyl methacrylate (a) homopolymer is preferably 50°C or higher, more preferably 60°C or higher, and even more preferably 80°C or higher.
  • There is no particular upper limit for the Tg of the alkyl methacrylate (a) homopolymer but it is usually 250°C or lower.
  • alkyl methacrylate (a) examples include alkyl methacrylates having a linear or branched alkyl group having 1 to 6 carbon atoms, such as methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, propyl methacrylate, isopropyl methacrylate, 3,3-dimethylbutyl methacrylate, and 3,3-dimethyl-2-butyl methacrylate, and n-stearyl methacrylate.
  • alkyl methacrylates having a linear or branched alkyl group having 1 to 6 carbon atoms such as methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, propyl methacrylate, isopropyl methacrylate, 3,3-d
  • the alkyl methacrylate (a) may be an alkyl methacrylate (cycloalkyl methacrylate) having an alicyclic structure.
  • the alicyclic structure may be a cycloparaffin structure having a carbon number of usually 5 or more, preferably about 5 to 7.
  • Specific examples of the alkyl methacrylate having an alicyclic structure include isobornyl methacrylate, cyclohexyl methacrylate, dicyclopentanyl methacrylate, trimethylcyclohexyl methacrylate, tert-butylcyclohexyl methacrylate, and 1-adamantyl methacrylate.
  • the alkyl methacrylate (a) may be used alone or in combination of two or more kinds.
  • alkyl methacrylate (a) an alkyl methacrylate having a linear or branched alkyl group having 1 to 4 carbon atoms, or an alkyl methacrylate having an alicyclic structure is preferred, and in particular, methyl methacrylate, tert-butyl methacrylate, isobornyl methacrylate, and cyclohexyl methacrylate are preferred.
  • the content of the structural units derived from alkyl methacrylate (a) is preferably 1 to 15 parts by mass, more preferably 3 to 13 parts by mass, even more preferably 4 to 12 parts by mass, and particularly preferably 5 to 11 parts by mass, per 100 parts by mass of all structural units constituting the (meth)acrylic resin (A). If it is within the above range, the mechanical strength is improved by improving the cohesiveness of the adhesive, and the flexibility and adhesiveness of the adhesive can be ensured, which is advantageous for heat resistance durability.
  • Hydroxy group-containing (meth)acrylate (b) can be a (meth)acrylate containing one or more hydroxy groups in the molecular chain.
  • Specific examples of hydroxy group-containing (meth)acrylate (b) include those represented by the following formula (1):
  • n represents an integer of 1 to 5;
  • a 1 represents a hydrogen atom or an alkyl group;
  • X1 represents a methylene group which may have a substituent.
  • n 2 or more, the X 1 may be the same or different.
  • Examples of the compound include compounds represented by the following formula:
  • examples of the alkyl group that can constitute A1 include alkyl groups having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a s-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. Of these, a methyl group is preferred.
  • examples of the substituent that the methylene group that can constitute X1 may have include, for example, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a s-butyl group, a tert-butyl group, a pentyl group, or a hexyl group, preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms), a cycloalkyl group (a cyclopentyl group, a cyclohexyl group, etc.), an aryl group (a phenyl group, an alkylphenyl group (a fluorine
  • halogen atom an alkyl group, an alkoxy group, an aryloxy group, etc. are preferred, and an alkyl group (e.g., a methyl group, an ethyl group, etc.) is particularly preferred.
  • n may be, for example, an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 2.
  • X 1 may be the same or different. That is, when n is 2 or more, X 1 may be composed of an unsubstituted methylene group, may be composed of an unsubstituted methylene group and a methylene group having a substituent, or may be composed of a methylene group having a substituent.
  • the substituents may be the same or different.
  • hydroxy group-containing (meth)acrylate (b) include 1-hydroxy C1 to C8 alkyl (meth)acrylates such as 1-hydroxymethyl (meth)acrylate, 1-hydroxyethyl (meth)acrylate, 1-hydroxyheptyl (meth)acrylate, 1-hydroxybutyl (meth)acrylate, and 1-hydroxypentyl (meth)acrylate; 2-hydroxy C2 to C9 alkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxypentyl (meth)acrylate, and 2-hydroxyhexyl (meth)acrylate; 3-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 3-hydroxybutyl (meth)acrylate; 3-hydroxy C3 to C10 alkyl (meth)acrylates such as 4-hydroxybutyl (meth)acrylate, 4-hydroxypentyl (
  • hydroxy-containing (meth)acrylates in which n is 2 such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate
  • hydroxy-containing (meth)acrylates in which n is 3 such as 3-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 3-hydroxypentyl (meth)acrylate
  • hydroxy-containing (meth)acrylates in which n is 2 are preferred, and among these, 2-hydroxyethyl (meth)acrylate is preferred.
  • 2-Hydroxyethyl (meth)acrylate is advantageous in forming a uniform crosslinked structure, and can improve mechanical strength and heat resistance durability.
  • the hydroxyl group-containing (meth)acrylate (b) may be used alone or in combination of two or more kinds.
  • the content of the structural units derived from the hydroxyl group-containing (meth)acrylate (b) is preferably from 0.3 to 5.5 parts by mass, more preferably from 0.4 to 4.0 parts by mass, even more preferably from 0.5 to 3.0 parts by mass, and particularly preferably from 0.5 to 2.5 parts by mass, relative to 100 parts by mass of all structural units constituting the (meth)acrylic resin (A).
  • the (meth)acrylic resin (A) is preferably a (meth)acrylic resin that contains 1 part by mass or more and 15 parts by mass or less of structural units derived from alkyl methacrylate (a) and 0.3 parts by mass or more and 5.5 parts by mass or less of structural units derived from hydroxyl group-containing (meth)acrylate (b) per 100 parts by mass of all structural units constituting the (meth)acrylic resin (A).
  • carboxyl group-containing monomer (c) examples include (meth)acrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, and carboxyalkyl (meth)acrylates (e.g., carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate). Of these, acrylic acid is preferred. Acrylic acid promotes the reaction between the hydroxyl group-containing (meth)acrylate (b) and the crosslinking agent, which is advantageous for the formation of a uniform crosslinked structure and can improve heat resistance and durability.
  • the carboxyl group-containing monomer (c) may be used alone or in combination of two or more types.
  • the content of the structural unit derived from the carboxyl group-containing monomer (c) may be 0.01 parts by mass or more and 5.5 parts by mass or less relative to 100 parts by mass of all structural units constituting the (meth)acrylic resin (A), and from the viewpoint of metal corrosion resistance and heat resistance durability, it is preferably 0.05 parts by mass or more and 3 parts by mass or less, and more preferably 0.1 parts by mass or more and 2 parts by mass or less.
  • the mass ratio (c)/(b) of the constituent units derived from the carboxyl group-containing monomer (c) to the constituent units derived from the hydroxyl group-containing (meth)acrylate (b) is preferably 0.06 or more and 1.0 or less, more preferably 0.06 or more and 0.9 or less, even more preferably 0.08 or more and 0.8 or less, and particularly preferably 0.1 or more and 0.7 or less, from the viewpoint of metal corrosion resistance and heat resistance durability.
  • the (meth)acrylic resin (A) may further contain structural units derived from alkyl acrylates, structural units derived from alkyl methacrylates having a homopolymer glass transition temperature (Tg) of less than 30°C, structural units derived from substituted alkyl (meth)acrylates, structural units derived from monomers having polar functional groups other than hydroxyl groups, structural units derived from (meth)acrylamide monomers, structural units derived from styrene monomers, structural units derived from vinyl monomers, structural units derived from monomers having multiple (meth)acryloyl groups in the molecule, etc.
  • Tg homopolymer glass transition temperature
  • the (meth)acrylic resin (A) preferably contains an alkyl acrylate having a homopolymer Tg of less than 0° C.
  • alkyl acrylates having a homopolymer Tg of less than 0° C. include linear or branched alkyl acrylates having an alkyl group with about 2 to 12 carbon atoms, such as ethyl acrylate, n- and i-propyl acrylate, n- and i-butyl acrylate, n-pentyl acrylate, n- and i-hexyl acrylate, n-heptyl acrylate, n- and i-octyl acrylate, 2-ethylhexyl acrylate, n- and i-nonyl acrylate, n- and i-decyl acrylate, and n-dodecyl acrylate.
  • the alkyl acrylate having a homopolymer Tg of less than 0°C may be an alkyl acrylate (cycloalkyl acrylate) having an alicyclic structure, but from the viewpoint of conformability (or flexibility or adhesion) to the optical film, an alkyl acrylate having 2 to 10 carbon atoms, preferably an alkyl acrylate having 3 to 8 carbon atoms, and more preferably an alkyl acrylate having 4 to 6 carbon atoms is preferred. Use of these alkyl acrylates can improve conformability, which is advantageous for, for example, peel resistance. These alkyl acrylates can be used alone or in combination of two or more kinds.
  • the (meth)acrylic resin (A) preferably contains an alkyl acrylate having a homopolymer Tg of 0°C or higher.
  • alkyl acrylates having a homopolymer Tg of 0°C or higher include methyl acrylate, stearyl acrylate, and t-butyl acrylate.
  • the alkyl acrylate having a homopolymer Tg of 0°C or higher may be an alkyl acrylate (cycloalkyl acrylate) having an alicyclic structure.
  • the use of these alkyl alkyl acrylates further improves the mechanical strength of the adhesive and is advantageous in terms of heat resistance and durability. These alkyl acrylates may be used alone or in combination of two or more.
  • the alicyclic structure may be a cycloparaffin structure having a carbon number of usually 5 or more, preferably about 5 to 7.
  • alkyl acrylates having a homopolymer with an alicyclic structure and a Tg of 0°C or higher include isobornyl acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, cyclododecyl acrylate, methylcyclohexyl acrylate, trimethylcyclohexyl acrylate, tert-butylcyclohexyl acrylate, cyclohexyl ⁇ -ethoxy acrylate, etc.
  • alkyl methacrylates with a homopolymer Tg of less than 30°C include linear or branched alkyl methacrylates with an alkyl group carbon number of about 4 to 12, such as n-butyl methacrylate, n-pentyl methacrylate, n- and i-hexyl methacrylate, n-heptyl methacrylate, n- and i-octyl methacrylate, 2-ethylhexyl methacrylate, n- and i-nonyl methacrylate, n-decyl methacrylate, and n-dodecyl methacrylate.
  • alkyl methacrylates can be used alone or in combination of two or more.
  • alkyl (meth)acrylate containing a substituent examples include alkyl (meth)acrylates in which a substituent has been introduced into the alkyl group in the alkyl (meth)acrylate (the hydrogen atom of the alkyl group has been replaced by a substituent).
  • the substituent may be, for example, an aryl group (such as a phenyl group), an aryloxy group (such as a phenoxy group), an alkoxy group (such as a methoxy group, an ethoxy group), etc.
  • alkyl acrylate containing a substituent examples include an alkoxyalkyl acrylate (such as 2-methoxyethyl acrylate, ethoxymethyl acrylate, etc.), an aryloxyalkyl acrylate (such as phenoxyethyl acrylate, etc.), an aryloxypolyalkylene glycol monoacrylate, a polyalkylene glycol monoacrylate, etc.
  • alkyl acrylates can be used alone or in combination of two or more kinds.
  • an alkyl acrylate containing an aromatic ring such as an aryl group or an aryloxy group, it is possible to improve the white spots of the polarizing plate during a durability test.
  • the alkylene group of the aryloxy polyalkylene glycol monoacrylate and polyalkylene glycol monoacrylate may be, for example, a C1-C6 alkylene group (preferably an ethylene group, etc.) such as a methylene group, an ethylene group, or a propylene group, and the repeating unit of the oxyalkylene group may be, for example, 2 to 7, preferably 2 to 5 (particularly 2), from the viewpoint of the durability of the adhesive layer formed from the adhesive composition.
  • phenoxy di- to hepta C1-C3 alkylene glycol monoacrylates such as phenoxy diethylene glycol acrylate
  • di- to hepta C1-C3 alkylene glycol monoacrylates such as diethylene glycol monoacrylate.
  • Monomers having a polar functional group other than a hydroxyl group include (meth)acrylates having a substituent such as a substituted or unsubstituted amino group, or a heterocyclic group such as an epoxy group.
  • Specific examples include monomers having a heterocyclic group such as acryloylmorpholine, vinylcaprolactam, N-vinyl-2-pyrrolidone, vinylpyridine, tetrahydrofurfuryl (meth)acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, glycidyl (meth)acrylate, and 2,5-dihydrofuran; and monomers having a substituted or unsubstituted amino group such as aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, and dimethylaminopropyl (meth)acryl
  • compositions can be used alone or in combination of two or more. From the viewpoint of preventing a decrease in the releasability of the separate film that can be laminated to the adhesive layer, it is preferable that the composition does not substantially contain structural units derived from monomers having an amino group. "Substantially free” means that the amount is less than 1.0 part by mass per 100 parts by mass of all structural units constituting the (meth)acrylic resin (A).
  • Examples of (meth)acrylamide monomers include N-methylol (meth)acrylamide, N-(2-hydroxyethyl) (meth)acrylamide, N-(3-hydroxypropyl) (meth)acrylamide, N-(4-hydroxybutyl) (meth)acrylamide, N-(5-hydroxypentyl) (meth)acrylamide, N-(6-hydroxyhexyl) (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, and N-isopropyl (meth)acrylamide.
  • styrene monomers include styrene; alkyl styrenes such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, and octylstyrene; halogenated styrenes such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, and iodostyrene; nitrostyrene; acetylstyrene; methoxystyrene; and divinylbenzene.
  • alkyl styrenes such as methylstyrene, dimethylstyrene, trimethylsty
  • Vinyl monomers include, for example, fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, and vinyl laurate; vinyl halides such as vinyl chloride and vinyl bromide; vinylidene halides such as vinylidene chloride; nitrogen-containing aromatic vinyls such as vinylpyridine, vinylpyrrolidone, and vinylcarbazole; and conjugated diene monomers such as butadiene, isoprene, and chloroprene.
  • Examples of monomers having multiple (meth)acryloyl groups in the molecule include monomers having two (meth)acryloyl groups in the molecule, such as 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and tripropylene glycol di(meth)acrylate; and monomers having three (meth)acryloyl groups in the molecule, such as trimethylolpropane tri(meth)acrylate.
  • the weight average molecular weight (Mw) of the (meth)acrylic resin (A) is preferably 1 million or more and 3.2 million or less, more preferably 1.1 million to 3.1 million, more preferably 1.2 million to 3 million, and particularly preferably 1.3 million to 2.9 million, from the viewpoint of metal corrosion resistance and heat resistance and durability.
  • the molecular weight distribution (Mw/Mn) which is expressed as the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is usually 1.5 to 10, preferably 2 to 8, and more preferably 2.5 to 7.
  • the weight average molecular weight can be analyzed by gel permeation chromatography and is a value converted into standard polystyrene.
  • the (meth)acrylic resin (A) preferably has a glass transition temperature (Tg) of -45°C or higher and -10°C or lower, more preferably -40°C or higher and -15°C or lower, and even more preferably -38°C or higher and -20°C or lower, from the viewpoints of mechanical strength and heat resistance and durability.
  • Tg glass transition temperature
  • the (meth)acrylic resin (A) (or a mixture of two or more types) is preferably dissolved in ethyl acetate to a concentration of 20% by mass, and the solution preferably exhibits a viscosity of 20 Pa ⁇ s or less at 25°C, and more preferably 0.1 Pa ⁇ s or more and 7 Pa ⁇ s or less.
  • the viscosity can be measured using a Brookfield viscometer.
  • the (meth)acrylic resin (A) can be produced by known methods such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization.
  • a polymerization initiator is usually used in the production of the (meth)acrylic resin (A).
  • the polymerization initiator is used in an amount of about 0.001 to 5 parts by mass per 100 parts by mass of the total of all monomers used in the production of the (meth)acrylic resin (A).
  • the (meth)acrylic resin (A) may also be produced by a method in which polymerization is advanced by active energy rays such as ultraviolet rays.
  • the polymerization initiator a thermal polymerization initiator or a photopolymerization initiator is used.
  • a photopolymerization initiator for example, 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone can be mentioned.
  • thermal polymerization initiator for example, azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl-2,2'-azobis(2-methylpropionate), and 2,2'-azobis(2-hydroxymethylpropionitrile); lauryl peroxide;
  • the peroxide include organic peroxides such as tert-butyl hydroperoxide, benzoyl peroxide, tert-butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, dipropyl peroxydicarbonate, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate
  • the solution polymerization method is preferred as a method for producing the (meth)acrylic resin (A).
  • One example of the solution polymerization method is to mix the monomer and an organic solvent, add a thermal polymerization initiator under a nitrogen atmosphere, and stir for about 3 to 10 hours at about 40 to 90°C, preferably about 60 to 80°C.
  • the monomer and the thermal polymerization initiator may be added continuously or intermittently during polymerization, or may be added in a dissolved state in an organic solvent.
  • organic solvents examples include aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as propyl alcohol and isopropyl alcohol; and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.
  • the pressure-sensitive adhesive composition further contains a crosslinking agent (B).
  • the crosslinking agent (B) can be a compound that reacts with a structural unit derived from a polar functional group-containing monomer in the (meth)acrylic resin (A) and crosslinks the (meth)acrylic resin (A).
  • Specific examples include isocyanate-based compounds, epoxy-based compounds, aziridine-based compounds, and metal chelate-based compounds. Of these, isocyanate-based compounds, epoxy-based compounds, and aziridine-based compounds have at least two functional groups in the molecule that can react with the polar functional group in the (meth)acrylic resin.
  • the crosslinking agent (B) may be used alone or in combination of two or more.
  • isocyanate compound a compound having at least two isocyanato groups (-NCO) in the molecule is preferred, and examples thereof include aliphatic isocyanate compounds (e.g., hexamethylene diisocyanate, etc.), alicyclic isocyanate compounds (e.g., isophorone diisocyanate), aromatic isocyanate compounds (e.g., tolylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, etc.).
  • aliphatic isocyanate compounds e.g., hexamethylene diisocyanate, etc.
  • alicyclic isocyanate compounds e.g., isophorone diisocyanate
  • aromatic isocyanate compounds
  • the crosslinking agent (B) may be an adduct of an isocyanate compound with a polyhydric alcohol compound (e.g., an adduct with glycerol, trimethylolpropane, etc.), an isocyanurate, a biuret-type compound, a urethane prepolymer type isocyanate compound obtained by addition reaction with a polyether polyol, a polyester polyol, an acrylic polyol, a polybutadiene polyol, a polyisoprene polyol, etc., or a derivative thereof.
  • the crosslinking agent (B) may be used alone or in combination of two or more.
  • representative examples include aromatic isocyanate compounds (e.g., tolylene diisocyanate, xylylene diisocyanate), aliphatic isocyanate compounds (e.g., hexamethylene diisocyanate), or adducts of these with polyhydric alcohol compounds (glycerol, trimethylolpropane).
  • aromatic isocyanate compounds e.g., tolylene diisocyanate, xylylene diisocyanate
  • aliphatic isocyanate compounds e.g., hexamethylene diisocyanate
  • adducts of these with polyhydric alcohol compounds glycerol, trimethylolpropane
  • Epoxy compounds are compounds that have at least two epoxy groups in the molecule.
  • Specific compounds include, for example, bisphenol A type epoxy resins, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, N,N-diglycidylaniline, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N'-diglycidylaminomethyl)cyclohexane, etc.
  • Two or more types of epoxy compounds can also be mixed and used.
  • Aziridine compounds are compounds that have at least two three-membered ring structures, also known as ethyleneimines, each consisting of one nitrogen atom and two carbon atoms. Specific examples of compounds include diphenylmethane-4,4'-bis(1-aziridinecarboxamide), toluene-2,4-bis(1-aziridinecarboxamide), triethylenemelamine, isophthaloylbis-1-(2-methylaziridine), tris-1-aziridinylphosphine oxide, hexamethylene-1,6-bis(1-aziridinecarboxamide), trimethylolpropane-tris- ⁇ -aziridinylpropionate, and tetramethylolmethane-tris- ⁇ -aziridinylpropionate.
  • metal chelate compounds include compounds in which acetylacetone or ethyl acetoacetate is coordinated with polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium.
  • isocyanate compounds are preferred, and aromatic isocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, and their adducts with polyhydric alcohol compounds (e.g., glycerol, trimethylolpropane, etc.) are more preferred.
  • polyhydric alcohol compounds e.g., glycerol, trimethylolpropane, etc.
  • the content of the crosslinking agent (B) is preferably 0.2 parts by mass or more and 5.0 parts by mass or less, more preferably 0.3 parts by mass or more and 2.0 parts by mass or less, based on 100 parts by mass of the solid content of the (meth)acrylic resin (A) (when two or more types are used, the total amount of the (meth)acrylic resin (A)).
  • the content is preferably 0.2 parts by mass or more and 5.0 parts by mass or less, more preferably 0.3 parts by mass or more and 2.0 parts by mass or less.
  • silane Compound (C) The silane compound (C) is represented by the following formula (I):
  • L represents an alkanediyl group having 1 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and —CH 2 — constituting the alkanediyl group or the alicyclic hydrocarbon group may be replaced by —O— or —C( ⁇ O)—;
  • a 1 represents an alkyl group having 1 to 5 carbon atoms;
  • a 2 , A 3 , A 4 , A 5 and A 6 each independently represent an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.
  • alkanediyl group having 1 to 20 carbon atoms that can constitute L include a methylene group, a 1,2-ethanediyl group, a 1,3-propanediyl group, a 1,4-butanediyl group, a 1,5-pentanediyl group, a 1,6-hexanediyl group, a 1,7-heptanediyl group, a 1,8-octanediyl group, a 1,9-nonanediyl group, a 1,10-decanediyl group, a 1,12-dodecanediyl group, a 1,14-tetradecanediyl group, a 1,16-hexadecanediyl group, a 1,18-octadecanediyl group, and a 1,20-icosanediyl group.
  • divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a 1,3-cyclopentanediyl group and a 1,4-cyclohexanediyl group.
  • alkanediyl group and the alicyclic hydrocarbon group in which —CH 2 — is replaced by —O— or —C( ⁇ O)— include —CH 2 CH 2 —O—CH 2 CH 2 —, —CH 2 CH 2 —O—CH 2 CH 2 —O—CH 2 CH 2 —, —CH 2 CH 2 —O—CH 2 CH 2 —O—CH 2 CH 2 —O—CH 2 CH 2 —O—CH 2 CH 2 —, —CH 2 CH 2 —C( ⁇ O)—O—CH 2 CH 2 —, —CH 2 CH 2 —O—CH 2 CH 2 —C( ⁇ O)—O—CH 2 CH 2 —, —CH 2 CH 2 —O—CH 2 CH 2 —C( ⁇ O)—
  • examples of the alkyl group having 1 to 5 carbon atoms which may constitute A 1 , A 2 , A 3 , A 4 , A 5 and A 6 include various pentyl groups such as methyl group, ethyl group, n- and i-propyl group, n-, i- and t-butyl group, and n-, i- and t-pentyl group.
  • examples of the alkoxy group having 1 to 5 carbon atoms which may constitute A 2 , A 3 , A 4 , A 5 and A 6 include various pentyloxy groups such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, t-butoxy group, n-, i- and t-pentyloxy groups, etc.
  • the number of carbon atoms in the alkyl group and alkoxy group is each independently preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2.
  • silane compound represented by formula (I) are shown below.
  • a 7 is an alkyl group having 1 to 5 carbon atoms
  • m is an integer from 1 to 20.
  • the silane compound (C) more preferably contains a silane compound represented by the above formula (II) in which m is an integer of 4 to 20, further preferably contains a silane compound represented by the above formula (II) in which m is an integer of 6 to 8, and particularly preferably contains a silane compound represented by the above formula (II) in which A 1 O and OA 7 are each independently an alkoxy group having 1 to 3 carbon atoms (e.g., 1 or 2 carbon atoms), and A 3 , A 4 , A 5 , and A 6 are each independently an alkyl group or alkoxy group having 1 to 3 carbon atoms (e.g., 1 or 2 carbon atoms), and A 1 O, A 3 , A 4 , A 5 , A 6 and OA More particularly preferred are silane compounds represented by the above formula (II) in which each 7 is independently an alkoxy group having 1 to 3 carbon atoms (e.g., 1 or 2 carbon atoms), such as 1,
  • the adhesive composition may contain one or more other silane compounds in addition to the silane compound represented by formula (I).
  • other silane compounds include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethoxydimethylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 8-glycidoxyoctyltrimethoxysilane.
  • silane compounds can include silicone oligomers.
  • Specific examples of silicone oligomers, expressed in the form of combinations of monomers, are as follows:
  • 3-mercaptopropyltrimethoxysilane-tetramethoxysilane oligomer 3-mercaptopropyltrimethoxysilane-tetraethoxysilane oligomer, 3-mercaptopropyltriethoxysilane-tetramethoxysilane oligomer, mercaptopropyl group-containing oligomers such as 3-mercaptopropyltriethoxysilane-tetraethoxysilane oligomer; mercaptomethyltrimethoxysilane-tetramethoxysilane oligomer, mercaptomethyltrimethoxysilane-tetraethoxysilane oligomer, mercaptomethyltriethoxysilane-tetramethoxysilane oligomer, mercaptomethyl group-containing oligomers such as mercaptomethyltriethoxysilane-tetraethoxysilane oligomers; 3-
  • 3-acryloyloxypropyltrimethoxysilane-tetramethoxysilane oligomer 3-acryloyloxypropyltrimethoxysilane-tetraethoxysilane oligomer, 3-acryloyloxypropyltriethoxysilane-tetramethoxysilane oligomer, 3-acryloyloxypropyltriethoxysilane-tetraethoxysilane oligomer, 3-acryloyloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer, 3-acryloyloxypropylmethyldimethoxysilane-tetraethoxysilane oligomer, 3-acryloyloxypropylmethyldiethoxysilane-tetramethoxysilane oligomer, acryloyloxypropyl group-containing oligomers such as 3-acryloyloxypropylmethyldiethoxysilane-t
  • 3-aminopropyltrimethoxysilane-tetramethoxysilane copolymer 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetramethoxysilane copolymer, Amino group-containing copolymers such as 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer.
  • the content of the silane compound represented by formula (I) in the total of all silane compounds is preferably 70% by weight or more, more preferably 80% by weight or more, and even more preferably 90% by weight or more, and it is particularly preferable that the adhesive composition contains only the silane compound represented by formula (I) as the silane compound (C).
  • the content of the silane compound (C) in the adhesive composition is preferably 0.01 parts by mass or more and 2.0 parts by mass or less, and more preferably 0.1 parts by mass or more and 1.5 parts by mass or less, per 100 parts by mass of the solid content of the (meth)acrylic resin (A) (when two or more types are used, the total amount of the (meth)acrylic resin (A)).
  • the content is preferably 0.01 parts by mass or more and 2.0 parts by mass or less, and more preferably 0.1 parts by mass or more and 1.5 parts by mass or less.
  • the ionic compound (D) may include a compound composed of a cation and an anion. From the viewpoint of metal corrosion resistance and heat resistance durability, the ionic compound (D) is preferably represented by the following formula:
  • the anion is selected from the group consisting of compounds represented by the formula:
  • the cation may be either an organic cation or an inorganic cation.
  • the ionic compound (D) may contain one or more kinds.
  • organic cations include pyridinium cation, imidazolium cation, piperidinium cation, pyrrolidinium cation, tetrahydropyridinium cation, dihydropyridinium cation, tetrahydropyrimidium cation, dihydropyrimidium cation, pyrazolium cation, pyrazolinium cation, ammonium cation, sulfonium cation, phosphonium cation, etc.
  • the organic cation may have a substituent.
  • inorganic cations include alkali metal ions such as lithium cation [Li + ], sodium cation [Na + ], potassium cation [K + ], and cesium cation [Cs + ]; and alkaline earth metal ions such as beryllium cation [Be 2+ ], magnesium cation [Mg 2+ ], and calcium cation [Ca 2+ ].
  • alkali metal ions such as lithium cation [Li + ], sodium cation [Na + ], potassium cation [K + ], and cesium cation [Cs + ]
  • alkaline earth metal ions such as beryllium cation [Be 2+ ], magnesium cation [Mg 2+ ], and calcium cation [Ca 2+ ].
  • the cation is preferably an organic cation from the viewpoint of compatibility with the (meth)acrylic resin (A), and more preferably a nitrogen atom-containing organic cation (which may have a substituent) such as a pyridinium cation, imidazolium cation, piperidinium cation, pyrrolidinium cation, tetrahydropyridinium cation, dihydropyridinium cation, tetrahydropyrimidium cation, dihydropyrimidium cation, pyrazolium cation, pyrazolinium cation, or ammonium cation from the viewpoint of antistatic performance.
  • a nitrogen atom-containing organic cation which may have a substituent
  • the content of the ionic compound (D) in the adhesive composition is preferably 0.2 parts by mass or more and 10 parts by mass or less, more preferably 0.3 parts by mass or more and 9 parts by mass or less, and even more preferably 0.5 parts by mass or more and 8 parts by mass or less, based on 100 parts by mass of the solid content of the (meth)acrylic resin (A) (when two or more types are used, the total of the (meth)acrylic resins (A)).
  • the adhesive composition may contain additives such as solvents, crosslinking catalysts, ultraviolet absorbers, weather stabilizers, tackifiers, plasticizers, softeners, dyes, pigments, inorganic fillers, light scattering fine particles, rust inhibitors, release agents, and resins other than the (meth)acrylic resin (A).
  • additives such as solvents, crosslinking catalysts, ultraviolet absorbers, weather stabilizers, tackifiers, plasticizers, softeners, dyes, pigments, inorganic fillers, light scattering fine particles, rust inhibitors, release agents, and resins other than the (meth)acrylic resin (A).
  • additives such as solvents, crosslinking catalysts, ultraviolet absorbers, weather stabilizers, tackifiers, plasticizers, softeners, dyes, pigments, inorganic fillers, light scattering fine particles, rust inhibitors, release agents, and resins other than the (meth)acrylic resin (A).
  • crosslinking catalysts include amine compounds such as hexamethylenediamine, ethylenediamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, isophoronediamine, trimethylenediamine, polyamino resins, and melamine resins.
  • the adhesive layer can be prepared by aging for a short period of time. Furthermore, when a crosslinking catalyst is contained, lifting or peeling at the interface between the adhesive layer and the adjacent film, and foaming of the adhesive layer can be more effectively suppressed, and metal corrosion resistance can also be improved.
  • crosslinking catalysts include amine-based compounds such as hexamethylenediamine, ethylenediamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, isophoronediamine, trimethylenediamine, polyamino resins, and melamine resins.
  • an isocyanate-based compound is preferable as the crosslinking agent (B).
  • the adhesive composition can be prepared by mixing the above components.
  • the adhesive composition may have a gel fraction of, for example, 50% or more and 98% or less, and preferably 60% or more and 95% or less.
  • the gel fraction can be measured according to the measurement method described in the Examples section below.
  • the adhesive composition may have, for example, three or less pits on the metal layer surface in a metal corrosion resistance test.
  • the metal corrosion resistance test can be carried out according to the method described in the Examples section below.
  • the adhesive composition may show little or no change in appearance, such as lifting, peeling, cracking, or foaming, in a heat resistance durability test, and preferably shows no change at all.
  • the heat resistance durability test can be carried out according to the method described in the Examples section below.
  • the pressure-sensitive adhesive layer of the present invention includes the pressure-sensitive adhesive composition of the present invention, and typically consists of the pressure-sensitive adhesive composition of the present invention.
  • the pressure-sensitive adhesive layer can be obtained by dissolving or dispersing each component constituting the pressure-sensitive adhesive composition in a solvent to obtain a solvent-containing pressure-sensitive adhesive composition, and then applying the composition onto a substrate film and drying the composition.
  • the pressure-sensitive adhesive layer has excellent metal corrosion resistance and heat resistance durability.
  • the base film is generally a plastic film, and a typical example is a release film (separator) that has been subjected to a release treatment.
  • the release film can be, for example, a film made of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyarene, etc., with a release treatment such as silicone treatment applied to the surface on which the adhesive layer is to be formed.
  • the adhesive composition may be directly applied to the surface of the optical film to form an adhesive layer, and if necessary, a release film may be laminated on the outer surface of the adhesive layer to form an optical film with an adhesive layer.
  • a surface activation treatment such as plasma treatment, corona treatment, etc. may be applied to the bonding surface of the optical film and/or the bonding surface of the adhesive layer.
  • the thickness of the adhesive layer may be, for example, 10 ⁇ m or more and 50 ⁇ m or less, and from the viewpoint of metal corrosion resistance and heat resistance durability, is preferably 15 ⁇ m or more and 40 ⁇ m or less, and more preferably 18 ⁇ m or more and 35 ⁇ m or less.
  • the pressure-sensitive adhesive layer-attached optical film according to the present invention can include, for example, an optical film and the above-mentioned pressure-sensitive adhesive layer laminated thereon.
  • optical films examples include polarizers; protective films provided to protect the surface of polarizers and the like; polarizing plates in which protective films are laminated on one or both sides of a polarizer; retardation films; optical compensation films other than retardation films; anti-glare films with uneven surfaces, films with anti-reflection surfaces; reflective films with reflective surfaces; semi-transmissive reflective films with both reflective and transmissive functions; light diffusion films; and hard coat films.
  • the optical film with adhesive layer can include one or more optical films, or may include two or more of the same type. When two or more optical films are included, a bonding layer may be used to laminate the two or more optical films, and in this case, the bonding layer can also be part of the optical film.
  • the thickness of the optical film is not particularly limited, but can be, for example, 5 ⁇ m or more and 300 ⁇ m or less.
  • a polarizing plate in which a protective film is laminated on one or both sides of a polarizer is also called a linear polarizing plate.
  • polarizers include those in which iodine is oriented in a polyvinyl alcohol resin layer, and those in which a liquid crystal compound and a dichroic dye are oriented.
  • the protective film is not particularly limited, but is preferably a thermoplastic resin film having translucency (preferably optically transparent).
  • the thermoplastic resin constituting such a film include polyolefin resins such as linear polyolefin resins (polyethylene resins, polypropylene resins, etc.) and cyclic polyolefin resins (norbornene resins, etc.); cellulose ester resins such as triacetyl cellulose, diacetyl cellulose, and cellulose acetate propionate; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polycarbonate resins; (meth)acrylic resins such as (meth)acrylic acid and polymethyl (meth)acrylate; vinyl alcohol resins such as polyvinyl alcohol and polyvinyl acetate; polystyrene resins; mixtures and copolymers thereof.
  • (meth)acrylic means “at least one of acrylic and methacrylic”. These resins may contain one or more additives such as lubricants, plasticizers, dispersants, heat stabilizers, UV absorbers, infrared absorbers, antistatic agents, antioxidants, and light diffusing agents such as fine particles.
  • additives such as lubricants, plasticizers, dispersants, heat stabilizers, UV absorbers, infrared absorbers, antistatic agents, antioxidants, and light diffusing agents such as fine particles.
  • Linear polyolefin resins include homopolymers of linear olefins such as polyethylene resin and polypropylene resin, as well as copolymers made of two or more types of linear olefins.
  • Cyclic polyolefin resin is a general term for resins polymerized using cyclic olefins as polymerization units.
  • Specific examples of cyclic polyolefin resins include ring-opening (co)polymers of cyclic olefins, addition polymers of cyclic olefins, copolymers (typically random copolymers) of cyclic olefins with linear olefins such as ethylene and propylene, graft polymers modified with unsaturated carboxylic acids or their derivatives, and hydrogenated versions of these.
  • norbornene resins using norbornene monomers such as norbornene or polycyclic norbornene monomers as the cyclic olefin are preferably used.
  • Cellulosic resins are partial or complete esters of cellulose, such as cellulose acetate, propionate, butyrate, and mixed esters thereof.
  • cellulose such as cellulose acetate, propionate, butyrate, and mixed esters thereof.
  • triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate, etc. are preferably used.
  • Polyester resins are resins other than the above-mentioned cellulose resins that have ester bonds, and are generally made of polycondensates of polycarboxylic acids or their derivatives with polyhydric alcohols.
  • polycarboxylic acids or their derivatives dicarboxylic acids or their derivatives can be used, such as terephthalic acid, isophthalic acid, dimethyl terephthalate, and dimethyl naphthalenedicarboxylate.
  • diols can be used, such as ethylene glycol, propanediol, butanediol, neopentyl glycol, and cyclohexanedimethanol.
  • polyester resins include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polycyclohexane dimethyl terephthalate, and polycyclohexane dimethyl naphthalate.
  • Polycarbonate-based resins consist of polymers in which monomer units are bonded via carbonate groups.
  • Polycarbonate-based resins may be modified polycarbonates, which are resins in which the polymer backbone has been modified, or copolymer polycarbonates, etc.
  • the (meth)acrylic resin can be a polymer containing a methacrylic acid ester as the main monomer, and is preferably a copolymer in which a small amount of other comonomer components are copolymerized.
  • the (meth)acrylic resin is more preferably a copolymer of methyl methacrylate and methyl acrylate, and may further be copolymerized with a third monofunctional monomer.
  • Examples of the third monofunctional monomer include methacrylic acid esters other than methyl methacrylate, such as ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, and 2-hydroxyethyl methacrylate; acrylic acid esters such as ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, and 2-hydroxyethyl acrylate; 2-(hydroxymethyl)methyl acrylate, 2-(1-hydroxy
  • Examples of the third monofunctional monomer include hydroxyalkyl acrylates such as methyl 2-(ethyl)acrylate, ethyl 2-(hydroxymethyl)acrylate, and butyl 2-(hydroxymethyl)acrylate; unsaturated acids such as me
  • a polyfunctional monomer may be further copolymerized into the (meth)acrylic resin.
  • polyfunctional monomers include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, and tetradecaethylene glycol di(meth)acrylate, which are esterified at both terminal hydroxyl groups of ethylene glycol or its oligomers with acrylic acid or methacrylic acid; propylene glycol or its oligomers with acrylic acid or methacrylic acid, which are esterified at both terminal hydroxyl groups of propylene glycol or its oligomers with acrylic acid or methacrylic acid; and dihydric alcohols such as neopentyl glycol di(meth)acrylate, hexanediol di(meth)acrylate, and butanediol di(meth)
  • the (meth)acrylic resin may be modified by further reacting the functional groups of the copolymer. Examples of such reactions include an intrapolymer chain demethanolization condensation reaction between the methyl ester group of methyl acrylate and the hydroxyl group of methyl 2-(hydroxymethyl)acrylate, and an intrapolymer chain dehydration condensation reaction between the carboxyl group of acrylic acid and the hydroxyl group of methyl 2-(hydroxymethyl)acrylate.
  • the (meth)acrylic resin may also have any of the following structures: a glutarimide derivative, a glutaric anhydride derivative, or a lactone ring structure.
  • the glass transition temperature of the (meth)acrylic resin is preferably 90 to 160°C, more preferably 110 to 160°C, and even more preferably 120 to 150°C.
  • the (meth)acrylic resin may contain additives as necessary.
  • additives include lubricants, antiblocking agents, heat stabilizers, antioxidants, antistatic agents, light resistance agents, impact resistance modifiers, surfactants, etc.
  • (Meth)acrylic resin may contain acrylic rubber particles as an impact modifier from the viewpoint of film formability and impact resistance of the film.
  • Acrylic rubber particles are particles whose essential component is an elastic polymer mainly composed of acrylic acid ester, and examples thereof include a single-layer structure consisting essentially of this elastic polymer, and a multi-layer structure having this elastic polymer as one layer.
  • An example of this elastic polymer is a cross-linked elastic copolymer in which alkyl acrylate is the main component and other copolymerizable vinyl monomers and cross-linkable monomers are copolymerized with this.
  • alkyl acrylates that are the main component of elastic polymers include those with an alkyl group having 1 to 8 carbon atoms, such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, and acrylic acid having an alkyl group having 4 or more carbon atoms is particularly preferred.
  • alkyl acrylates include compounds having one polymerizable carbon-carbon double bond in the molecule, and more specifically, methacrylic acid esters such as methyl methacrylate, aromatic vinyl compounds such as styrene, and vinyl cyan compounds such as acrylonitrile.
  • crosslinkable monomers include crosslinkable compounds having at least two polymerizable carbon-carbon double bonds in the molecule, and more specifically, examples include (meth)acrylates of polyhydric alcohols such as ethylene glycol di(meth)acrylate and butanediol di(meth)acrylate, alkenyl esters of (meth)acrylic acid such as allyl (meth)acrylate, and divinylbenzene.
  • polyhydric alcohols such as ethylene glycol di(meth)acrylate and butanediol di(meth)acrylate
  • alkenyl esters of (meth)acrylic acid such as allyl (meth)acrylate
  • divinylbenzene divinylbenzene
  • the protective film can also be a laminate of a film made of acrylic resin that does not contain rubber particles and a film made of acrylic resin that does contain rubber particles.
  • the retardation film is an optical film that exhibits optical anisotropy.
  • the resins that can be used for the protective film it can be a stretched film obtained by stretching a resin film made of, for example, polyvinyl alcohol resin, polyarylate resin, polyimide resin, polyethersulfone resin, polyvinylidene fluoride/polymethyl methacrylate resin, liquid crystal polyester resin, saponified ethylene-vinyl acetate copolymer, polyvinyl chloride resin, etc., by about 1.01 to 6 times.
  • stretched films obtained by uniaxially or biaxially stretching a polycarbonate resin film, a cycloolefin resin film, a (meth)acrylic resin film, or a cellulose resin film are preferred.
  • zero retardation films are also included in the retardation film (however, they can also be used as protective films).
  • films called uniaxial retardation films, wide viewing angle retardation films, low photoelasticity retardation films, etc. can also be used as retardation films.
  • the retardation film may be a film having an optically anisotropic layer made of a polymer formed by polymerizing a polymerizable liquid crystal compound in an oriented state on a substrate.
  • the substrate may be the thermoplastic resin film used in the protective film.
  • the retardation film can be, for example, a 1/4 wavelength retardation layer with reverse wavelength dispersion, a positive C plate, a 1/2 wavelength retardation layer with positive wavelength dispersion, a 1/4 wavelength retardation layer with positive wavelength dispersion, etc.
  • the retardation film may be composed of two or more retardation layers, and may have, for example, a configuration in which a 1/4 wavelength retardation layer with reverse wavelength dispersion is combined with a positive C plate, or a configuration in which a 1/2 wavelength retardation layer with positive wavelength dispersion is combined with a 1/4 wavelength retardation layer with positive wavelength dispersion, etc.
  • the retardation film or protective film may have a moisture permeability of 500 g/(m 2 ⁇ 24 hr) or less, measured at a temperature of 40° C. and a relative humidity of 90% by the cup method specified in JIS Z 0208.
  • a surface protective film is a film used for the purpose of protecting the surface of an object to be protected, such as an optical film, from scratches and dirt.
  • various optical films such as polarizers, protective films, retardation films, light diffusion sheets, and reflective sheets, which are optical films for liquid crystal display devices, are usually distributed with a surface protective film attached to their surface (the surface opposite the adhesive layer, if the optical film has an adhesive layer on one side).
  • the surface protective film is usually peeled off and removed after the optical film is attached to a liquid crystal cell, etc.
  • substrates for surface protection films include polyolefin resins such as polyethylene, polypropylene, and polymethylpentene; fluorinated polyolefin resins such as polyvinyl fluoride, polyvinylidene fluoride, and polyethylene fluoride; polyester resins such as polyethylene naphthalate, polyethylene terephthalate, polybutylene terephthalate, and polyethylene terephthalate/isophthalate copolymers; polyamides such as nylon 6 and nylon 6,6; vinyl polymers such as polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, and vinylon; cellulose resins such as triacetyl cellulose, diacetyl cellulose, and cellophane; (meth)acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, polyethyl
  • the lamination layer may be an adhesive layer or an adhesive layer.
  • an adhesive layer other than the above-mentioned adhesive layer may be used for the lamination layer.
  • the adhesive layer may be composed of an adhesive composition mainly composed of a resin such as a (meth)acrylic resin, a rubber resin, a urethane resin, an ester resin, a silicone resin, or a polyvinyl ether resin.
  • an adhesive composition having a (meth)acrylic resin as a base polymer which is excellent in transparency, weather resistance, heat resistance, etc., is preferable.
  • the adhesive composition may be an active energy ray curable type or a heat curable type.
  • the (meth)acrylic resin (base polymer) used in the adhesive composition is preferably a polymer or copolymer having one or more monomers of (meth)acrylic acid esters such as butyl (meth)acrylate, ethyl (meth)acrylate, isooctyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. It is preferable to copolymerize a polar monomer into the base polymer.
  • polar monomers include monomers having a carboxyl group, hydroxyl group, amide group, amino group, epoxy group, etc., such as (meth)acrylic acid, 2-hydroxypropyl (meth)acrylate, hydroxyethyl (meth)acrylate, (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylate, and glycidyl (meth)acrylate.
  • the adhesive composition may contain only the base polymer, but usually also contains a crosslinking agent.
  • crosslinking agents include divalent or higher metal ions that form metal carboxylates with carboxyl groups; polyamine compounds that form amide bonds with carboxyl groups; polyepoxy compounds or polyols that form ester bonds with carboxyl groups; and polyisocyanate compounds that form amide bonds with carboxyl groups. Of these, polyisocyanate compounds are preferred.
  • the thickness of the attachment layer is preferably 1 ⁇ m or more and 200 ⁇ m or less, more preferably 2 ⁇ m or more and 100 ⁇ m or less, even more preferably 2 ⁇ m or more and 80 ⁇ m or less, and particularly preferably 3 ⁇ m or more and 50 ⁇ m or less.
  • the lamination layer is an adhesive layer
  • any suitable adhesive can be used.
  • the adhesive can be a water-based adhesive, an active energy ray curing adhesive, or the like.
  • the thickness of the adhesive when applied can be set to any appropriate value. For example, it is set so that an adhesive layer having the desired thickness is obtained after curing or heating (drying).
  • the thickness of the adhesive layer is preferably 0.01 ⁇ m or more and 7 ⁇ m or less, more preferably 0.01 ⁇ m or more and 5 ⁇ m or less, even more preferably 0.01 ⁇ m or more and 2 ⁇ m or less, and most preferably 0.01 ⁇ m or more and 1 ⁇ m or less.
  • water-based adhesives examples include aqueous polyvinyl alcohol resin solutions and water-based two-component urethane emulsion adhesives.
  • the active energy ray-curable adhesive is an adhesive containing a curable compound that cures when exposed to active energy rays such as ultraviolet light, visible light, electron beams, and X-rays, and is preferably an ultraviolet ray-curable adhesive.
  • the curable compound may be a cationic polymerizable curable compound or a radical polymerizable curable compound.
  • the cationic polymerizable curable compound include an epoxy compound (a compound having one or more epoxy groups in the molecule), an oxetane compound (a compound having one or more oxetane rings in the molecule), or a combination of these.
  • the radical polymerizable curable compound include a (meth)acrylic compound (a compound having one or more (meth)acryloyloxy groups in the molecule), other vinyl compounds having a radical polymerizable double bond, or a combination of these.
  • a cationic polymerizable curable compound and a radical polymerizable curable compound may be used in combination.
  • An active energy ray curable adhesive usually further includes at least one of a cationic polymerization initiator and a radical polymerization initiator for initiating the curing reaction of the curable compound.
  • a surface activation treatment may be applied to at least one of the laminating surfaces of the laminating layer and the optical film.
  • the surface activation treatment include dry treatments such as corona treatment, plasma treatment, discharge treatment (glow discharge treatment, etc.), ozone treatment, UV ozone treatment, and ionizing active ray treatment (ultraviolet ray treatment, electron beam treatment, etc.). These surface activation treatments may be performed alone or in combination of two or more. Among them, corona treatment is preferred. Corona treatment may be performed with an output of, for example, 1 kJ/m 2 or more and 50 kJ/m 2 or less. The time for performing corona treatment may be, for example, 1 second or more and 1 minute or less.
  • optical film with an adhesive layer it is preferable to attach the above-mentioned release film to the surface of the adhesive layer and provide temporary protection until use.
  • the optical film with an adhesive layer according to this embodiment with a release film attached can be manufactured by a method of applying an adhesive composition onto a release film to form an adhesive layer and further laminating a resin film onto the resulting adhesive layer, or a method of applying an adhesive composition onto a resin film to form an adhesive layer and laminating a release film onto the adhesive surface.
  • the optical film with adhesive layer can be used in displays such as organic electroluminescence (organic EL) displays and liquid crystal displays, and can be attached to the viewing side of the image display element of these displays.
  • organic EL organic electroluminescence
  • the laminated structure of the optical film with adhesive layer is not particularly limited as long as it includes an optical film and an adhesive layer laminated on the optical film.
  • the adhesive layer-attached optical film 10 shown in FIG. 1 includes a linear polarizer 11 and an adhesive layer 12.
  • the linear polarizer 11 includes, in this order, a first protective film 13, an adhesive layer 14, a polarizer 15, an adhesive layer 16, and a second protective film 17.
  • the adhesive layer 12 can be used to attach to a liquid crystal cell, which is an image display element of a liquid crystal display device.
  • a separator (release film) (not shown) may be provided on the surface of the adhesive layer 12 opposite the linear polarizer 11.
  • the adhesive layer-attached optical film 20 shown in FIG. 2 includes, in this order, an adhesive layer 21, a retardation film 22, an attachment layer 23, and a linear polarizer 24.
  • the linear polarizer 24 includes, in this order, a first protective film 25, an adhesive layer 26, a polarizer 27, an adhesive layer 28, and a second protective film 29.
  • the adhesive layer 21 can be used to attach to a liquid crystal cell, which is an image display element of a liquid crystal display device.
  • a separator peeleling film (not shown) may be provided on the surface of the adhesive layer 21 opposite the retardation film 22.
  • optical films 10 and 20 with adhesive layers shown in Figures 1 and 2 are merely examples, and may have a laminate structure other than that described above.
  • the protective film may have further layers such as a hard coat film, a film with anti-glare function, or a film with surface anti-reflection function.
  • the optical laminate according to the present invention includes the above-mentioned pressure-sensitive adhesive layer-attached optical film and a metal layer.
  • Fig. 3 is a schematic cross-sectional view showing an example of the layer structure of the optical laminate.
  • the optical laminate 30 shown in Fig. 3 includes a pressure-sensitive adhesive layer-attached optical film 10 including a linear polarizing plate 11 and a pressure-sensitive adhesive layer 12, and a metal layer 31 laminated on the pressure-sensitive adhesive layer 12.
  • the pressure-sensitive adhesive layer-attached optical film 10 is laminated on the metal layer 31 so that the pressure-sensitive adhesive layer 12 is in direct contact with the metal layer 31. According to the present invention, even in an optical laminate having such a configuration that the pressure-sensitive adhesive layer 12 is in direct contact with the metal layer 31, corrosion of the metal layer 31 can be effectively suppressed.
  • FIG. 4 is a schematic cross-sectional view showing another example of the layer structure of the optical laminate according to the present invention.
  • the adhesive layer 12 of the adhesive layer-attached optical film 10 including the linear polarizer 11 and the adhesive layer 12 is laminated to the metal layer 42 via the resin layer 41.
  • the adhesive layer 12 is in direct contact with the resin layer 41.
  • the corrosion of the metal layer 42 can also be effectively suppressed.
  • the resin layer 41 disposed between the adhesive layer 12 and the metal layer 42 may be, for example, a cured layer of a curable resin.
  • the curable resin capable of forming the resin layer 41 a known one can be used, and examples thereof include those described in JP-A-2009-217037.
  • the metal layer can be, for example, a layer containing one or more metals selected from the group consisting of aluminum, copper, silver, gold, iron, tin, zinc, nickel, molybdenum, chromium, tungsten, lead, and alloys containing two or more metals selected from these. From the viewpoint of electrical conductivity, it is preferably a layer containing a metal element selected from the group consisting of aluminum, copper, silver, and gold. From the viewpoint of electrical conductivity and cost, it is more preferably a layer containing aluminum element, and even more preferably a layer containing aluminum element as the main component. "Containing as the main component” means that the metal component constituting the metal layer is 30% by weight or more, and even more preferably 50% by weight or more of the total metal components.
  • the metal layer may be, for example, a metal oxide layer such as ITO, but since the pressure-sensitive adhesive layer-attached optical film according to the present invention has particularly good corrosion resistance against simple metals and alloys, it is preferable that the metal layer contains a simple metal composed of the above metal elements and/or an alloy containing two or more of the above metal elements.
  • the optical laminate may have a transparent electrode layer composed of a metal oxide such as ITO in addition to such a metal layer.
  • the form (e.g., thickness, etc.) and preparation method of the metal layer are not particularly limited, and it can be a metal foil, or it may be formed by vacuum deposition, sputtering, ion plating, inkjet printing, or gravure printing. However, it is preferably a metal layer formed by sputtering, inkjet printing, or gravure printing, and more preferably a metal layer formed by sputtering.
  • a metal layer formed by sputtering tends to have poorer corrosion resistance than a metal foil, but the optical laminate of the present invention has good metal corrosion resistance even against a metal layer formed by sputtering.
  • the thickness of the metal layer is usually 3 ⁇ m or less, preferably 1 ⁇ m or less, and more preferably 0.8 ⁇ m or less.
  • the thickness of the metal layer is usually 0.01 ⁇ m or more.
  • the line width of the metal wiring of the metal wiring layer is usually 10 ⁇ m or less, preferably 5 ⁇ m or less, and more preferably 3 ⁇ m or less.
  • the line width of the metal wiring is usually 0.01 ⁇ m or more, preferably 0.1 ⁇ m or more, and more preferably 0.5 ⁇ m or more.
  • the optical laminate of the present invention exhibits good metal corrosion resistance even against such thin metal layers and metal layers consisting of fine metal wiring.
  • the metal wiring has a thickness of 3 ⁇ m or less and a line width of 10 ⁇ m or less, or a thickness of 3 ⁇ m or less and a line width of 10 ⁇ m or less and is formed by a sputtering method, corrosion, particularly pitting corrosion, can be suppressed.
  • the metal layer can be, for example, a metal wiring layer (i.e., an electrode layer) of a touch input element of a touch input type liquid crystal display device.
  • the metal layer is usually patterned into a predetermined shape.
  • the adhesive may have a portion that is not in contact with the metal layer.
  • the metal layer may be a continuous film containing the above metal or alloy.
  • the metal layer may have a single layer structure, or a multi-layer structure of two or more layers.
  • An example of a multi-layer metal layer is a metal-containing layer (such as a metal mesh) with a three-layer structure represented by molybdenum/aluminum/molybdenum.
  • a metal layer which is a metal wiring layer, may be formed on a substrate, and in this case, the optical laminate according to the present invention may include this substrate.
  • the metal layer may be formed on the substrate by, for example, sputtering.
  • the substrate may be a transparent substrate that constitutes a liquid crystal cell included in a touch input element.
  • the substrate is preferably a glass substrate. Examples of materials for the glass substrate include soda lime glass, low alkali glass, and non-alkali glass.
  • the metal layer may be formed on the entire surface of the substrate, or may be formed on a part of it.
  • the adhesive layer in the optical laminate according to the present invention has excellent adhesion to glass, the optical laminate and the liquid crystal display device including the same have excellent heat resistance and durability in such cases.
  • the display device includes the pressure-sensitive adhesive layer-attached optical film described above.
  • the pressure-sensitive adhesive layer-attached optical film described above can be suitably used in displays such as organic EL displays, liquid crystal displays, inorganic electroluminescence (inorganic EL) displays, and electron emission displays.
  • the display device 50 shown in FIG. 5 is a liquid crystal display device including the optical film 10 with adhesive layer shown in FIG. 1 and a liquid crystal display element 51.
  • the optical film 10 with adhesive layer can be disposed on the viewing side and/or the back side of the liquid crystal display element 51 via the adhesive layer 12.
  • the glass transition temperature (Tg) of the resulting (meth)acrylic resin was measured.
  • the Tg was measured using a differential scanning calorimeter (DSC) "EXSTAR DSC6000" manufactured by SII NanoTechnology Co., Ltd. under conditions of a nitrogen atmosphere, a measurement temperature range of -80 to 50°C, and a heating rate of 10°C/min.
  • DSC differential scanning calorimeter
  • Mw and Mn were measured in terms of standard polystyrene using a GPC apparatus with three columns in series, one "TSKgel guard column HHR-H(S)” manufactured by Tosoh Corporation and two “TSKgel GMHHR-H", and tetrahydrofuran as an eluent under the conditions of a sample concentration of 2 mg/mL, a sample introduction amount of 100 ⁇ L, a temperature of 40° C., and a flow rate of 1 mL/min.
  • Table 1 shows the monomer composition of the monomer mixture used, as well as the Tg, Mw and molecular weight distribution (Mw/Mn) of the resulting (meth)acrylic resin.
  • Adhesive layer The adhesive composition prepared in (1) above was applied to the release-treated surface of a separate film made of a release-treated polyethylene terephthalate film ["Diafoil MRV38 (V04)" manufactured by Mitsubishi Chemical Corporation] using an applicator so that the thickness after drying would be 25 ⁇ m, and the coating was dried at 100° C. for 1 minute to prepare an adhesive layer (adhesive sheet).
  • the laminate is folded four times so as to encase the adhesive layer and stapled, and then weighed, and its mass is designated as Wb.
  • the mesh stapled in [b] above is placed in a glass container, 60 mL of ethyl acetate is added to soak it, and the glass container is then stored at room temperature for 3 days.
  • the mesh is removed from the glass container, dried at 120° C. for 4 hours, and then weighed. The mass is designated as Wa, and the weight is calculated by the following formula:
  • the pressure-sensitive adhesive layer-attached optical film was cut into a test piece measuring 50 mm x 50 mm, and attached to the metal layer side of a metal-layer-attached glass substrate via the pressure-sensitive adhesive layer.
  • the obtained optical laminate was stored in an oven at a temperature of 85°C and a relative humidity of 85% for 360 hours, and then the state of the metal layer at the portion where the pressure-sensitive adhesive layer-attached optical film was attached was observed through a magnifying glass (loupe) from the polarizing plate surface by applying light from the back side of the glass substrate, and pitting corrosion (the occurrence of holes with a diameter of 0.1 mm or more that can transmit light) was evaluated according to the following criteria.
  • the results are shown in Table 3.
  • B The number of pitting corrosion that occurred on the metal layer surface was 11 or more, and some parts were cloudy.
  • Polarizing Plate A polarizing plate was prepared by laminating, via a water-based adhesive, 40 ⁇ m-thick protective films made of saponified triacetyl cellulose resin to both sides of a 12 ⁇ m-thick polarizer in which iodine was adsorbed and oriented on a uniaxially stretched polyvinyl alcohol film.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

(Abstract) (Problem) To provide an adhesive that exhibits excellent heat resistant durability and metal corrosion resistance. (Solution) An adhesive composition containing a (meth)acrylic resin (A), a crosslinking agent (B), a silane compound (C), and an ionic compound (D), in which the (meth)acrylic resin (A) contains a structural unit derived from an alkyl methacrylate (a) having a homopolymer glass transition temperature of 30°C or higher, a structural unit derived from a hydroxy group-containing (meth)acrylate (b), and a structural unit derived from a carboxy group-containing monomer (c) and the silane compound (C) contains a compound represented by formula (I).

Description

粘着剤組成物、粘着剤層、粘着剤層付光学フィルムおよび表示装置Pressure-sensitive adhesive composition, pressure-sensitive adhesive layer, pressure-sensitive adhesive layer-attached optical film, and display device
　本発明は、粘着剤組成物に関し、さらには粘着剤組成物を含む粘着剤層、および粘着剤層付光学フィルムにも関する。 The present invention relates to a pressure-sensitive adhesive composition, and further to a pressure-sensitive adhesive layer containing the pressure-sensitive adhesive composition, and an optical film with a pressure-sensitive adhesive layer.
　液晶表示装置や有機エレクトロルミネッセンス（有機ＥＬ）表示装置等の画像表示装置に用いられる偏光板等の光学フィルムは、粘着剤層を介して他の部材（例えば液晶表示装置における液晶セル等の画像表示素子）に貼合して用いられることが多い。画像表示装置は、スマートフォンやタブレット型端末のようなタッチ入力式表示装置用途に展開されている。このようなタッチ入力式表示装置において、粘着剤層が金属配線から構成される金属層上に配置されることがある。しかしながら、金属層と粘着剤層とを組み合わせた構成においては、高温高湿環境下において金属層が腐食することがあった。 Optical films such as polarizing plates used in image display devices such as liquid crystal display devices and organic electroluminescence (organic EL) display devices are often attached to other components (for example, image display elements such as liquid crystal cells in liquid crystal display devices) via an adhesive layer. Image display devices are being deployed in touch input display device applications such as smartphones and tablet terminals. In such touch input display devices, an adhesive layer may be disposed on a metal layer composed of metal wiring. However, in configurations in which a metal layer and an adhesive layer are combined, the metal layer may corrode in high temperature and high humidity environments.
　特許文献１には、金属層の腐食を抑制することができる粘着剤組成物として、（メタ）アクリル系樹脂と、特定のシラン化合物およびイオン性化合物とを含む粘着剤組成物が提案されている。 Patent Document 1 proposes an adhesive composition that contains a (meth)acrylic resin, a specific silane compound, and an ionic compound as an adhesive composition that can inhibit corrosion of a metal layer.
特開２０１６－１９４０７１号公報JP 2016-194071 A
　近年、車載用途等の光学フィルムに用いられる粘着剤には、より過酷な条件において、良好な耐熱耐久性および耐金属腐食性を有することが要求されている。しかしながら、粘着剤層において、耐熱耐久性および耐金属腐食性をいずれも向上させることは困難であった。 In recent years, adhesives used in optical films for in-vehicle applications, etc., are required to have good heat resistance and metal corrosion resistance under more severe conditions. However, it has been difficult to improve both the heat resistance and metal corrosion resistance of the adhesive layer.
　本発明の目的は、優れた耐熱耐久性および耐金属腐食性を示す粘着剤を提供することである。 The object of the present invention is to provide an adhesive that exhibits excellent heat resistance and durability and metal corrosion resistance.
　本発明は、以下の粘着剤組成物、粘着剤層、粘着剤層付光学フィルムおよび表示装置を提供する。
［１］　（メタ）アクリル系樹脂（Ａ）と、架橋剤（Ｂ）と、シラン化合物（Ｃ）と、イオン性化合物（Ｄ）とを含有し、
　前記（メタ）アクリル系樹脂（Ａ）は、ホモポリマーのガラス転移温度が３０℃以上であるアルキルメタクリレート（ａ）由来の構成単位と、ヒドロキシ基含有（メタ）アクリレート（ｂ）由来の構成単位と、カルボキシ基含有モノマー（ｃ）由来の構成単位とを含み、
　前記シラン化合物（Ｃ）は、下記式（Ｉ）： The present invention provides the following pressure-sensitive adhesive composition, pressure-sensitive adhesive layer, pressure-sensitive adhesive layer-attached optical film, and display device.
[1] A composition comprising a (meth)acrylic resin (A), a crosslinking agent (B), a silane compound (C), and an ionic compound (D),
The (meth)acrylic resin (A) contains a structural unit derived from an alkyl methacrylate (a) having a homopolymer glass transition temperature of 30° C. or higher, a structural unit derived from a hydroxyl group-containing (meth)acrylate (b), and a structural unit derived from a carboxyl group-containing monomer (c),
The silane compound (C) is represented by the following formula (I):
Figure JPOXMLDOC01-appb-C000003
 ［式（Ｉ）中、
　Ｌは、炭素数１～２０のアルカンジイル基または炭素数３～２０の２価の脂環式炭化水素基を表し、該アルカンジイル基および該脂環式炭化水素基を構成する－ＣＨ２－は、－Ｏ－または－Ｃ（＝Ｏ）－に置き換わっていてもよく、
　Ａ１は、炭素数１～５のアルキル基を表し、
　Ａ２、Ａ３、Ａ４、Ａ５およびＡ６は、互いに独立して、炭素数１～５のアルキル基または炭素数１～５のアルコキシ基を表す］
で表される化合物を含む、粘着剤組成物。
［２］　前記（メタ）アクリル系樹脂（Ａ）１００質量部に対して前記シラン化合物（Ｃ）を０．０１質量部以上２．０質量部以下含有する、［１］に記載の粘着剤組成物。
［３］　前記（メタ）アクリル系樹脂（Ａ）を構成する全構成単位１００質量部に対して、前記ホモポリマーのガラス転移温度が３０℃以上であるアルキルメタクリレート（ａ）由来の構成単位を１質量部以上１５質量部以下、前記ヒドロキシ基含有（メタ）アクリレート（ｂ）由来の構成単位を０．３質量部以上５．５質量部以下含有する、［１］または［２］に記載の粘着剤組成物。
［４］　前記ヒドロキシ基含有（メタ）アクリレート（ｂ）由来の構成単位に対する前記カルボキシ基含有モノマー（ｃ）由来の構成単位の質量比（ｃ）／（ｂ）が０．０６以上１．０以下である、［１］～［３］のいずれかに記載の粘着剤組成物。
［５］　前記ホモポリマーのガラス転移温度が３０℃以上であるアルキルメタクリレート（ａ）のホモポリマーのガラス転移温度が８０℃以上である、［１］～［４］に記載の粘着剤組成物。
［６］　前記ホモポリマーのガラス転移温度が３０℃以上であるアルキルメタクリレート（ａ）はメチルメタクリレート、ｔｅｒｔ－ブチルメタクリレート、イソボルニルメタクリレートおよびシクロヘキシルメタクリレートからなる群から選択される少なくとも１種を含む、［１］～［５］のいずれかに記載の粘着剤組成物。
［７］　前記（メタ）アクリル系樹脂（Ａ）の重量平均分子量が１００万以上３２０万以下である、［１］～［６］のいずれかに記載の粘着剤組成物。
［８］　前記式（Ｉ）において、Ｌは、炭素数２～１０のアルカンジイル基を表す、［１］～［７］のいずれかに記載の粘着剤組成物。
［９］　前記架橋剤（Ｂ）は芳香族系イソシアネート化合物を含み、前記（メタ）アクリル系樹脂（Ａ）１００質量部に対して前記架橋剤（Ｂ）を０．２質量部以上５．０質量部以下含有する、［１］～［８］のいずれかに記載の粘着剤組成物。
［１０］　前記（メタ）アクリル系樹脂（Ａ）１００質量部に対して前記イオン性化合物（Ｄ）を０．１質量部以上１０．０質量部以下含有する、［１］～［９］のいずれかに記載の粘着剤組成物。
［１１］　前記イオン性化合物（Ｄ）は、下記式：
Figure JPOXMLDOC01-appb-C000003
 [In formula (I),
L represents an alkanediyl group having 1 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and —CH 2 — constituting the alkanediyl group or the alicyclic hydrocarbon group may be replaced by —O— or —C(═O)—;
A 1 represents an alkyl group having 1 to 5 carbon atoms;
A 2 , A 3 , A 4 , A 5 and A 6 each independently represent an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.
A pressure-sensitive adhesive composition comprising a compound represented by the formula:
[2] The pressure-sensitive adhesive composition according to [1], containing 0.01 parts by mass or more and 2.0 parts by mass or less of the silane compound (C) per 100 parts by mass of the (meth)acrylic resin (A).
[3] The pressure-sensitive adhesive composition according to [1] or [2], containing, relative to 100 parts by mass of all structural units constituting the (meth)acrylic resin (A), 1 part by mass or more and 15 parts by mass or less of a structural unit derived from an alkyl methacrylate (a) having a homopolymer glass transition temperature of 30° C. or more and 0.3 parts by mass or more and 5.5 parts by mass or less of a structural unit derived from the hydroxy group-containing (meth)acrylate (b).
[4] The pressure-sensitive adhesive composition according to any one of [1] to [3], wherein a mass ratio (c)/(b) of the structural unit derived from the carboxyl group-containing monomer (c) to the structural unit derived from the hydroxyl group-containing (meth)acrylate (b) is 0.06 or more and 1.0 or less.
[5] The pressure-sensitive adhesive composition according to any one of [1] to [4], wherein the homopolymer of the alkyl methacrylate (a) having a glass transition temperature of 30° C. or higher has a glass transition temperature of 80° C. or higher.
[6] The pressure-sensitive adhesive composition according to any one of [1] to [5], wherein the alkyl methacrylate (a) having a homopolymer glass transition temperature of 30° C. or higher includes at least one selected from the group consisting of methyl methacrylate, tert-butyl methacrylate, isobornyl methacrylate, and cyclohexyl methacrylate.
[7] The pressure-sensitive adhesive composition according to any one of [1] to [6], wherein the (meth)acrylic resin (A) has a weight average molecular weight of 1,000,000 or more and 3,200,000 or less.
[8] The pressure-sensitive adhesive composition according to any one of [1] to [7], wherein in formula (I), L represents an alkanediyl group having 2 to 10 carbon atoms.
[9] The pressure-sensitive adhesive composition according to any one of [1] to [8], wherein the crosslinking agent (B) contains an aromatic isocyanate compound, and the crosslinking agent (B) is contained in an amount of 0.2 parts by mass or more and 5.0 parts by mass or less per 100 parts by mass of the (meth)acrylic resin (A).
[10] The pressure-sensitive adhesive composition according to any one of [1] to [9], comprising 0.1 parts by mass or more and 10.0 parts by mass or less of the ionic compound (D) per 100 parts by mass of the (meth)acrylic resin (A).
[11] The ionic compound (D) is represented by the following formula:
Figure JPOXMLDOC01-appb-C000004
 で表される化合物からなる群から選択されるアニオンを含有する、［１］～［１０］のいずれかに記載の粘着剤組成物。
［１２］　［１］～［１１］のいずれかに記載の粘着剤組成物を含む粘着剤層。
［１３］　光学フィルムと、前記光学フィルム上に積層された［１２］に記載の粘着剤層とを含む、粘着剤層付光学フィルム。
［１４］　前記光学フィルムは偏光子を含む、［１３］に記載の粘着剤層付光学フィルム。
［１５］　［１３］または［１４］に記載の粘着剤層付光学フィルムを含む表示装置。
Figure JPOXMLDOC01-appb-C000004
 The pressure-sensitive adhesive composition according to any one of [1] to [10], containing an anion selected from the group consisting of compounds represented by the following formula:
[12] A pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition according to any one of [1] to [11].
[13] A pressure-sensitive adhesive layer-attached optical film comprising an optical film and the pressure-sensitive adhesive layer according to [12] laminated on the optical film.
[14] The pressure-sensitive adhesive layer-attached optical film according to [13], wherein the optical film includes a polarizer.
[15] A display device comprising the pressure-sensitive adhesive layer-attached optical film according to [13] or [14].
　本発明によれば、優れた耐熱耐久性および耐金属腐食性を示す粘着剤を提供することができる。 The present invention provides an adhesive that exhibits excellent heat resistance and durability and metal corrosion resistance.
本発明に係る粘着剤層付光学フィルムの一例を示す概略断面図である。1 is a schematic cross-sectional view showing an example of a pressure-sensitive adhesive layer-attached optical film according to the present invention. 本発明に係る粘着剤層付光学フィルムの他の一例を示す概略断面図である。FIG. 2 is a schematic cross-sectional view showing another example of a pressure-sensitive adhesive layer-attached optical film according to the present invention. 本発明に係る光学積層体の一例を示す概略断面図である。FIG. 1 is a schematic cross-sectional view showing an example of an optical laminate according to the present invention. 本発明に係る光学積層体の他の一例を示す概略断面図である。FIG. 2 is a schematic cross-sectional view showing another example of the optical laminate according to the present invention. 本発明に係る画像表示装置の一例を示す概略断面図である。1 is a schematic cross-sectional view showing an example of an image display device according to the present invention.
　以下、図面を参照しつつ本発明の実施形態を説明するが、本発明は以下の実施形態に限定されるものではない。以下の全ての図面においては、各構成要素を理解し易くするために縮尺を適宜調整して示しており、図面に示される各構成要素の縮尺と実際の構成要素の縮尺とは必ずしも一致しない。 Below, an embodiment of the present invention will be described with reference to the drawings, but the present invention is not limited to the following embodiment. In all of the drawings, the scale of each component has been appropriately adjusted to make it easier to understand, and the scale of each component shown in the drawings does not necessarily match the scale of the actual component.
　＜粘着剤組成物＞
（１）（メタ）アクリル系樹脂（Ａ）
　本発明に係る粘着剤組成物が含む（メタ）アクリル系樹脂（Ａ）は、ホモポリマーのガラス転移温度が３０℃以上であるアルキルメタクリレート（ａ）［以下、アルキルメタクリレート（ａ）ともいう］由来の構成単位と、ヒドロキシ基含有（メタ）アクリレート（ｂ）由来の構成単位と、カルボキシ基含有モノマー（ｃ）由来の構成単位とを含む。なお本明細書において、（メタ）アクリルとは、アクリルまたはメタクリルのいずれでもよいことを意味する。（メタ）アクリレートとは、アクリレートまたはメタクリレートのいずれでもよいことを意味する。 <Adhesive Composition>
(1) (Meth)acrylic resin (A)
The (meth)acrylic resin (A) contained in the pressure-sensitive adhesive composition according to the present invention contains a structural unit derived from an alkyl methacrylate (a) [hereinafter also referred to as alkyl methacrylate (a)] having a homopolymer glass transition temperature of 30° C. or higher, a structural unit derived from a hydroxyl group-containing (meth)acrylate (b), and a structural unit derived from a carboxyl group-containing monomer (c). In this specification, (meth)acrylic means that it may be either acrylic or methacrylic. (Meth)acrylate means that it may be either acrylate or methacrylate.
　アルキルメタクリレート（ａ）は、ホモポリマーのガラス転移温度（Ｔｇ）が３０℃以上であるアルキルメタクリレートである。アルキルメタクリレートのホモポリマーのＴｇは、例えばＰＯＬＹＭＥＲ　ＨＡＮＤＢＯＯＫ（Ｗｉｌｅｙ－Ｉｎｔｅｒｓｃｉｅｎｃｅ）などの文献値を採用することができる。アルキルメタクリレート（ａ）のホモポリマーのＴｇは、耐熱耐久性の観点から好ましくは５０℃以上、より好ましくは６０℃以上、さらに好ましくは８０℃以上である。アルキルメタクリレート（ａ）のホモポリマーのＴｇの上限は特に限定されないが、通常２５０℃以下である。 The alkyl methacrylate (a) is an alkyl methacrylate having a homopolymer glass transition temperature (Tg) of 30°C or higher. For the Tg of the alkyl methacrylate homopolymer, a literature value such as that in the POLYMER HANDBOOK (Wiley-Interscience) can be used. From the viewpoint of heat resistance and durability, the Tg of the alkyl methacrylate (a) homopolymer is preferably 50°C or higher, more preferably 60°C or higher, and even more preferably 80°C or higher. There is no particular upper limit for the Tg of the alkyl methacrylate (a) homopolymer, but it is usually 250°C or lower.
　アルキルメタクリレート（ａ）の具体例としては、メチルメタクリレート、エチルメタクリレート、イソブチルメタクリレート、ｓｅｃ‐ブチルメタクリレート、ｔｅｒｔ－ブチルメタクリレート、プロピルメタクリレート、イソプロピルメタクリレート、３，３－ジメチルブチルメタクリレート、３，３－ジメチル－２－ブチルメタクリレート等の炭素数が１～６の直鎖状又は分岐状のアルキル基を有するアルキルメタクリレート、ｎ－ステアリルメタクリレート等が挙げられる。アルキルメタクリレート（ａ）は、脂環式構造を有するアルキルメタクリレート（シクロアルキルメタクリレート）であってもよい。脂環式構造は、炭素数が通常５以上、好ましくは５～７程度のシクロパラフィン構造であることができる。脂環式構造を有するアルキルメタクリレートの具体例は、イソボルニルメタクリレート、シクロヘキシルメタクリレート、ジシクロペンタニルメタクリレート、トリメチルシクロヘキシルメタクリレート、ｔｅｒｔ－ブチルシクロヘキシルメタクリレート、１－アダマンチルメタクリレート等が挙げられる。アルキルメタクリレート（ａ）は、１種のみを単独で用いてもよいし、２種以上を併用してもよい。
　アルキルメタクリレート（ａ）としては、炭素数が１～４の直鎖状又は分岐状のアルキル基を有するアルキルメタクリレート、又は脂環式構造を有するアルキルメタクリレートが好ましく、特に、メチルメタアクリレート、ｔｅｒｔ－ブチルメタクリレート、イソボルニルメタクリレート、シクロヘキシルメタクリレートが好ましい。 Specific examples of the alkyl methacrylate (a) include alkyl methacrylates having a linear or branched alkyl group having 1 to 6 carbon atoms, such as methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, propyl methacrylate, isopropyl methacrylate, 3,3-dimethylbutyl methacrylate, and 3,3-dimethyl-2-butyl methacrylate, and n-stearyl methacrylate. The alkyl methacrylate (a) may be an alkyl methacrylate (cycloalkyl methacrylate) having an alicyclic structure. The alicyclic structure may be a cycloparaffin structure having a carbon number of usually 5 or more, preferably about 5 to 7. Specific examples of the alkyl methacrylate having an alicyclic structure include isobornyl methacrylate, cyclohexyl methacrylate, dicyclopentanyl methacrylate, trimethylcyclohexyl methacrylate, tert-butylcyclohexyl methacrylate, and 1-adamantyl methacrylate. The alkyl methacrylate (a) may be used alone or in combination of two or more kinds.
As the alkyl methacrylate (a), an alkyl methacrylate having a linear or branched alkyl group having 1 to 4 carbon atoms, or an alkyl methacrylate having an alicyclic structure is preferred, and in particular, methyl methacrylate, tert-butyl methacrylate, isobornyl methacrylate, and cyclohexyl methacrylate are preferred.
　アルキルメタクリレート（ａ）由来の構成単位の含有量は、耐金属腐食性および耐熱耐久性の観点から好ましくは（メタ）アクリル系樹脂（Ａ）を構成する全構成単位１００質量部に対して１質量部以上１５質量部以下、より好ましくは３質量部以上１３質量部以下、さらに好ましくは４質量部以上１２質量部以下、特に好ましくは５質量部以上１１質量部以下である。上記範囲内であると、粘着剤の凝集性を向上させることにより機械強度が向上し、かつ粘着剤の柔軟性や粘着性を確保できるため、耐熱耐久性に有利である。 From the viewpoint of metal corrosion resistance and heat resistance durability, the content of the structural units derived from alkyl methacrylate (a) is preferably 1 to 15 parts by mass, more preferably 3 to 13 parts by mass, even more preferably 4 to 12 parts by mass, and particularly preferably 5 to 11 parts by mass, per 100 parts by mass of all structural units constituting the (meth)acrylic resin (A). If it is within the above range, the mechanical strength is improved by improving the cohesiveness of the adhesive, and the flexibility and adhesiveness of the adhesive can be ensured, which is advantageous for heat resistance durability.
　ヒドロキシ基含有（メタ）アクリレート（ｂ）は、分子鎖中に１以上のヒドロキシ基を含有する（メタ）アクリレートであることができる。ヒドロキシ基含有（メタ）アクリレート（ｂ）の具体例としては、下記式（１）： Hydroxy group-containing (meth)acrylate (b) can be a (meth)acrylate containing one or more hydroxy groups in the molecular chain. Specific examples of hydroxy group-containing (meth)acrylate (b) include those represented by the following formula (1):
Figure JPOXMLDOC01-appb-C000005
 ［式（１）中、
　ｎは１～５の整数を示し、
　Ａ１は水素原子またはアルキル基を示し、
　Ｘ１は置換基を有していてもよいメチレン基を示す。
　ｎが２以上のとき、前記Ｘ１は同一であってよく、または異なっていてもよい］
で表される化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000005
 [In formula (1),
n represents an integer of 1 to 5;
A 1 represents a hydrogen atom or an alkyl group;
X1 represents a methylene group which may have a substituent.
When n is 2 or more, the X 1 may be the same or different.
Examples of the compound include compounds represented by the following formula:
　式（１）において、Ａ１を構成し得るアルキル基としては、例えばメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｓ－ブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ヘキシル基等の炭素数１～１０のアルキル基等が挙げられる。中でも好ましくはメチル基である。 In formula (1), examples of the alkyl group that can constitute A1 include alkyl groups having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a s-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. Of these, a methyl group is preferred.
　式（１）において、Ｘ１を構成し得るメチレン基が有していてもよい置換基としては、例えばハロゲン原子（フッ素原子、塩素原子、臭素原子、ヨウ素原子）、アルキル基（例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｓ－ブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ヘキシル基等の炭素数１～１０のアルキル基、好ましくは炭素数１～６のアルキル基、さらに好ましくは炭素数１～３のアルキル基）、シクロアルキル基（シクロペンチル基、シクロへキシル基等）、アリール基（フェニル基、アルキルフェニル基（トリル基、キシリル基等））、アラルキル基（ベンジル基等）、アルコキシ基（例えば、メトキシ基、エトキシ基等の炭素数１～４のアルコキシ基）、ポリオキシアルキレン基（例えば、ジオキシエチレン基等）、シクロアルコキシ基（例えば、シクロへキシルオキシ基等の炭素数５～１０シクロアルキルオキシ基等）、アリールオキシ基（例えば、フェノキシ基等）、アラルキルオキシ基（例えば、ベンジルオキシ基等）、アルキルチオ基（例えば、メチルチオ基、エチルチオ基等の炭素数１～４アルキルチオ基等）、シクロアルキルチオ基（例えば、シクロへキシルチオ基等）、アリールチオ基（例えば、チオフェノキシ基等）、アラルキルチオ基（例えば、ベンジルチオ基等）、アシル基（例えば、アセチル基等）、ニトロ基、シアノ基等が挙げられる。これらのうち、ハロゲン原子、アルキル基、アルコキシ基、アリールオキシ基等が好ましく、特にアルキル基（例えばメチル基、エチル基等）が好ましい。 In formula (1), examples of the substituent that the methylene group that can constitute X1 may have include, for example, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a s-butyl group, a tert-butyl group, a pentyl group, or a hexyl group, preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms), a cycloalkyl group (a cyclopentyl group, a cyclohexyl group, etc.), an aryl group (a phenyl group, an alkylphenyl group (a tolyl group, a xylyl group, etc.)), an aralkyl group (a benzyl group, etc.), an alkoxy group (for example, a methoxy group, an ethoxy group, etc.), Examples of the alkyl group include an alkoxy group having 1 to 4 carbon atoms), a polyoxyalkylene group (e.g., a dioxyethylene group, etc.), a cycloalkoxy group (e.g., a cycloalkyloxy group having 5 to 10 carbon atoms, such as a cyclohexyloxy group), an aryloxy group (e.g., a phenoxy group, etc.), an aralkyloxy group (e.g., a benzyloxy group, etc.), an alkylthio group (e.g., an alkylthio group having 1 to 4 carbon atoms, such as a methylthio group, an ethylthio group, etc.), a cycloalkylthio group (e.g., a cyclohexylthio group, etc.), an arylthio group (e.g., a thiophenoxy group, etc.), an aralkylthio group (e.g., a benzylthio group, etc.), an acyl group (e.g., an acetyl group, etc.), a nitro group, and a cyano group. Among these, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, etc. are preferred, and an alkyl group (e.g., a methyl group, an ethyl group, etc.) is particularly preferred.
　式（１）において、ｎは例えば１～４の整数であってよく、好ましくは１～３の整数であり、より好ましくは２である。ｎが２以上の場合、Ｘ１は同一であってもよく、異なっていてもよい。すなわち、ｎが２以上の場合、Ｘ１は無置換のメチレン基から構成されていてもよく、無置換のメチレン基と置換基を有するメチレン基から構成されていてもよく、置換基を有するメチレン基から構成されていてもよい。また、式（１）において、置換基を２つ以上有するときは、置換基は同じであっても、異なっていてもよい。
 In formula (1), n may be, for example, an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 2. When n is 2 or more, X 1 may be the same or different. That is, when n is 2 or more, X 1 may be composed of an unsubstituted methylene group, may be composed of an unsubstituted methylene group and a methylene group having a substituent, or may be composed of a methylene group having a substituent. In addition, when formula (1) has two or more substituents, the substituents may be the same or different.
　ヒドロキシ基含有（メタ）アクリレート（ｂ）の具体例としては、１－ヒドロキシメチル（メタ）アクリレート、１－ヒドロキシエチル（メタ）アクリレート、１－ヒドロキシヘプチル（メタ）アクリレート、１－ヒドロキシブチル（メタ）アクリレート、１－ヒドロキシペンチル（メタ）アクリレート等の１－ヒドロキシＣ１～Ｃ８アルキル（メタ）アクリレート；２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、２－ヒドロキシペンチル（メタ）アクリレート、２－ヒドロキシヘキシル（メタ）アクリレート等の２－ヒドロキシＣ２～Ｃ９アルキル（メタ）アクリレート；３－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシブチル（メタ）アクリレート、３－ヒドロキシペンチル（メタ）アクリレート、３－ヒドロキシヘキシル（メタ）アクリレート、３－ヒドロキシヘプチル（メタ）アクリレート等の３－ヒドロキシＣ３～Ｃ１０アルキル（メタ）アクリレート；４－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシペンチル（メタ）アクリレート、４－ヒドロキシヘキシル（メタ）アクリレート、４－ヒドロキシヘプチル（メタ）アクリレート、４－ヒドロキシオクチル（メタ）アクリレート等の４－ヒドロキシＣ４～Ｃ１１アルキル（メタ）アクリレート；２－クロロ－２－ヒドロキシプロピル（メタ）アクリレート、３－クロロ－２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート等が挙げられる。
　これらのうち、耐金属腐食性および耐熱耐久性の観点から、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート等のｎが２であるヒドロキシ含有（メタ）アクリレート；３－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシブチル（メタ）アクリレート、３－ヒドロキシペンチル（メタ）アクリレート等のｎが３であるヒドロキシ含有（メタ）アクリレートが好ましい。特に、ｎが２であるヒドロキシ含有（メタ）アクリレートが好ましく、これらの中でも２－ヒドロキシエチル（メタ）アクリレートが好ましい。２－ヒドロキシエチル（メタ）アクリレートは、均一な架橋構造の形成に有利であり、機械強度および耐熱耐久性を向上させることができる。
　ヒドロキシ基含有（メタ）アクリレート（ｂ）は、１種のみを単独で用いてもよいし、２種以上を併用してもよい。 Specific examples of the hydroxy group-containing (meth)acrylate (b) include 1-hydroxy C1 to C8 alkyl (meth)acrylates such as 1-hydroxymethyl (meth)acrylate, 1-hydroxyethyl (meth)acrylate, 1-hydroxyheptyl (meth)acrylate, 1-hydroxybutyl (meth)acrylate, and 1-hydroxypentyl (meth)acrylate; 2-hydroxy C2 to C9 alkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxypentyl (meth)acrylate, and 2-hydroxyhexyl (meth)acrylate; 3-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 3-hydroxybutyl (meth)acrylate; 3-hydroxy C3 to C10 alkyl (meth)acrylates such as 4-hydroxybutyl (meth)acrylate, 4-hydroxypentyl (meth)acrylate, 4-hydroxyhexyl (meth)acrylate, 4-hydroxyheptyl (meth)acrylate, and 4-hydroxy C4 to C11 alkyl (meth)acrylates such as 4-hydroxybutyl (meth)acrylate, 4-hydroxypentyl (meth)acrylate, 4-hydroxyhexyl (meth)acrylate, 4-hydroxyheptyl (meth)acrylate, and 4-hydroxyoctyl (meth)acrylate; 2-chloro-2-hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate.
Among these, from the viewpoint of metal corrosion resistance and heat resistance durability, hydroxy-containing (meth)acrylates in which n is 2, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate, and hydroxy-containing (meth)acrylates in which n is 3, such as 3-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 3-hydroxypentyl (meth)acrylate, are preferred. In particular, hydroxy-containing (meth)acrylates in which n is 2 are preferred, and among these, 2-hydroxyethyl (meth)acrylate is preferred. 2-Hydroxyethyl (meth)acrylate is advantageous in forming a uniform crosslinked structure, and can improve mechanical strength and heat resistance durability.
The hydroxyl group-containing (meth)acrylate (b) may be used alone or in combination of two or more kinds.
　ヒドロキシ基含有（メタ）アクリレート（ｂ）由来の構成単位の含有量は、耐金属腐食性および耐熱耐久性の観点から好ましくは（メタ）アクリル系樹脂（Ａ）を構成する全構成単位１００質量部に対して０．３質量部以上５．５質量部以下、より好ましくは０．４質量部以上４．０質量部以下、さらに好ましくは０．５質量部以上３．０質量部以下、特に好ましくは０．５質量部以上２．５質量部以下である。 From the viewpoint of metal corrosion resistance and heat resistance and durability, the content of the structural units derived from the hydroxyl group-containing (meth)acrylate (b) is preferably from 0.3 to 5.5 parts by mass, more preferably from 0.4 to 4.0 parts by mass, even more preferably from 0.5 to 3.0 parts by mass, and particularly preferably from 0.5 to 2.5 parts by mass, relative to 100 parts by mass of all structural units constituting the (meth)acrylic resin (A).
　（メタ）アクリル系樹脂（Ａ）は、耐金属腐食性および耐熱耐久性の観点から好ましくは（メタ）アクリル系樹脂（Ａ）を構成する全構成単位１００質量部に対してアルキルメタクリレート（ａ）由来の構成単位を１質量部以上１５質量部以下、およびヒドロキシ基含有（メタ）アクリレート（ｂ）由来の構成単位を０．３質量部以上５．５質量部以下含有する（メタ）アクリル系樹脂である。 From the viewpoint of metal corrosion resistance and heat resistance and durability, the (meth)acrylic resin (A) is preferably a (meth)acrylic resin that contains 1 part by mass or more and 15 parts by mass or less of structural units derived from alkyl methacrylate (a) and 0.3 parts by mass or more and 5.5 parts by mass or less of structural units derived from hydroxyl group-containing (meth)acrylate (b) per 100 parts by mass of all structural units constituting the (meth)acrylic resin (A).
　カルボキシ基含有モノマー（ｃ）の具体例としては、(メタ)アクリル酸、マレイン酸、無水マレイン酸、フマル酸、クロトン酸、カルボキシアルキル（メタ）アクリレート（例えばカルボキシエチル（メタ）アクリレート、カルボキシペンチル（メタ）アクリレート）等が挙げられる。中でもアクリル酸が好ましい。アクリル酸はヒドロキシ基含有(メタ)クリレート（ｂ）と架橋剤との反応を促進し、均一な架橋構造の形成に有利であり、耐熱耐久性を向上させることができる。カルボキシ基含有モノマー（ｃ）は１種のみを単独で用いてもよいし、２種以上を併用してもよい。 Specific examples of the carboxyl group-containing monomer (c) include (meth)acrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, and carboxyalkyl (meth)acrylates (e.g., carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate). Of these, acrylic acid is preferred. Acrylic acid promotes the reaction between the hydroxyl group-containing (meth)acrylate (b) and the crosslinking agent, which is advantageous for the formation of a uniform crosslinked structure and can improve heat resistance and durability. The carboxyl group-containing monomer (c) may be used alone or in combination of two or more types.
　カルボキシ基含有モノマー（ｃ）由来の構成単位の含有量は、（メタ）アクリル系樹脂（Ａ）を構成する全構成単位１００質量部に対して０．０１質量部以上５．５質量部以下であってよく、耐金属腐食性および耐熱耐久性の観点から好ましくは０．０５質量部以上３質量部以下、より好ましくは０．１質量部以上２質量部以下である。 The content of the structural unit derived from the carboxyl group-containing monomer (c) may be 0.01 parts by mass or more and 5.5 parts by mass or less relative to 100 parts by mass of all structural units constituting the (meth)acrylic resin (A), and from the viewpoint of metal corrosion resistance and heat resistance durability, it is preferably 0.05 parts by mass or more and 3 parts by mass or less, and more preferably 0.1 parts by mass or more and 2 parts by mass or less.
　ヒドロキシ基含有（メタ）アクリレート（ｂ）由来の構成単位に対するカルボキシ基含有モノマー（ｃ）由来の構成単位の質量比（ｃ）／（ｂ）［以下、質量比（ｃ）／（ｂ）ともいう］は、耐金属腐食性および耐熱耐久性の観点から好ましくは０．０６以上１．０以下であり、より好ましくは０．０６以上０．９以下、さらに好ましくは０．０８以上０．８以下、特に好ましくは０．１以上０．７以下である。 The mass ratio (c)/(b) of the constituent units derived from the carboxyl group-containing monomer (c) to the constituent units derived from the hydroxyl group-containing (meth)acrylate (b) [hereinafter also referred to as the mass ratio (c)/(b)] is preferably 0.06 or more and 1.0 or less, more preferably 0.06 or more and 0.9 or less, even more preferably 0.08 or more and 0.8 or less, and particularly preferably 0.1 or more and 0.7 or less, from the viewpoint of metal corrosion resistance and heat resistance durability.
　（メタ）アクリル系樹脂（Ａ）は、さらに、アルキルアクリレート由来の構成単位、ホモポリマーのガラス転移温度（Ｔｇ）が３０℃未満のアルキルメタクリレート由来の構成単位、置換基含有アルキル（メタ）アクリレート由来の構成単位、ヒドロキシ基以外の極性官能基を有する単量体に由来する構成単位、（メタ）アクリルアミド系単量体に由来する構成単位、スチレン系単量体に由来する構成単位、ビニル系単量体に由来する構成単位、分子内に複数の（メタ）アクリロイル基を有する単量体に由来する構成単位等を含んでいてもよい。 The (meth)acrylic resin (A) may further contain structural units derived from alkyl acrylates, structural units derived from alkyl methacrylates having a homopolymer glass transition temperature (Tg) of less than 30°C, structural units derived from substituted alkyl (meth)acrylates, structural units derived from monomers having polar functional groups other than hydroxyl groups, structural units derived from (meth)acrylamide monomers, structural units derived from styrene monomers, structural units derived from vinyl monomers, structural units derived from monomers having multiple (meth)acryloyl groups in the molecule, etc.
　（メタ）アクリル系樹脂（Ａ）は、ホモポリマーのＴｇが０℃未満のアルキルアクリレートを含んでいることが好ましい。ホモポリマーのＴｇが０℃未満のアルキルアクリレートとしては、例えば、エチルアクリレート、ｎ－及びｉ－プロピルアクリレート、ｎ－及びｉ－ブチルアクリレート、ｎ－ペンチルアクリレート、ｎ－及びｉ－へキシルアクリレート、ｎ－ヘプチルアクリレート、ｎ－及びｉ－オクチルアクリレート、２－エチルへキシルアクリレート、ｎ－及びｉ－ノニルアクリレート、ｎ－及びｉ－デシルアクリレート、ｎ－ドデシルアクリレートなどのアルキル基の炭素数が２～１２程度の直鎖状又は分岐鎖状アルキルアクリレートなどが挙げられる。ホモポリマーのＴｇが０℃未満のアルキルアクリレートは、脂環式構造を有するアルキルアクリレート（シクロアルキルアクリレート）であってもよいが、光学フィルムに対する追従性（又は柔軟性や粘着性）などの観点から、炭素数が２～１０のアルキルアクリレート、好ましくは炭素数が３～８のアルキルアクリレート、さらに好ましくは炭素数が４～６のアルキルアクリレートが好ましい。これらのアルキルアクリレートを用いると、追従性を高くでき、例えば耐剥がれ性などに有利である。これらのアルキルアクリレートは単独又は二種以上組み合わせて使用できる。 The (meth)acrylic resin (A) preferably contains an alkyl acrylate having a homopolymer Tg of less than 0° C. Examples of alkyl acrylates having a homopolymer Tg of less than 0° C. include linear or branched alkyl acrylates having an alkyl group with about 2 to 12 carbon atoms, such as ethyl acrylate, n- and i-propyl acrylate, n- and i-butyl acrylate, n-pentyl acrylate, n- and i-hexyl acrylate, n-heptyl acrylate, n- and i-octyl acrylate, 2-ethylhexyl acrylate, n- and i-nonyl acrylate, n- and i-decyl acrylate, and n-dodecyl acrylate. The alkyl acrylate having a homopolymer Tg of less than 0°C may be an alkyl acrylate (cycloalkyl acrylate) having an alicyclic structure, but from the viewpoint of conformability (or flexibility or adhesion) to the optical film, an alkyl acrylate having 2 to 10 carbon atoms, preferably an alkyl acrylate having 3 to 8 carbon atoms, and more preferably an alkyl acrylate having 4 to 6 carbon atoms is preferred. Use of these alkyl acrylates can improve conformability, which is advantageous for, for example, peel resistance. These alkyl acrylates can be used alone or in combination of two or more kinds.
　（メタ）アクリル系樹脂（Ａ）は、ホモポリマーのＴｇが０℃以上のアルキルアクリレートを含んでいることが好ましい。ホモポリマーのＴｇが０℃以上のアルキルアクリレートとしてはメチルアクリレート、ステアリルアクリレート、ｔ－ブチルアクリレートなどが挙げられる。ホモポリマーのＴｇが０℃以上のアルキルアクリレートとしては、脂環式構造を有するアルキルアクリレート（シクロアルキルアクリレート）であってもよい。これらのアルキルアルキルアクリレートを用いると、粘着剤の機械強度がさらに向上し、耐熱耐久性に対して有利である。これらのアルキルアクリレートは、１種のみを用いてもよいが、２種以上を組み合せて用いてもよい。脂環式構造は、炭素数が通常５以上、好ましくは５～７程度のシクロパラフィン構造であることができる。脂環式構造を有するホモポリマーのＴｇが０℃以上のアルキルアクリレートの具体例は、イソボルニルアクリレート、シクロヘキシルアクリレート、ジシクロペンタニルアクリレート、シクロドデシルアクリレート、メチルシクロヘキシルアクリレート、トリメチルシクロヘキシルアクリレート、ｔｅｒｔ－ブチルシクロヘキシルアクリレート、シクロヘキシルα－エトキシアクリレート等を含む。 The (meth)acrylic resin (A) preferably contains an alkyl acrylate having a homopolymer Tg of 0°C or higher. Examples of alkyl acrylates having a homopolymer Tg of 0°C or higher include methyl acrylate, stearyl acrylate, and t-butyl acrylate. The alkyl acrylate having a homopolymer Tg of 0°C or higher may be an alkyl acrylate (cycloalkyl acrylate) having an alicyclic structure. The use of these alkyl alkyl acrylates further improves the mechanical strength of the adhesive and is advantageous in terms of heat resistance and durability. These alkyl acrylates may be used alone or in combination of two or more. The alicyclic structure may be a cycloparaffin structure having a carbon number of usually 5 or more, preferably about 5 to 7. Specific examples of alkyl acrylates having a homopolymer with an alicyclic structure and a Tg of 0°C or higher include isobornyl acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, cyclododecyl acrylate, methylcyclohexyl acrylate, trimethylcyclohexyl acrylate, tert-butylcyclohexyl acrylate, cyclohexyl α-ethoxy acrylate, etc.
　ホモポリマーのＴｇが３０℃未満のアルキルメタクリレートとしては、例えば、ｎ－ブチルメタクリレート、ｎ－ペンチルメタクリレート、ｎ－及びｉ－へキシルメタクリレート、ｎ－ヘプチルメタクリレート、ｎ－及びｉ－オクチルメタクリレート、２－エチルへキシルメタクリレート、ｎ－及びｉ－ノニルメタクリレート、ｎ－デシルメタクリレート、ｎ－ドデシルメタクリレートなどのアルキル基の炭素数が４～１２程度の直鎖状又は分岐鎖状アルキルメタクリレートなどが挙げられる。これらのアルキルメタクリレートは単独又は二種以上組み合わせて使用できる。 Examples of alkyl methacrylates with a homopolymer Tg of less than 30°C include linear or branched alkyl methacrylates with an alkyl group carbon number of about 4 to 12, such as n-butyl methacrylate, n-pentyl methacrylate, n- and i-hexyl methacrylate, n-heptyl methacrylate, n- and i-octyl methacrylate, 2-ethylhexyl methacrylate, n- and i-nonyl methacrylate, n-decyl methacrylate, and n-dodecyl methacrylate. These alkyl methacrylates can be used alone or in combination of two or more.
　置換基含有アルキル（メタ）アクリレートとしては、例えば、アルキル（メタ）アクリレートにおけるアルキル基に置換基が導入された（アルキル基の水素原子が置換基により置換された）アルキル（メタ）アクリレートが挙げられる。該置換基としては、例えば、アリール基（フェニル基等）、アリールオキシ基（フェノキシ基）、アルコキシ基（例えばメトキシ基、エトキシ基等）等であってもよい。置換基含有アルキルアクリレートとしては、例えば、アルコキシアルキルアクリレート（例えば２－メトキシエチルアクリレート、エトキシメチルアクリレートなど）、アリールオキシアルキルアクリレート（例えばフェノキシエチルアクリレートなど）、アリールオキシポリアルキレングリコールモノアクリレート、ポリアルキレングリコールモノアクリレートなどが挙げられる。これらのアルキルアクリレートは単独又は２種以上組み合わせて使用できる。アリール基やアリールオキシ基などの芳香環を含有するアルキルアクリレートを含むことで、耐久試験時の偏光板の白抜けを改善することができる。またアリールオキシポリアルキレングリコールモノアクリレート及びポリアルキレングリコールモノアクリレートのアルキレン基は、例えばメチレン基、エチレン基、プロピレン基などのＣ１－Ｃ６アルキレン基（好ましくはエチレン基等）などであってもよく、オキシアルキレン基の繰り返し単位は、粘着剤組成物から形成される粘着層の耐久性の観点から、例えば２～７、好ましくは２～５（特に２）であってもよい。具体的には、例えばフェノキシジエチレングリコールアクリレートなどのフェノキシジ乃至ヘプタＣ１－Ｃ３アルキレングリコールモノアクリレート、ジエチレングリコールモノアクリレートなどのジ乃至ヘプタＣ１－Ｃ３アルキレングリコールモノアクリレートなどが挙げられる。 Examples of the alkyl (meth)acrylate containing a substituent include alkyl (meth)acrylates in which a substituent has been introduced into the alkyl group in the alkyl (meth)acrylate (the hydrogen atom of the alkyl group has been replaced by a substituent). The substituent may be, for example, an aryl group (such as a phenyl group), an aryloxy group (such as a phenoxy group), an alkoxy group (such as a methoxy group, an ethoxy group), etc. Examples of the alkyl acrylate containing a substituent include an alkoxyalkyl acrylate (such as 2-methoxyethyl acrylate, ethoxymethyl acrylate, etc.), an aryloxyalkyl acrylate (such as phenoxyethyl acrylate, etc.), an aryloxypolyalkylene glycol monoacrylate, a polyalkylene glycol monoacrylate, etc. These alkyl acrylates can be used alone or in combination of two or more kinds. By including an alkyl acrylate containing an aromatic ring such as an aryl group or an aryloxy group, it is possible to improve the white spots of the polarizing plate during a durability test. The alkylene group of the aryloxy polyalkylene glycol monoacrylate and polyalkylene glycol monoacrylate may be, for example, a C1-C6 alkylene group (preferably an ethylene group, etc.) such as a methylene group, an ethylene group, or a propylene group, and the repeating unit of the oxyalkylene group may be, for example, 2 to 7, preferably 2 to 5 (particularly 2), from the viewpoint of the durability of the adhesive layer formed from the adhesive composition. Specific examples include phenoxy di- to hepta C1-C3 alkylene glycol monoacrylates such as phenoxy diethylene glycol acrylate, and di- to hepta C1-C3 alkylene glycol monoacrylates such as diethylene glycol monoacrylate.
　ヒドロキシ基以外の極性官能基を有する単量体としては、置換若しくは無置換アミノ基、エポキシ基等の複素環基などの置換基を有する（メタ）アクリレートが挙げられる。具体的には、アクリロイルモルホリン、ビニルカプロラクタム、Ｎ－ビニル－２－ピロリドン、ビニルピリジン、テトラヒドロフルフリル（メタ）アクリレート、カプロラクトン変性テトラヒドロフルフリルアクリレート、３，４－エポキシシクロヘキシルメチル（メタ）アクリレート、グリシジル（メタ）アクリレート、２，５－ジヒドロフラン等の複素環基を有する単量体；アミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、ジメチルアミノプロピル（メタ）アクリレート等の置換若しくは無置換アミノ基を有する単量体などが挙げられる。これらの単量体は単独又は二種以上組み合わせて使用できる。なお、粘着剤層に積層可能なセパレートフィルムの剥離性の低下を防止する観点から、アミノ基を有する単量体由来の構成単位を実質的に含まないことが好ましい。なお、実質的に含まないとは、（メタ）アクリル系樹脂（Ａ）を構成する全構成単位１００質量部に対して、１．０質量部未満であることをいう。 Monomers having a polar functional group other than a hydroxyl group include (meth)acrylates having a substituent such as a substituted or unsubstituted amino group, or a heterocyclic group such as an epoxy group. Specific examples include monomers having a heterocyclic group such as acryloylmorpholine, vinylcaprolactam, N-vinyl-2-pyrrolidone, vinylpyridine, tetrahydrofurfuryl (meth)acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, glycidyl (meth)acrylate, and 2,5-dihydrofuran; and monomers having a substituted or unsubstituted amino group such as aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, and dimethylaminopropyl (meth)acrylate. These monomers can be used alone or in combination of two or more. From the viewpoint of preventing a decrease in the releasability of the separate film that can be laminated to the adhesive layer, it is preferable that the composition does not substantially contain structural units derived from monomers having an amino group. "Substantially free" means that the amount is less than 1.0 part by mass per 100 parts by mass of all structural units constituting the (meth)acrylic resin (A).
　（メタ）アクリルアミド系単量体としては、例えば、Ｎ－メチロール（メタ）アクリルアミド、Ｎ－（２－ヒドロキシエチル）（メタ）アクリルアミド、Ｎ－（３－ヒドロキシプロピル）（メタ）アクリルアミド、Ｎ－（４－ヒドロキシブチル）（メタ）アクリルアミド、Ｎ－（５－ヒドロキシペンチル）（メタ）アクリルアミド、Ｎ－（６－ヒドロキシヘキシル）（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド、Ｎ－イソプロピル（メタ）アクリルアミド、Ｎ－（３－ジメチルアミノプロピル）（メタ）アクリルアミド、Ｎ－（１，１－ジメチル－３－オキソブチル）（メタ）アクリルアミド、Ｎ－〔２－（２－オキソ－１－イミダゾリジニル）エチル〕（メタ）アクリルアミド、２－（メタ）アクリロイルアミノ－２－メチル－１－プロパンスルホン酸、Ｎ－（メトキシメチル）（メタ）アクリルアミド、Ｎ－（エトキシメチル）（メタ）アクリルアミド、Ｎ－（プロポキシメチル）（メタ）アクリルアミド、Ｎ－（１－メチルエトキシメチル）（メタ）アクリルアミド、Ｎ－（１－メチルプロポキシメチル）（メタ）アクリルアミド、Ｎ－（２－メチルプロポキシメチル）（メタ）アクリルアミド〔別名：Ｎ－（イソブトキシメチル）（メタ）アクリルアミド〕、Ｎ－（ブトキシメチル）（メタ）アクリルアミド、Ｎ－（１，１－ジメチルエトキシメチル）（メタ）アクリルアミド、Ｎ－（２－メトキシエチル）（メタ）アクリルアミド、Ｎ－（２－エトキシエチル）（メタ）アクリルアミド、Ｎ－（２－プロポキシエチル）（メタ）アクリルアミド、Ｎ－〔２－（１－メチルエトキシ）エチル〕（メタ）アクリルアミド、Ｎ－〔２－（１－メチルプロポキシ）エチル〕（メタ）アクリルアミド、Ｎ－〔２－（２－メチルプロポキシ）エチル〕（メタ）アクリルアミド〔別名：Ｎ－（２－イソブトキシエチル）アクリルアミド〕、Ｎ－（２－ブトキシエチル）（メタ）アクリルアミド、Ｎ－〔２－（１，１－ジメチルエトキシ）エチル〕（メタ）アクリルアミド等を挙げることができる。（メタ）アクリルアミド単量体に由来する構成単位は、１種のみを用いてもよいが、２種以上を組み合せて用いてもよい。 Examples of (meth)acrylamide monomers include N-methylol (meth)acrylamide, N-(2-hydroxyethyl) (meth)acrylamide, N-(3-hydroxypropyl) (meth)acrylamide, N-(4-hydroxybutyl) (meth)acrylamide, N-(5-hydroxypentyl) (meth)acrylamide, N-(6-hydroxyhexyl) (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, and N-isopropyl (meth)acrylamide. isopropyl(meth)acrylamide, N-(3-dimethylaminopropyl)(meth)acrylamide, N-(1,1-dimethyl-3-oxobutyl)(meth)acrylamide, N-[2-(2-oxo-1-imidazolidinyl)ethyl](meth)acrylamide, 2-(meth)acryloylamino-2-methyl-1-propanesulfonic acid, N-(methoxymethyl)(meth)acrylamide, N-(ethoxymethyl)(meth)acrylamide, N-(propoxymethyl)(meth)acrylamide , N-(1-methylethoxymethyl)(meth)acrylamide, N-(1-methylpropoxymethyl)(meth)acrylamide, N-(2-methylpropoxymethyl)(meth)acrylamide [alias: N-(isobutoxymethyl)(meth)acrylamide], N-(butoxymethyl)(meth)acrylamide, N-(1,1-dimethylethoxymethyl)(meth)acrylamide, N-(2-methoxyethyl)(meth)acrylamide, N-(2-ethoxyethyl)(meth)acrylamide, N Examples of the constituent units derived from the (meth)acrylamide monomer include N-(2-propoxyethyl)(meth)acrylamide, N-[2-(1-methylethoxy)ethyl](meth)acrylamide, N-[2-(1-methylpropoxy)ethyl](meth)acrylamide, N-[2-(2-methylpropoxy)ethyl](meth)acrylamide (also known as N-(2-isobutoxyethyl)acrylamide), N-(2-butoxyethyl)(meth)acrylamide, and N-[2-(1,1-dimethylethoxy)ethyl](meth)acrylamide. Only one type of constituent unit derived from the (meth)acrylamide monomer may be used, or two or more types may be used in combination.
　スチレン系単量体としては、例えば、スチレン；メチルスチレン、ジメチルスチレン、トリメチルスチレン、エチルスチレン、ジエチルスチレン、トリエチルスチレン、プロピルスチレン、ブチルスチレン、ヘキシルスチレン、ヘプチルスチレン、オクチルスチレン等のアルキルスチレン；フルオロスチレン、クロロスチレン、ブロモスチレン、ジブロモスチレン、ヨードスチレン等のハロゲン化スチレン；ニトロスチレン；アセチルスチレン；メトキシスチレン；ジビニルベンゼン等が挙げられる。 Examples of styrene monomers include styrene; alkyl styrenes such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, and octylstyrene; halogenated styrenes such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, and iodostyrene; nitrostyrene; acetylstyrene; methoxystyrene; and divinylbenzene.
　ビニル系単量体としては、例えば、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、２－エチルヘキサン酸ビニル、ラウリン酸ビニル等の脂肪酸ビニルエステル；塩化ビニル、臭化ビニル等のハロゲン化ビニル；塩化ビニリデン等のハロゲン化ビニリデン；ビニルピリジン、ビニルピロリドン、ビニルカルバゾール等の含窒素芳香族ビニル；ブタジエン、イソプレン、クロロプレン等の共役ジエン単量体等が挙げられる。 Vinyl monomers include, for example, fatty acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, and vinyl laurate; vinyl halides such as vinyl chloride and vinyl bromide; vinylidene halides such as vinylidene chloride; nitrogen-containing aromatic vinyls such as vinylpyridine, vinylpyrrolidone, and vinylcarbazole; and conjugated diene monomers such as butadiene, isoprene, and chloroprene.
　分子内に複数の（メタ）アクリロイル基を有する単量体としては、例えば、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート等の分子内に２個の（メタ）アクリロイル基を有する単量体；トリメチロールプロパントリ（メタ）アクリレート等の分子内に３個の（メタ）アクリロイル基を有する単量体等が挙げられる。 Examples of monomers having multiple (meth)acryloyl groups in the molecule include monomers having two (meth)acryloyl groups in the molecule, such as 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and tripropylene glycol di(meth)acrylate; and monomers having three (meth)acryloyl groups in the molecule, such as trimethylolpropane tri(meth)acrylate.
　（メタ）アクリル系樹脂（Ａ）の重量平均分子量（Ｍｗ）は、耐金属腐食性および耐熱耐久性の観点から好ましくは１００万以上３２０万以下であり、より好ましくは１１０万～３１０万であり、より好ましくは１２０万～３００万であり、特に好ましくは１３０万～２９０万である。また、重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比で表される分子量分布（Ｍｗ／Ｍｎ）は、通常１．５以上１０以下、好ましくは２以上８以下、より好ましくは２．５以上７以下である。重量平均分子量は、ゲルパーミエーションクロマトグラフィにより分析でき、標準ポリスチレン換算の値である。 The weight average molecular weight (Mw) of the (meth)acrylic resin (A) is preferably 1 million or more and 3.2 million or less, more preferably 1.1 million to 3.1 million, more preferably 1.2 million to 3 million, and particularly preferably 1.3 million to 2.9 million, from the viewpoint of metal corrosion resistance and heat resistance and durability. The molecular weight distribution (Mw/Mn), which is expressed as the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is usually 1.5 to 10, preferably 2 to 8, and more preferably 2.5 to 7. The weight average molecular weight can be analyzed by gel permeation chromatography and is a value converted into standard polystyrene.
　（メタ）アクリル系樹脂（Ａ）はガラス転移温度（Ｔｇ）が、機械強度および耐熱耐久性の観点から好ましくは－４５℃以上－１０℃以下、より好ましくは－４０℃以上－１５℃以下、さらに好ましくは－３８℃以上－２０℃以下である。 The (meth)acrylic resin (A) preferably has a glass transition temperature (Tg) of -45°C or higher and -10°C or lower, more preferably -40°C or higher and -15°C or lower, and even more preferably -38°C or higher and -20°C or lower, from the viewpoints of mechanical strength and heat resistance and durability.
　（メタ）アクリル系樹脂（Ａ）（２種類以上を組み合わせる場合はそれらの混合物）は、それを酢酸エチルに溶かして濃度２０質量％に調整した溶液が、２５℃において２０Ｐａ・ｓ以下、さらには０．１Ｐａ・ｓ以上７Ｐａ・ｓ以下の粘度を示すことが好ましい。粘度は、ブルックフィールド粘度計によって測定できる。 The (meth)acrylic resin (A) (or a mixture of two or more types) is preferably dissolved in ethyl acetate to a concentration of 20% by mass, and the solution preferably exhibits a viscosity of 20 Pa·s or less at 25°C, and more preferably 0.1 Pa·s or more and 7 Pa·s or less. The viscosity can be measured using a Brookfield viscometer.
　（メタ）アクリル系樹脂（Ａ）は、例えば、溶液重合法、塊状重合法、懸濁重合法、乳化重合法等、公知の方法によって製造することができる。（メタ）アクリル系樹脂（Ａ）の製造においては通常、重合開始剤が用いられる。重合開始剤は、（メタ）アクリル系樹脂（Ａ）の製造に用いられる全ての単量体の合計１００質量部に対して、０．００１～５質量部程度使用される。また、（メタ）アクリル系樹脂（Ａ）は、例えば紫外線等の活性エネルギー線によって重合を進行させる方法により製造してもよい。 The (meth)acrylic resin (A) can be produced by known methods such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization. A polymerization initiator is usually used in the production of the (meth)acrylic resin (A). The polymerization initiator is used in an amount of about 0.001 to 5 parts by mass per 100 parts by mass of the total of all monomers used in the production of the (meth)acrylic resin (A). The (meth)acrylic resin (A) may also be produced by a method in which polymerization is advanced by active energy rays such as ultraviolet rays.
　重合開始剤としては、熱重合開始剤や光重合開始剤等が用いられる。光重合開始剤として、例えば、４－（２－ヒドロキシエトキシ）フェニル（２－ヒドロキシ－２－プロピル）ケトン等を挙げることができる。熱重合開始剤として、例えば、２，２’－アゾビスイソブチロニトリル、２，２’－アゾビス（２－メチルブチロニトリル）、１，１’－アゾビス（シクロヘキサン－１－カルボニトリル）、２，２’－アゾビス（２，４－ジメチルバレロニトリル）、２，２’－アゾビス（２，４－ジメチル－４－メトキシバレロニトリル）、ジメチル－２，２’－アゾビス（２－メチルプロピオネート）、２，２’－アゾビス（２－ヒドロキシメチルプロピオニトリル）のようなアゾ系化合物；ラウリルパーオキサイド、ｔｅｒｔ－ブチルハイドロパーオキサイド、過酸化ベンゾイル、ｔｅｒｔ－ブチルパーオキシベンゾエート、クメンハイドロパーオキサイド、ジイソプロピルパーオキシジカーボネート、ジプロピルパーオキシジカーボネート、ｔｅｒｔ－ブチルパーオキシネオデカノエート、ｔｅｒｔ－ブチルパーオキシピバレート、（３，５，５－トリメチルヘキサノイル）パーオキサイドのような有機過酸化物；過硫酸カリウム、過硫酸アンモニウム、過酸化水素のような無機過酸化物等を挙げることができる。また、過酸化物と還元剤を併用したレドックス系開始剤等も、重合開始剤として使用しうる。 As the polymerization initiator, a thermal polymerization initiator or a photopolymerization initiator is used. As the photopolymerization initiator, for example, 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone can be mentioned. As the thermal polymerization initiator, for example, azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl-2,2'-azobis(2-methylpropionate), and 2,2'-azobis(2-hydroxymethylpropionitrile); lauryl peroxide; Examples of the peroxide include organic peroxides such as tert-butyl hydroperoxide, benzoyl peroxide, tert-butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, dipropyl peroxydicarbonate, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, and (3,5,5-trimethylhexanoyl) peroxide; and inorganic peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide. Redox initiators that use a peroxide in combination with a reducing agent can also be used as the polymerization initiator.
　（メタ）アクリル系樹脂（Ａ）の製造方法としては、上に示した方法の中でも溶液重合法が好ましい。溶液重合法の一例は、単量体および有機溶媒を混合し、窒素雰囲気下、熱重合開始剤を添加して、４０～９０℃程度、好ましくは６０～８０℃程度にて３～１０時間程度攪拌することである。反応を制御するために、単量体や熱重合開始剤を重合中に連続的または間歇的に添加したり、有機溶媒に溶解した状態で添加したりしてもよい。有機溶媒としては、例えば、トルエン、キシレンのような芳香族炭化水素類；酢酸エチル、酢酸ブチルのようなエステル類；プロピルアルコール、イソプロピルアルコールのような脂肪族アルコール類；アセトン、メチルエチルケトン、メチルイソブチルケトンのようなケトン類等を用いることができる。 Among the above methods, the solution polymerization method is preferred as a method for producing the (meth)acrylic resin (A). One example of the solution polymerization method is to mix the monomer and an organic solvent, add a thermal polymerization initiator under a nitrogen atmosphere, and stir for about 3 to 10 hours at about 40 to 90°C, preferably about 60 to 80°C. To control the reaction, the monomer and the thermal polymerization initiator may be added continuously or intermittently during polymerization, or may be added in a dissolved state in an organic solvent. Examples of organic solvents that can be used include aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; aliphatic alcohols such as propyl alcohol and isopropyl alcohol; and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.
　（２）架橋剤（Ｂ）
　粘着剤組成物は、架橋剤（Ｂ）をさらに含有する。架橋剤（Ｂ）は、（メタ）アクリル系樹脂（Ａ）中の特に極性官能基含有単量体に由来する構造単位と反応し、（メタ）アクリル系樹脂（Ａ）を架橋させる化合物であることができる。具体的には、イソシアネート系化合物、エポキシ系化合物、アジリジン系化合物、金属キレート系化合物等が例示される。これらのうち、イソシアネート系化合物、エポキシ系化合物およびアジリジン系化合物は、（メタ）アクリル樹脂中の極性官能基と反応しうる官能基を分子内に少なくとも２個有する。架橋剤（Ｂ）は、１種のみを単独で使用してもよいし、２種以上を併用してもよい。 (2) Crosslinking agent (B)
The pressure-sensitive adhesive composition further contains a crosslinking agent (B). The crosslinking agent (B) can be a compound that reacts with a structural unit derived from a polar functional group-containing monomer in the (meth)acrylic resin (A) and crosslinks the (meth)acrylic resin (A). Specific examples include isocyanate-based compounds, epoxy-based compounds, aziridine-based compounds, and metal chelate-based compounds. Of these, isocyanate-based compounds, epoxy-based compounds, and aziridine-based compounds have at least two functional groups in the molecule that can react with the polar functional group in the (meth)acrylic resin. The crosslinking agent (B) may be used alone or in combination of two or more.
　イソシアネート系化合物としては、分子内に少なくとも２個のイソシアナト基（－ＮＣＯ）を有する化合物が好ましく、例えば、脂肪族イソシアネート系化合物（例えばヘキサメチレンジイソシアネート等）、脂環族イソシアネート系化合物（例えばイソホロンジイソシアネート）、芳香族イソシアネート系化合物（例えばトリレンジイソシアネート、キシリレンジイソシアネート、水添キシリレンジイソシアネート、ジフェニルメタンジイソシアネート、水添ジフェニルメタンジイソシアネート、ナフタレンジイソシアネート、トリフェニルメタントリイソシアネート等）等が挙げられる。また、架橋剤（Ｂ）は、イソシアネート化合物の多価アルコール化合物による付加体（アダクト体）（例えば、グリセロール、トリメチロールプロパン等による付加体）、イソシアヌレート化物、ビュレット型化合物、ポリエーテルポリオール、ポリエステルポリオール、アクリルポリオール、ポリブタジエンポリオール、ポリイソプレンポリオール等と付加反応させたウレタンプレポリマー型のイソシアネート化合物等の誘導体であってもよい。架橋剤（Ｂ）は単独または二種以上を組み合わせて使用できる。これらのうち、代表的には芳香族イソシアネート系化合物（例えばトリレンジイソシアネート、キシリレンジイソシアネート）、脂肪族イソシアネート系化合物（例えばヘキサメチレンジイソシアネート）またはこれらの多価アルコール化合物（グリセロール、トリメチロールプロパン）による付加体が挙げられる。架橋剤（Ｂ）が、芳香族イソシアネート系化合物および／またはこれらの多価アルコール化合物による付加体を含む場合、均一な架橋構造を形成しやすく、耐金属腐食性および耐熱耐久性を向上し易い傾向にある。 As the isocyanate compound, a compound having at least two isocyanato groups (-NCO) in the molecule is preferred, and examples thereof include aliphatic isocyanate compounds (e.g., hexamethylene diisocyanate, etc.), alicyclic isocyanate compounds (e.g., isophorone diisocyanate), aromatic isocyanate compounds (e.g., tolylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, etc.). The crosslinking agent (B) may be an adduct of an isocyanate compound with a polyhydric alcohol compound (e.g., an adduct with glycerol, trimethylolpropane, etc.), an isocyanurate, a biuret-type compound, a urethane prepolymer type isocyanate compound obtained by addition reaction with a polyether polyol, a polyester polyol, an acrylic polyol, a polybutadiene polyol, a polyisoprene polyol, etc., or a derivative thereof. The crosslinking agent (B) may be used alone or in combination of two or more. Among these, representative examples include aromatic isocyanate compounds (e.g., tolylene diisocyanate, xylylene diisocyanate), aliphatic isocyanate compounds (e.g., hexamethylene diisocyanate), or adducts of these with polyhydric alcohol compounds (glycerol, trimethylolpropane). When the crosslinking agent (B) contains an adduct of an aromatic isocyanate compound and/or these with a polyhydric alcohol compound, it tends to form a uniform crosslinked structure and to improve metal corrosion resistance and heat resistance durability.
　エポキシ系化合物は、分子内に少なくとも２個のエポキシ基を有する化合物である。具体的な化合物としては、例えば、ビスフェノールＡ型のエポキシ樹脂、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、Ｎ，Ｎ－ジグリシジルアニリン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラグリシジル－ｍ－キシレンジアミン、１，３－ビス（Ｎ，Ｎ’－ジグリシジルアミノメチル）シクロヘキサン等が挙げられる。２種以上のエポキシ系化合物を混合して用いることもできる。 Epoxy compounds are compounds that have at least two epoxy groups in the molecule. Specific compounds include, for example, bisphenol A type epoxy resins, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, N,N-diglycidylaniline, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N'-diglycidylaminomethyl)cyclohexane, etc. Two or more types of epoxy compounds can also be mixed and used.
　アジリジン系化合物は、エチレンイミンとも呼ばれる１個の窒素原子と２個の炭素原子とからなる３員環の骨格を分子内に少なくとも２個有する化合物である。具体的な化合物として、例えば、ジフェニルメタン－４，４’－ビス（１－アジリジンカルボキサミド）、トルエン－２，４－ビス（１－アジリジンカルボキサミド）、トリエチレンメラミン、イソフタロイルビス－１－（２－メチルアジリジン）、トリス－１－アジリジニルホスフィンオキサイド、ヘキサメチレン－１，６－ビス（１－アジリジンカルボキサミド）、トリメチロールプロパン－トリス－β－アジリジニルプロピオネート、テトラメチロールメタン－トリス－β－アジリジニルプロピオネート等が挙げられる。 Aziridine compounds are compounds that have at least two three-membered ring structures, also known as ethyleneimines, each consisting of one nitrogen atom and two carbon atoms. Specific examples of compounds include diphenylmethane-4,4'-bis(1-aziridinecarboxamide), toluene-2,4-bis(1-aziridinecarboxamide), triethylenemelamine, isophthaloylbis-1-(2-methylaziridine), tris-1-aziridinylphosphine oxide, hexamethylene-1,6-bis(1-aziridinecarboxamide), trimethylolpropane-tris-β-aziridinylpropionate, and tetramethylolmethane-tris-β-aziridinylpropionate.
　金属キレート化合物としては、例えば、アルミニウム、鉄、銅、亜鉛、スズ、チタン、ニッケル、アンチモン、マグネシウム、バナジウム、クロムおよびジルコニウム等の多価金属に、アセチルアセトンやアセト酢酸エチルが配位した化合物等が挙げられる。 Examples of metal chelate compounds include compounds in which acetylacetone or ethyl acetoacetate is coordinated with polyvalent metals such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium.
　中でも好ましくはイソシアネート系化合物であり、より好ましくは芳香族イソシアネート系化合物、例えばトリレンジイソシアネート、キシリレンジイソシアネート、水添キシリレンジイソシアネート、ジフェニルメタンジイソシアネート、水添ジフェニルメタンジイソシアネート、ナフタレンジイソシアネート、トリフェニルメタントリイソシアネート等およびその多価アルコール化合物（例えば、グリセロール、トリメチロールプロパン等）による付加体（アダクト体）である。 Among these, isocyanate compounds are preferred, and aromatic isocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, and their adducts with polyhydric alcohol compounds (e.g., glycerol, trimethylolpropane, etc.) are more preferred.
　架橋剤（Ｂ）の含有量は、（メタ）アクリル系樹脂（Ａ）（２種以上用いる場合はそれらの合計）の固形分１００質量部に対し、耐金属腐食性および耐熱耐久性の観点から好ましくは０．２質量部以上５．０質量部以下、より好ましくは０．３質量部以上２．０質量部以下である。 The content of the crosslinking agent (B) is preferably 0.2 parts by mass or more and 5.0 parts by mass or less, more preferably 0.3 parts by mass or more and 2.0 parts by mass or less, based on 100 parts by mass of the solid content of the (meth)acrylic resin (A) (when two or more types are used, the total amount of the (meth)acrylic resin (A)). From the viewpoint of metal corrosion resistance and heat resistance and durability, the content is preferably 0.2 parts by mass or more and 5.0 parts by mass or less, more preferably 0.3 parts by mass or more and 2.0 parts by mass or less.
　（３）シラン化合物（Ｃ）
　シラン化合物（Ｃ）は、下記式（Ｉ）： (3) Silane Compound (C)
The silane compound (C) is represented by the following formula (I):
Figure JPOXMLDOC01-appb-C000006
 ［式（Ｉ）中、
　Ｌは、炭素数１～２０のアルカンジイル基または炭素数３～２０の２価の脂環式炭化水素基を表し、該アルカンジイル基および該脂環式炭化水素基を構成する－ＣＨ２－は、－Ｏ－または－Ｃ（＝Ｏ）－に置き換わっていてもよく、
　Ａ１は、炭素数１～５のアルキル基を表し、
　Ａ２、Ａ３、Ａ４、Ａ５およびＡ６は、互いに独立して、炭素数１～５のアルキル基または炭素数１～５のアルコキシ基を表す］
で表されるシラン化合物を含む。シラン化合物（Ｃ）を含有することにより耐金属腐食性および耐熱耐久性に優れる傾向にある。
Figure JPOXMLDOC01-appb-C000006
 [In formula (I),
L represents an alkanediyl group having 1 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and —CH 2 — constituting the alkanediyl group or the alicyclic hydrocarbon group may be replaced by —O— or —C(═O)—;
A 1 represents an alkyl group having 1 to 5 carbon atoms;
A 2 , A 3 , A 4 , A 5 and A 6 each independently represent an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.
By including the silane compound (C), the metal corrosion resistance and heat resistance and durability tend to be excellent.
　式（Ｉ）中、Ｌを構成し得る炭素数１～２０のアルカンジイル基の具体例としては、メチレン基、１，２－エタンジイル基、１，３－プロパンジイル基、１，４－ブタンジイル基、１，５－ペンタンジイル基、１，６－ヘキサンジイル基、１，７－ヘプタンジイル基、１，８－オクタンジイル基、１，９－ノナンジイル基、１，１０－デカンジイル基、１，１２－ドデカンジイル基、１，１４－テトラデカンジイル基、１，１６－ヘキサデカンジイル基、１，１８－オクタデカンジイル基、１，２０－イコサンジイル基を含む。炭素数３～２０の２価の脂環式炭化水素基の具体例は、１，３－シクロペンタンジイル基、１，４－シクロヘキサンジイル基を含む。上記アルカンジイル基および上記脂環式炭化水素基を構成する－ＣＨ2－が－Ｏ－又は－Ｃ（＝Ｏ）－に置き換わった基の具体例は、－ＣＨ2ＣＨ2－Ｏ－ＣＨ2ＣＨ2－、－ＣＨ2ＣＨ2－Ｏ－ＣＨ2ＣＨ2－Ｏ－ＣＨ2ＣＨ2－、－ＣＨ2ＣＨ2－Ｏ－ＣＨ2ＣＨ2－Ｏ－ＣＨ2ＣＨ2－Ｏ－ＣＨ2ＣＨ2－、－ＣＨ2ＣＨ2－Ｃ（＝Ｏ）－Ｏ－ＣＨ2ＣＨ2－、－ＣＨ2ＣＨ2－Ｏ－ＣＨ2ＣＨ2－Ｃ（＝Ｏ）－Ｏ－ＣＨ2ＣＨ2－、－ＣＨ2ＣＨ2ＣＨ2ＣＨ2－Ｏ－ＣＨ2ＣＨ2－、－ＣＨ2ＣＨ2ＣＨ2ＣＨ2－Ｏ－ＣＨ2ＣＨ2ＣＨ2ＣＨ2－を含む。 In formula (I), specific examples of the alkanediyl group having 1 to 20 carbon atoms that can constitute L include a methylene group, a 1,2-ethanediyl group, a 1,3-propanediyl group, a 1,4-butanediyl group, a 1,5-pentanediyl group, a 1,6-hexanediyl group, a 1,7-heptanediyl group, a 1,8-octanediyl group, a 1,9-nonanediyl group, a 1,10-decanediyl group, a 1,12-dodecanediyl group, a 1,14-tetradecanediyl group, a 1,16-hexadecanediyl group, a 1,18-octadecanediyl group, and a 1,20-icosanediyl group. Specific examples of the divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a 1,3-cyclopentanediyl group and a 1,4-cyclohexanediyl group. Specific examples of the alkanediyl group and the alicyclic hydrocarbon group in which —CH 2 — is replaced by —O— or —C(═O)— include —CH 2 CH 2 —O—CH 2 CH 2 —, —CH 2 CH 2 —O—CH 2 CH 2 —O—CH 2 CH 2 —, —CH 2 CH 2 —O—CH 2 CH 2 —O—CH 2 CH 2 —O—CH 2 CH 2 —O—CH 2 CH 2 —, —CH 2 CH 2 —C(═O)—O—CH 2 CH 2 —, —CH 2 CH 2 —O—CH 2 CH 2 —C(═O)—O—CH 2 CH 2 —, —CH 2 CH 2 —O—CH 2 CH 2 —C(═O)—O—CH 2 CH 2 —, —CH 2 CH 2 CH 2 —O—CH 2 CH 2 —O—CH 2 CH 2 —, —CH 2 CH 2 Includes CH2CH2 - O - CH2CH2CH2CH2CH2- .
　式（Ｉ）中、Ａ１、Ａ２、Ａ３、Ａ４、Ａ５およびＡ６を構成し得る炭素数１～５のアルキル基は、メチル基、エチル基、ｎ－及びｉ－プロピル基、ｎ－、ｉ－及びｔ－ブチル基、ｎ－、ｉ－及びｔ－ペンチル基等の各種ペンチル基が挙げられる。 In formula (I), examples of the alkyl group having 1 to 5 carbon atoms which may constitute A 1 , A 2 , A 3 , A 4 , A 5 and A 6 include various pentyl groups such as methyl group, ethyl group, n- and i-propyl group, n-, i- and t-butyl group, and n-, i- and t-pentyl group.
　式（Ｉ）中、Ａ２、Ａ３、Ａ４、Ａ５およびＡ６を構成し得る炭素数１～５のアルコキシ基としては、メトキシ基、エトキシ基、ｎ－プロポキシ基、ｉ－プロポキシ基、ｎ－ブトキシ基、ｉ－ブトキシ基、ｔ－ブトキシ基、ｎ－、ｉ－及びｔ－ペンチルオキシ基等の各種ペンチルオキシ基が挙げられる。当該アルキル基及びアルコキシ基の炭素数は、それぞれ独立して、好ましくは１～４であり、より好ましくは１～３であり、さらに好ましくは１又は２である。 In formula (I), examples of the alkoxy group having 1 to 5 carbon atoms which may constitute A 2 , A 3 , A 4 , A 5 and A 6 include various pentyloxy groups such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, t-butoxy group, n-, i- and t-pentyloxy groups, etc. The number of carbon atoms in the alkyl group and alkoxy group is each independently preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2.
　式（Ｉ）で示されるシラン化合物の具体例を以下に示す。
　ビス（トリメトキシシリル）メタン、
　ビス（トリエトキシシリル）メタン、
　ビス（トリプロポキシシリル）メタン、
　ビス（トリブトキシシリル）メタン、
　ビス（トリペンチルオキシシリル）メタン、
　ビス（ジメトキシメチルシリル）メタン、
　ビス（ジメトキシエチルシリル）メタン、
　ビス（ジメトキシプロピルシリル）メタン、
　ビス（ジエトキシメチルシリル）メタン、
　ビス（ジプロポキシメチルシリル）メタン、
　ビス（メトキシジメチルシリル）メタン、
　１－（トリメチルシリル）－１－（メトキシジメチルシリル）メタン、
　１－（トリメチルシリル）－１－（ジメトキシメチルシリル）メタン、
　１－（トリメトキシシリル）－１－（トリエトキシシリル）メタン、
　ビス（ジメトキシエトキシシリル）メタン、
　１，２－ビス（トリメトキシシリル）エタン、
　１，２－ビス（トリエトキシシリル）エタン、
　１，２－ビス（トリプロポキシシリル）エタン、
　１，２－ビス（トリブトキシシリル）エタン、
　１，２－ビス（トリペンチルオキシシリル）エタン、
　１，２－ビス（ジメトキシメチルシリル）エタン、
　１，２－ビス（ジメトキシエチルシリル）エタン、
　１，２－ビス（ジメトキシプロピルシリル）エタン、
　１，２－ビス（ジメトキシエチルシリル）エタン、
　１，２－ビス（ジメトキシプロピルシリル）エタン、
　１，２－ビス（ジエトキシメチルシリル）エタン、
　１，２－ビス（ジプロポキシメチルシリル）エタン、
　１，２－ビス（メトキシジメチルシリル）エタン、 Specific examples of the silane compound represented by formula (I) are shown below.
bis(trimethoxysilyl)methane,
Bis(triethoxysilyl)methane,
bis(trippropoxysilyl)methane,
Bis(tributoxysilyl)methane,
Bis(tripentyloxysilyl)methane,
Bis(dimethoxymethylsilyl)methane,
Bis(dimethoxyethylsilyl)methane,
bis(dimethoxypropylsilyl)methane,
Bis(diethoxymethylsilyl)methane,
Bis(dipropoxymethylsilyl)methane,
Bis(methoxydimethylsilyl)methane,
1-(trimethylsilyl)-1-(methoxydimethylsilyl)methane,
1-(trimethylsilyl)-1-(dimethoxymethylsilyl)methane,
1-(trimethoxysilyl)-1-(triethoxysilyl)methane,
bis(dimethoxyethoxysilyl)methane,
1,2-bis(trimethoxysilyl)ethane,
1,2-bis(triethoxysilyl)ethane,
1,2-bis(trippropoxysilyl)ethane,
1,2-bis(tributoxysilyl)ethane,
1,2-bis(tripentyloxysilyl)ethane,
1,2-bis(dimethoxymethylsilyl)ethane,
1,2-bis(dimethoxyethylsilyl)ethane,
1,2-bis(dimethoxypropylsilyl)ethane,
1,2-bis(dimethoxyethylsilyl)ethane,
1,2-bis(dimethoxypropylsilyl)ethane,
1,2-bis(diethoxymethylsilyl)ethane,
1,2-bis(dipropoxymethylsilyl)ethane,
1,2-bis(methoxydimethylsilyl)ethane,
　１－（トリメチルシリル）－２－（メトキシジメチルシリル）エタン、
　１－（トリメチルシリル）－２－（ジメトキシメチルシリル）エタン、
　１－（トリメトキシシリル）－２－（トリエトキシシリル）エタン、
　１，２－ビス（ジメトキシエトキシシリル）エタン、
　１，３－ビス（トリメトキシシリル）プロパン、
　１，３－ビス（トリエトキシシリル）プロパン、
　１，３－ビス（トリプロポキシシリル）プロパン、
　１，４－ビス（トリメトキシシリル）ブタン、
　１，４－ビス（トリエトキシシリル）ブタン、
　１，４－ビス（トリプロポキシシリル）ブタン、
　１，４－ビス（トリブトキシシリル）ブタン、
　１，４－ビス（トリペンチルオキシシリル）ブタン、
　１，４－ビス（ジメトキシメチルシリル）ブタン、
　１，４－ビス（ジメトキシエチルシリル）ブタン、
　１，４－ビス（ジメトキシプロピルシリル）ブタン、
　１，４－ビス（ジエトキシメチルシリル）ブタン、
　１，４－ビス（ジプロポキシメチルシリル）ブタン、
　１，４－ビス（メトキシジメチルシリル）ブタン、
　１－（トリメチルシリル）－４－（メトキシジメチルシリル）ブタン、
　１－（トリメチルシリル）－４－（ジメトキシメチルシリル）ブタン、
　１－（トリメトキシシリル）－４－（トリエトキシシリル）ブタン、 1-(trimethylsilyl)-2-(methoxydimethylsilyl)ethane,
1-(trimethylsilyl)-2-(dimethoxymethylsilyl)ethane,
1-(trimethoxysilyl)-2-(triethoxysilyl)ethane,
1,2-bis(dimethoxyethoxysilyl)ethane,
1,3-bis(trimethoxysilyl)propane,
1,3-bis(triethoxysilyl)propane,
1,3-bis(tripropoxysilyl)propane,
1,4-bis(trimethoxysilyl)butane,
1,4-bis(triethoxysilyl)butane,
1,4-bis(tripropoxysilyl)butane,
1,4-bis(tributoxysilyl)butane,
1,4-bis(tripentyloxysilyl)butane,
1,4-bis(dimethoxymethylsilyl)butane,
1,4-bis(dimethoxyethylsilyl)butane,
1,4-bis(dimethoxypropylsilyl)butane,
1,4-bis(diethoxymethylsilyl)butane,
1,4-bis(dipropoxymethylsilyl)butane,
1,4-bis(methoxydimethylsilyl)butane,
1-(trimethylsilyl)-4-(methoxydimethylsilyl)butane,
1-(trimethylsilyl)-4-(dimethoxymethylsilyl)butane,
1-(trimethoxysilyl)-4-(triethoxysilyl)butane,
　１，４－ビス（ジメトキシエトキシシリル）ブタン、
　１，５－ビス（トリメトキシシリル）ペンタン、
　１，５－ビス（トリエトキシシリル）ペンタン、
　１，５－ビス（トリプロポキシシリル）ペンタン、
　１，６－ビス（トリメトキシシリル）ヘキサン、
　１，６－ビス（トリエトキシシリル）ヘキサン、
　１，６－ビス（トリプロポキシシリル）ヘキサン、
　１，６－ビス（トリブトキシシリル）ヘキサン、
　１，６－ビス（トリペンチルオキシシリル）ヘキサン、
　１，６－ビス（ジメトキシメチルシリル）ヘキサン、
　１，６－ビス（ジメトキシエチルシリル）ヘキサン、
　１，６－ビス（ジメトキシプロピルシリル）ヘキサン、
　１，６－ビス（ジメトキシエチルシリル）ヘキサン、
　１，６－ビス（ジメトキシプロピルシリル）ヘキサン、
　１，６－ビス（ジエトキシメチルシリル）ヘキサン、
　１，６－ビス（ジプロポキシメチルシリル）ヘキサン、
　１，６－ビス（メトキシジメチルシリル）ヘキサン、
　１－（トリメチルシリル）－６－（メトキシジメチルシリル）ヘキサン、
　１－（トリメチルシリル）－６－（ジメトキシメチルシリル）ヘキサン、
　１－（トリメトキシシリル）－６－（トリエトキシシリル）ヘキサン、
　１，６－ビス（ジメトキシエトキシシリル）ヘキサン、
　１，８－ビス（トリメトキシシリル）オクタン、 1,4-bis(dimethoxyethoxysilyl)butane,
1,5-bis(trimethoxysilyl)pentane,
1,5-bis(triethoxysilyl)pentane,
1,5-bis(tripropoxysilyl)pentane,
1,6-bis(trimethoxysilyl)hexane,
1,6-bis(triethoxysilyl)hexane,
1,6-bis(trippropoxysilyl)hexane,
1,6-bis(tributoxysilyl)hexane,
1,6-bis(tripentyloxysilyl)hexane,
1,6-bis(dimethoxymethylsilyl)hexane,
1,6-bis(dimethoxyethylsilyl)hexane,
1,6-bis(dimethoxypropylsilyl)hexane,
1,6-bis(dimethoxyethylsilyl)hexane,
1,6-bis(dimethoxypropylsilyl)hexane,
1,6-bis(diethoxymethylsilyl)hexane,
1,6-bis(dipropoxymethylsilyl)hexane,
1,6-bis(methoxydimethylsilyl)hexane,
1-(trimethylsilyl)-6-(methoxydimethylsilyl)hexane,
1-(trimethylsilyl)-6-(dimethoxymethylsilyl)hexane,
1-(trimethoxysilyl)-6-(triethoxysilyl)hexane,
1,6-bis(dimethoxyethoxysilyl)hexane,
1,8-bis(trimethoxysilyl)octane,
　１，８－ビス（トリエトキシシリル）オクタン、
　１，８－ビス（トリプロポキシシリル）オクタン、
　１，８－ビス（トリブトキシシリル）オクタン、
　１，８－ビス（トリペンチルオキシシリル）オクタン、
　１，８－ビス（ジメトキシメチルシリル）オクタン、
　１，８－ビス（ジメトキシエチルシリル）オクタン、
　１，８－ビス（ジメトキシプロピルシリル）オクタン、
　１，８－ビス（ジメトキシエチルシリル）オクタン、
　１，８－ビス（ジメトキシプロピルシリル）オクタン、
　１，８－ビス（ジエトキシメチルシリル）オクタン、
　１，８－ビス（ジプロポキシメチルシリル）オクタン、
　１，８－ビス（メトキシジメチルシリル）オクタン、
　１－（トリメチルシリル）－８－（メトキシジメチルシリル）オクタン、
　１－（トリメチルシリル）－８－（ジメトキシメチルシリル）オクタン、
　１－（トリメトキシシリル）－８－（トリエトキシシリル）オクタン、
　１，８－ビス（ジメトキシエトキシシリル）オクタン、
　１，１０－ビス（トリメトキシシリル）デカン、
　１，１２－ビス（トリメトキシシリル）ドデカン、
　１，１４－ビス（トリメトキシシリル）テトラデカン、
　１，１６－ビス（トリメトキシシリル）ヘキサデカン、
　１，１８－ビス（トリメトキシシリル）オクタデカン、
　１，２０－ビス（トリメトキシシリル）イコサンなど。 1,8-bis(triethoxysilyl)octane,
1,8-bis(tripropoxysilyl)octane,
1,8-bis(tributoxysilyl)octane,
1,8-bis(tripentyloxysilyl)octane,
1,8-bis(dimethoxymethylsilyl)octane,
1,8-bis(dimethoxyethylsilyl)octane,
1,8-bis(dimethoxypropylsilyl)octane,
1,8-bis(dimethoxyethylsilyl)octane,
1,8-bis(dimethoxypropylsilyl)octane,
1,8-bis(diethoxymethylsilyl)octane,
1,8-bis(dipropoxymethylsilyl)octane,
1,8-bis(methoxydimethylsilyl)octane,
1-(trimethylsilyl)-8-(methoxydimethylsilyl)octane,
1-(trimethylsilyl)-8-(dimethoxymethylsilyl)octane,
1-(trimethoxysilyl)-8-(triethoxysilyl)octane,
1,8-bis(dimethoxyethoxysilyl)octane,
1,10-bis(trimethoxysilyl)decane,
1,12-bis(trimethoxysilyl)dodecane,
1,14-bis(trimethoxysilyl)tetradecane,
1,16-bis(trimethoxysilyl)hexadecane,
1,18-bis(trimethoxysilyl)octadecane,
1,20-bis(trimethoxysilyl)icosane, etc.
　中でも、耐金属腐食性および耐熱耐久性の観点から好ましくは、下記式（ＩＩ）： Among them, from the viewpoint of metal corrosion resistance and heat resistance and durability, the following formula (II):
Figure JPOXMLDOC01-appb-C000007
 （式中、Ａ１、Ａ３、Ａ４、Ａ５およびＡ６はそれぞれ上記と同一の意味を表し、Ａ７は炭素数１～５のアルキル基を表し、ｍは１～２０の整数を表す。）で表されるシラン化合物を含むことが好ましい。Ａ７を構成し得る炭素数１～５のアルキル基の具体例は、上記と同様である。上と同様の観点から、シラン化合物（Ｃ）は、ｍが４～２０の整数である上記式（ＩＩ）で表されるシラン化合物を含むことがより好ましく、ｍが６～８の整数である上記式（ＩＩ）で表されるシラン化合物を含むことがさらに好ましく、Ａ１ＯおよびＯＡ７がそれぞれ独立して炭素数１～３（例えば炭素数１又は２）のアルコキシ基であり、およびＡ３、Ａ４、Ａ５およびＡ６がそれぞれ独立して炭素数１～３（例えば炭素数１又は２）のアルキル基またはアルコキシ基である上記式（ＩＩ）で表されるシラン化合物を含むことが特に好ましく、Ａ１Ｏ、Ａ３、Ａ４、Ａ５、Ａ６およびＯＡ７がそれぞれ独立して炭素数１～３（例えば炭素数１又は２）のアルコキシ基である上記式（ＩＩ）で表されるシラン化合物、例えば１，６－ビス（トリメトキシシリル）ヘキサン、１，６－ビス（トリエトキシシリル）ヘキサン、１，８－ビス（トリメトキシシリル）オクタン、１，８－ビス（トリエトキシシリル）オクタン等を含むことがより特に好ましい。好適なｍの例は、６又は８である。
Figure JPOXMLDOC01-appb-C000007
 (wherein A 1 , A 3 , A 4 , A 5 and A 6 are each the same as defined above, A 7 is an alkyl group having 1 to 5 carbon atoms, and m is an integer from 1 to 20.) Specific examples of the alkyl group having 1 to 5 carbon atoms that can constitute A 7 are the same as those mentioned above. From the same viewpoint as above, the silane compound (C) more preferably contains a silane compound represented by the above formula (II) in which m is an integer of 4 to 20, further preferably contains a silane compound represented by the above formula (II) in which m is an integer of 6 to 8, and particularly preferably contains a silane compound represented by the above formula (II) in which A 1 O and OA 7 are each independently an alkoxy group having 1 to 3 carbon atoms (e.g., 1 or 2 carbon atoms), and A 3 , A 4 , A 5 , and A 6 are each independently an alkyl group or alkoxy group having 1 to 3 carbon atoms (e.g., 1 or 2 carbon atoms), and A 1 O, A 3 , A 4 , A 5 , A 6 and OA More particularly preferred are silane compounds represented by the above formula (II) in which each 7 is independently an alkoxy group having 1 to 3 carbon atoms (e.g., 1 or 2 carbon atoms), such as 1,6-bis(trimethoxysilyl)hexane, 1,6-bis(triethoxysilyl)hexane, 1,8-bis(trimethoxysilyl)octane, 1,8-bis(triethoxysilyl)octane, etc. Suitable examples of m are 6 and 8.
　粘着剤組成物は、式（Ｉ）で表されるシラン化合物とともに、これ以外の他のシラン化合物を１種又は２種以上含むことができる。他のシラン化合物としては、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（２－メトキシエトキシ）シラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルトリエトキシシラン、３－グリシドキシプロピルメチルジメトキシシラン、３－グリシドキシプロピルエトキシジメチルシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、３－クロロプロピルメチルジメトキシシラン、３－クロロプロピルトリメトキシシラン、３－メタクリロイルオキシプロピルトリメトキシシラン、３－メルカプトプロピルトリメトキシシラン、８－グリシドキシオクチルトリメトキシシラン等が挙げられる。 The adhesive composition may contain one or more other silane compounds in addition to the silane compound represented by formula (I). Examples of other silane compounds include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethoxydimethylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 8-glycidoxyoctyltrimethoxysilane.
　他のシラン化合物は、シリコーンオリゴマータイプのものを含むことができる。シリコーンオリゴマーの具体例を、モノマー同士の組み合わせの形で表記すると次のとおりである。 Other silane compounds can include silicone oligomers. Specific examples of silicone oligomers, expressed in the form of combinations of monomers, are as follows:
　３－メルカプトプロピルトリメトキシシラン－テトラメトキシシランオリゴマー、
　３－メルカプトプロピルトリメトキシシラン－テトラエトキシシランオリゴマー、
　３－メルカプトプロピルトリエトキシシラン－テトラメトキシシランオリゴマー、
　３－メルカプトプロピルトリエトキシシラン－テトラエトキシシランオリゴマー
等のメルカプトプロピル基含有オリゴマー；
　メルカプトメチルトリメトキシシラン－テトラメトキシシランオリゴマー、
　メルカプトメチルトリメトキシシラン－テトラエトキシシランオリゴマー、
　メルカプトメチルトリエトキシシラン－テトラメトキシシランオリゴマー、
　メルカプトメチルトリエトキシシラン－テトラエトキシシランオリゴマー
等のメルカプトメチル基含有オリゴマー；
　３－グリジドキシプロピルトリメトキシシラン－テトラメトキシシランコポリマー、
　３－グリジドキシプロピルトリメトキシシラン－テトラエトキシシランコポリマー、
　３－グリジドキシプロピルトリエトキシシラン－テトラメトキシシランコポリマー、
　３－グリジドキシプロピルトリエトキシシラン－テトラエトキシシランコポリマー、
　３－グリジドキシプロピルメチルジメトキシシラン－テトラメトキシシランコポリマー、
　３－グリジドキシプロピルメチルジメトキシシラン－テトラエトキシシランコポリマー、
　３－グリジドキシプロピルメチルジエトキシシラン－テトラメトキシシランコポリマー、
　３－グリジドキシプロピルメチルジエトキシシラン－テトラエトキシシランコポリマー等の３－グリジドキシプロピル基含有のコポリマー；
　３－メタクリロイルオキシプロピルトリメトキシシラン－テトラメトキシシランオリゴマー、
　３－メタクリロイルオキシプロピルトリメトキシシラン－テトラエトキシシランオリゴマー、
　３－メタクリロイルオキシプロピルトリエトキシシラン－テトラメトキシシランオリゴマー、
　３－メタクリロイルオキシプロピルトリエトキシシラン－テトラエトキシシランオリゴマー、
　３－メタクリロイルオキシプロピルメチルジメトキシシラン－テトラメトキシシランオリゴマー、
　３－メタクリロイルオキシプロピルメチルジメトキシシラン－テトラエトキシシランオリゴマー、
　３－メタクリロイルオキシプロピルメチルジエトキシシラン－テトラメトキシシランオリゴマー、
　３－メタクリロイルオキシプロピルメチルジエトキシシラン－テトラエトキシシランオリゴマー
等のメタクリロイルオキシプロピル基含有オリゴマー； 3-mercaptopropyltrimethoxysilane-tetramethoxysilane oligomer,
3-mercaptopropyltrimethoxysilane-tetraethoxysilane oligomer,
3-mercaptopropyltriethoxysilane-tetramethoxysilane oligomer,
mercaptopropyl group-containing oligomers such as 3-mercaptopropyltriethoxysilane-tetraethoxysilane oligomer;
mercaptomethyltrimethoxysilane-tetramethoxysilane oligomer,
mercaptomethyltrimethoxysilane-tetraethoxysilane oligomer,
mercaptomethyltriethoxysilane-tetramethoxysilane oligomer,
mercaptomethyl group-containing oligomers such as mercaptomethyltriethoxysilane-tetraethoxysilane oligomers;
3-glycidoxypropyltrimethoxysilane-tetramethoxysilane copolymer,
3-glycidoxypropyltrimethoxysilane-tetraethoxysilane copolymer,
3-glycidoxypropyltriethoxysilane-tetramethoxysilane copolymer,
3-glycidoxypropyltriethoxysilane-tetraethoxysilane copolymer,
3-glycidoxypropylmethyldimethoxysilane-tetramethoxysilane copolymer,
3-glycidoxypropylmethyldimethoxysilane-tetraethoxysilane copolymer,
3-glycidoxypropylmethyldiethoxysilane-tetramethoxysilane copolymer,
Copolymers containing 3-glycidoxypropyl groups, such as 3-glycidoxypropylmethyldiethoxysilane-tetraethoxysilane copolymer;
3-methacryloyloxypropyltrimethoxysilane-tetramethoxysilane oligomer,
3-methacryloyloxypropyltrimethoxysilane-tetraethoxysilane oligomer,
3-methacryloyloxypropyltriethoxysilane-tetramethoxysilane oligomer,
3-methacryloyloxypropyltriethoxysilane-tetraethoxysilane oligomer,
3-methacryloyloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer,
3-methacryloyloxypropylmethyldimethoxysilane-tetraethoxysilane oligomer,
3-methacryloyloxypropylmethyldiethoxysilane-tetramethoxysilane oligomer,
methacryloyloxypropyl group-containing oligomers such as 3-methacryloyloxypropylmethyldiethoxysilane-tetraethoxysilane oligomer;
　３－アクリロイルオキシプロピルトリメトキシシラン－テトラメトキシシランオリゴマー、
　３－アクリロイルオキシプロピルトリメトキシシラン－テトラエトキシシランオリゴマー、
　３－アクリロイルオキシプロピルトリエトキシシラン－テトラメトキシシランオリゴマー、
　３－アクリロイルオキシプロピルトリエトキシシラン－テトラエトキシシランオリゴマー、
　３－アクリロイルオキシプロピルメチルジメトキシシラン－テトラメトキシシランオリゴマー、
　３－アクリロイルオキシプロピルメチルジメトキシシラン－テトラエトキシシランオリゴマー、
　３－アクリロイルオキシプロピルメチルジエトキシシラン－テトラメトキシシランオリゴマー、
　３－アクリロイルオキシプロピルメチルジエトキシシラン－テトラエトキシシランオリゴマー
等のアクリロイルオキシプロピル基含有オリゴマー；
　ビニルトリメトキシシラン－テトラメトキシシランオリゴマー、
　ビニルトリメトキシシラン－テトラエトキシシランオリゴマー、
　ビニルトリエトキシシラン－テトラメトキシシランオリゴマー、
　ビニルトリエトキシシラン－テトラエトキシシランオリゴマー、
　ビニルメチルジメトキシシラン－テトラメトキシシランオリゴマー、
　ビニルメチルジメトキシシラン－テトラエトキシシランオリゴマー、
　ビニルメチルジエトキシシラン－テトラメトキシシランオリゴマー、
　ビニルメチルジエトキシシラン－テトラエトキシシランオリゴマー
等のビニル基含有オリゴマー； 3-acryloyloxypropyltrimethoxysilane-tetramethoxysilane oligomer,
3-acryloyloxypropyltrimethoxysilane-tetraethoxysilane oligomer,
3-acryloyloxypropyltriethoxysilane-tetramethoxysilane oligomer,
3-acryloyloxypropyltriethoxysilane-tetraethoxysilane oligomer,
3-acryloyloxypropylmethyldimethoxysilane-tetramethoxysilane oligomer,
3-acryloyloxypropylmethyldimethoxysilane-tetraethoxysilane oligomer,
3-acryloyloxypropylmethyldiethoxysilane-tetramethoxysilane oligomer,
acryloyloxypropyl group-containing oligomers such as 3-acryloyloxypropylmethyldiethoxysilane-tetraethoxysilane oligomer;
Vinyltrimethoxysilane-tetramethoxysilane oligomer,
Vinyltrimethoxysilane-tetraethoxysilane oligomer,
Vinyltriethoxysilane-tetramethoxysilane oligomer,
Vinyltriethoxysilane-tetraethoxysilane oligomer,
Vinylmethyldimethoxysilane-tetramethoxysilane oligomer,
Vinylmethyldimethoxysilane-tetraethoxysilane oligomer,
Vinylmethyldiethoxysilane-tetramethoxysilane oligomer,
Vinyl group-containing oligomers such as vinylmethyldiethoxysilane-tetraethoxysilane oligomers;
　３－アミノプロピルトリメトキシシラン－テトラメトキシシランコポリマー、
　３－アミノプロピルトリメトキシシラン－テトラエトキシシランコポリマー、
　３－アミノプロピルトリエトキシシラン－テトラメトキシシランコポリマー、
　３－アミノプロピルトリエトキシシラン－テトラエトキシシランコポリマー、
　３－アミノプロピルメチルジメトキシシラン－テトラメトキシシランコポリマー、
　３－アミノプロピルメチルジメトキシシラン－テトラエトキシシランコポリマー、
　３－アミノプロピルメチルジエトキシシラン－テトラメトキシシランコポリマー、
　３－アミノプロピルメチルジエトキシシラン－テトラエトキシシランコポリマー
等のアミノ基含有のコポリマーなど。 3-aminopropyltrimethoxysilane-tetramethoxysilane copolymer,
3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer,
3-aminopropyltriethoxysilane-tetramethoxysilane copolymer,
3-aminopropyltriethoxysilane-tetraethoxysilane copolymer,
3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer,
3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer,
3-aminopropylmethyldiethoxysilane-tetramethoxysilane copolymer,
Amino group-containing copolymers such as 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer.
　ただし、耐金属腐食性および耐熱耐久性の観点から、式（Ｉ）で表されるシラン化合物の含有量は、すべてのシラン化合物の合計中、好ましくは７０重量％以上であり、より好ましくは８０重量％以上であり、さらに好ましくは９０重量％以上であり、粘着剤組成物は、シラン化合物（Ｃ）として式（Ｉ）で表されるシラン化合物のみを含有することが特に好ましい。 However, from the viewpoint of metal corrosion resistance and heat resistance and durability, the content of the silane compound represented by formula (I) in the total of all silane compounds is preferably 70% by weight or more, more preferably 80% by weight or more, and even more preferably 90% by weight or more, and it is particularly preferable that the adhesive composition contains only the silane compound represented by formula (I) as the silane compound (C).
　粘着剤組成物におけるシラン化合物（Ｃ）の含有量は、（メタ）アクリル系樹脂（Ａ）（２種以上用いる場合はそれらの合計）の固形分１００質量部に対して、耐金属腐食性および耐熱耐久性の観点から好ましくは０．０１質量部以上２．０質量部以下であり、より好ましくは０．１質量部以上１．５質量部以下である。 The content of the silane compound (C) in the adhesive composition is preferably 0.01 parts by mass or more and 2.0 parts by mass or less, and more preferably 0.1 parts by mass or more and 1.5 parts by mass or less, per 100 parts by mass of the solid content of the (meth)acrylic resin (A) (when two or more types are used, the total amount of the (meth)acrylic resin (A)). From the viewpoints of metal corrosion resistance and heat resistance durability, the content is preferably 0.01 parts by mass or more and 2.0 parts by mass or less, and more preferably 0.1 parts by mass or more and 1.5 parts by mass or less.
　（４）イオン性化合物（Ｄ）
　イオン性化合物（Ｄ）は、カチオンとアニオンとで構成される化合物を含むことができる。イオン性化合物（Ｄ）は、耐金属腐食性および耐熱耐久性の観点から好ましくは下記式： (4) Ionic Compound (D)
The ionic compound (D) may include a compound composed of a cation and an anion. From the viewpoint of metal corrosion resistance and heat resistance durability, the ionic compound (D) is preferably represented by the following formula:
Figure JPOXMLDOC01-appb-C000008
 で表される化合物からなる群から選択されるアニオンを含有する。カチオンは有機カチオン、無機カチオンのいずれであってもよい。イオン性化合物（Ｄ）を用いることにより、良好な帯電防止性能を付与することができるだけでなく、優れた耐金属腐食性および耐熱耐久性を付与することができる。イオン性化合物（Ｄ）は、１種又は２種以上含んでいてもよい。
Figure JPOXMLDOC01-appb-C000008
 The anion is selected from the group consisting of compounds represented by the formula: The cation may be either an organic cation or an inorganic cation. By using the ionic compound (D), not only can good antistatic performance be imparted, but also excellent metal corrosion resistance and heat resistance durability can be imparted. The ionic compound (D) may contain one or more kinds.
　有機カチオンの具体例は、ピリジニウムカチオン、イミダゾリウムカチオン、ピペリジニウムカチオン、ピロリジニウムカチオン、テトラヒドロピリジニウムカチオン、ジヒドロピリジニウムカチオン、テトラヒドロピリミジウムカチオン、ジヒドロピリミジウムカチオン、ピラゾリウムカチオン、ピラゾリニウムカチオン、アンモニウムカチオン、スルホニウムカチオン、ホスホニウムカチオン等を含む。有機カチオンは、置換基を有していてもよい。無機カチオンの具体例は、リチウムカチオン〔Ｌｉ+〕、ナトリウムカチオン〔Ｎａ+〕、カリウムカチオン〔Ｋ+〕、セシウムカチオン〔Ｃｓ+〕等のアルカリ金属イオン；ベリリウムカチオン〔Ｂｅ2+〕、マグネシウムカチオン〔Ｍｇ2+〕、カルシウムカチオン〔Ｃａ2+〕等のアルカリ土類金属イオン等を含む。 Specific examples of organic cations include pyridinium cation, imidazolium cation, piperidinium cation, pyrrolidinium cation, tetrahydropyridinium cation, dihydropyridinium cation, tetrahydropyrimidium cation, dihydropyrimidium cation, pyrazolium cation, pyrazolinium cation, ammonium cation, sulfonium cation, phosphonium cation, etc. The organic cation may have a substituent. Specific examples of inorganic cations include alkali metal ions such as lithium cation [Li + ], sodium cation [Na + ], potassium cation [K + ], and cesium cation [Cs + ]; and alkaline earth metal ions such as beryllium cation [Be 2+ ], magnesium cation [Mg 2+ ], and calcium cation [Ca 2+ ].
　中でもカチオンは、（メタ）アクリル系樹脂（Ａ）との相溶性の観点から有機カチオンであることが好ましく、帯電防止性能の観点から、ピリジニウムカチオン、イミダゾリウムカチオン、ピペリジニウムカチオン、ピロリジニウムカチオン、テトラヒドロピリジニウムカチオン、ジヒドロピリジニウムカチオン、テトラヒドロピリミジウムカチオン、ジヒドロピリミジウムカチオン、ピラゾリウムカチオン、ピラゾリニウムカチオン、アンモニウムカチオン等の窒素原子含有有機カチオン（置換基を有していてもよい。）であることがより好ましい。 Among these, the cation is preferably an organic cation from the viewpoint of compatibility with the (meth)acrylic resin (A), and more preferably a nitrogen atom-containing organic cation (which may have a substituent) such as a pyridinium cation, imidazolium cation, piperidinium cation, pyrrolidinium cation, tetrahydropyridinium cation, dihydropyridinium cation, tetrahydropyrimidium cation, dihydropyrimidium cation, pyrazolium cation, pyrazolinium cation, or ammonium cation from the viewpoint of antistatic performance.
　粘着剤組成物におけるイオン性化合物（Ｄ）の含有量は、（メタ）アクリル系樹脂（Ａ）（２種以上用いる場合はそれらの合計）の固形分１００質量部に対して、耐金属腐食性および耐熱耐久性の観点から好ましくは０．２質量部以上１０質量部以下であり、より好ましくは０．３質量部以上９質量部以下、さらに好ましくは０．５質量部以上８質量部以下である。 The content of the ionic compound (D) in the adhesive composition is preferably 0.2 parts by mass or more and 10 parts by mass or less, more preferably 0.3 parts by mass or more and 9 parts by mass or less, and even more preferably 0.5 parts by mass or more and 8 parts by mass or less, based on 100 parts by mass of the solid content of the (meth)acrylic resin (A) (when two or more types are used, the total of the (meth)acrylic resins (A)).
　（５）その他の成分
　粘着剤組成物は、溶剤、架橋触媒、紫外線吸収剤、耐候安定剤、タッキファイヤー、可塑剤、軟化剤、染料、顔料、無機フィラー、光散乱性微粒子、防錆剤、剥離剤、（メタ）アクリル系樹脂（Ａ）以外の樹脂等の添加剤を含有することができる。そのほか、粘着剤組成物に紫外線硬化性化合物を配合し、粘着剤層を形成した後に紫外線を照射して硬化させ、より硬い粘着剤層とすることも有用である。架橋触媒としては、例えばヘキサメチレンジアミン、エチレンジアミン、ポリエチレンイミン、ヘキサメチレンテトラミン、ジエチレントリアミン、トリエチレンテトラミン、イソホロンジアミン、トリメチレンジアミン、ポリアミノ樹脂及びメラミン樹脂等のアミン系化合物などが挙げられる。 (5) Other components The adhesive composition may contain additives such as solvents, crosslinking catalysts, ultraviolet absorbers, weather stabilizers, tackifiers, plasticizers, softeners, dyes, pigments, inorganic fillers, light scattering fine particles, rust inhibitors, release agents, and resins other than the (meth)acrylic resin (A). In addition, it is also useful to blend an ultraviolet curing compound into the adhesive composition, form an adhesive layer, and then irradiate ultraviolet light to cure the adhesive layer to make it harder. Examples of crosslinking catalysts include amine compounds such as hexamethylenediamine, ethylenediamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, isophoronediamine, trimethylenediamine, polyamino resins, and melamine resins.
　粘着剤組成物が、架橋剤（Ｂ）とともに架橋触媒を含有する場合、粘着剤層を短時間の熟成で調製することができる。また、架橋触媒を含有させると、粘着剤層とこれに隣接するフィルムとの界面での浮きや剥れ、粘着剤層の発泡をより効果的に抑制でき、また耐金属腐食性も一層良好になることがある。架橋触媒としては、例えば、ヘキサメチレンジアミン、エチレンジアミン、ポリエチレンイミン、ヘキサメチレンテトラミン、ジエチレントリアミン、トリエチレンテトラミン、イソホロンジアミン、トリメチレンジアミン、ポリアミノ樹脂およびメラミン樹脂等のアミン系化合物を挙げることができる。粘着剤組成物に架橋触媒としてアミン系化合物を配合する場合、架橋剤（Ｂ）としてはイソシアネート系化合物が好適である。 When the adhesive composition contains a crosslinking catalyst together with the crosslinking agent (B), the adhesive layer can be prepared by aging for a short period of time. Furthermore, when a crosslinking catalyst is contained, lifting or peeling at the interface between the adhesive layer and the adjacent film, and foaming of the adhesive layer can be more effectively suppressed, and metal corrosion resistance can also be improved. Examples of crosslinking catalysts include amine-based compounds such as hexamethylenediamine, ethylenediamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, isophoronediamine, trimethylenediamine, polyamino resins, and melamine resins. When an amine-based compound is blended as a crosslinking catalyst in the adhesive composition, an isocyanate-based compound is preferable as the crosslinking agent (B).
　粘着剤組成物は、上記成分を混合することにより調製することができる。粘着剤組成物は、ゲル分率が例えば５０％以上９８％以下であってよく、好ましくは６０％以上９５％以下である。ゲル分率は後述の実施例の欄における測定方法に従って測定することができる。 The adhesive composition can be prepared by mixing the above components. The adhesive composition may have a gel fraction of, for example, 50% or more and 98% or less, and preferably 60% or more and 95% or less. The gel fraction can be measured according to the measurement method described in the Examples section below.
　粘着剤組成物は、耐金属腐食性試験において金属層表面の発生した孔食の数が例えば３個以下であってよい。耐金属腐食性試験は後述の実施例の欄において説明する方法に従って行うことができる。 The adhesive composition may have, for example, three or less pits on the metal layer surface in a metal corrosion resistance test. The metal corrosion resistance test can be carried out according to the method described in the Examples section below.
　粘着剤組成物は、耐熱耐久性試験において、例えば浮き、剥れ、割れ、発泡等の外観変化が少し認められるか、または全く認められないものであってよく、好ましくは全く認められないものである。耐熱耐久性試験は後述の実施例の欄において説明する方法に従って行うことができる。 The adhesive composition may show little or no change in appearance, such as lifting, peeling, cracking, or foaming, in a heat resistance durability test, and preferably shows no change at all. The heat resistance durability test can be carried out according to the method described in the Examples section below.
　＜粘着剤層＞
　本発明の粘着剤層は、上述の本発明に係る粘着剤組成物を含むものであり、典型的には本発明に係る粘着剤組成物からなる。粘着剤層は、上記粘着剤組成物を構成する各成分を溶剤に溶解または分散して溶剤含有の粘着剤組成物とし、次いで、基材フィルム上に塗布し、乾燥させることによって得ることができる。粘着剤層は、耐金属腐食性および耐熱耐久性に優れている。 <Adhesive Layer>
The pressure-sensitive adhesive layer of the present invention includes the pressure-sensitive adhesive composition of the present invention, and typically consists of the pressure-sensitive adhesive composition of the present invention. The pressure-sensitive adhesive layer can be obtained by dissolving or dispersing each component constituting the pressure-sensitive adhesive composition in a solvent to obtain a solvent-containing pressure-sensitive adhesive composition, and then applying the composition onto a substrate film and drying the composition. The pressure-sensitive adhesive layer has excellent metal corrosion resistance and heat resistance durability.
　基材フィルムは、プラスチックフィルムであるのが一般的であり、その典型的な例として離型処理が施された剥離フィルム（セパレーター）を挙げることができる。剥離フィルムは、例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリカーボネート、ポリアレート等の各種樹脂からなるフィルムの粘着剤層が形成される面に、シリコーン処理等の離型処理が施されたものであることができる。また、光学フィルムの表面に粘着剤組成物を直接塗布して粘着剤層を形成し、必要に応じて粘着剤層の外面に剥離フィルムを積層して粘着剤層付光学フィルムとしてもよい。粘着剤層を光学フィルムの表面に設ける際には、必要に応じて光学フィルムの貼合面および／または粘着剤層の貼合面に表面活性化処理、例えばプラズマ処理、コロナ処理等を施してもよい。 The base film is generally a plastic film, and a typical example is a release film (separator) that has been subjected to a release treatment. The release film can be, for example, a film made of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyarene, etc., with a release treatment such as silicone treatment applied to the surface on which the adhesive layer is to be formed. Alternatively, the adhesive composition may be directly applied to the surface of the optical film to form an adhesive layer, and if necessary, a release film may be laminated on the outer surface of the adhesive layer to form an optical film with an adhesive layer. When providing an adhesive layer on the surface of the optical film, if necessary, a surface activation treatment such as plasma treatment, corona treatment, etc. may be applied to the bonding surface of the optical film and/or the bonding surface of the adhesive layer.
　粘着剤層の厚みは、例えば１０μｍ以上５０μｍ以下であってよく、耐金属腐食性および耐熱耐久性の観点から好ましくは１５μｍ以上４０μｍ以下、より好ましくは１８μｍ以上３５μｍ以下である。 The thickness of the adhesive layer may be, for example, 10 μm or more and 50 μm or less, and from the viewpoint of metal corrosion resistance and heat resistance durability, is preferably 15 μm or more and 40 μm or less, and more preferably 18 μm or more and 35 μm or less.
　＜粘着剤層付光学フィルム＞
　本発明に係る粘着剤層付光学フィルムは、例えば光学フィルムと、その上に積層された上述の粘着剤層とを含むことができる。 <Optical film with pressure-sensitive adhesive layer>
The pressure-sensitive adhesive layer-attached optical film according to the present invention can include, for example, an optical film and the above-mentioned pressure-sensitive adhesive layer laminated thereon.
　光学フィルムとしては、偏光子；偏光子等の表面を保護するために設けられる保護フィルム；偏光子の片面または両面に保護フィルムが積層された偏光板；位相差フィルム；；位相差フィルム以外の光学補償フィルム；表面に凹凸形状を有する防眩機能付きフィルム、表面反射防止機能付きフィルム；表面に反射機能を有する反射フィルム；反射機能と透過機能とを併せ持つ半透過反射フィルム；光拡散フィルム；ハードコートフィルム等を挙げることができる。粘着剤層付光学フィルムは、１種または２種以上の光学フィルムを含むことができ、同種のものを２以上含んでいてもよい。２以上の光学フィルムを含む場合、２以上の光学フィルムを積層するために、貼合層を用いてもよく、この場合、貼合層も光学フィルムの一部となり得る。光学フィルムの厚みは特に限定されないが、例えば５μｍ以上３００μｍ以下とすることができる。本明細書において、偏光子の片面または両面に保護フィルムが積層された偏光板は直線偏光板ともいう。 Examples of optical films include polarizers; protective films provided to protect the surface of polarizers and the like; polarizing plates in which protective films are laminated on one or both sides of a polarizer; retardation films; optical compensation films other than retardation films; anti-glare films with uneven surfaces, films with anti-reflection surfaces; reflective films with reflective surfaces; semi-transmissive reflective films with both reflective and transmissive functions; light diffusion films; and hard coat films. The optical film with adhesive layer can include one or more optical films, or may include two or more of the same type. When two or more optical films are included, a bonding layer may be used to laminate the two or more optical films, and in this case, the bonding layer can also be part of the optical film. The thickness of the optical film is not particularly limited, but can be, for example, 5 μm or more and 300 μm or less. In this specification, a polarizing plate in which a protective film is laminated on one or both sides of a polarizer is also called a linear polarizing plate.
　偏光子としては、例えば、ポリビニルアルコール系樹脂層にヨウ素が配向しているものや、液晶化合物と二色性色素とが配向したもの等を挙げることができる。 Examples of polarizers include those in which iodine is oriented in a polyvinyl alcohol resin layer, and those in which a liquid crystal compound and a dichroic dye are oriented.
　保護フィルムとしては、特に限定されないが、透光性を有する（好ましくは光学的に透明な）熱可塑性樹脂フィルムであることが好ましい。このようなフィルムを構成する熱可塑性樹脂として、例えば、鎖状ポリオレフィン系樹脂（ポリエチレン系樹脂、ポリプロピレン系樹脂等）、環状ポリオレフィン系樹脂（ノルボルネン系樹脂等）等のポリオレフィン系樹脂；トリアセチルセルロース、ジアセチルセルロースおよびセルロースアセテートプロピオネート等のセルロースエステル系樹脂；ポリエチレンテレフタレート、ポリエチレンナフタレート等のポリエステル系樹脂；ポリカーボネート系樹脂；（メタ）アクリル酸、ポリ（メタ）アクリル酸メチル等の（メタ）アクリル系樹脂；ポリビニルアルコールおよびポリ酢酸ビニル等のビニルアルコール系樹脂；ポリスチレン系樹脂；これらの混合物、共重合物等を挙げることができる。なお、本明細書において「（メタ）アクリル系」とは、「アクリル系およびメタクリル系の少なくとも１種」を意味する。これらの樹脂は、滑剤、可塑剤、分散剤、熱安定剤、紫外線吸収剤、赤外線吸収剤、帯電防止剤、酸化防止剤、微粒子等の光拡散剤等の添加剤を１種または２種以上含有していてもよい。 The protective film is not particularly limited, but is preferably a thermoplastic resin film having translucency (preferably optically transparent). Examples of the thermoplastic resin constituting such a film include polyolefin resins such as linear polyolefin resins (polyethylene resins, polypropylene resins, etc.) and cyclic polyolefin resins (norbornene resins, etc.); cellulose ester resins such as triacetyl cellulose, diacetyl cellulose, and cellulose acetate propionate; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; polycarbonate resins; (meth)acrylic resins such as (meth)acrylic acid and polymethyl (meth)acrylate; vinyl alcohol resins such as polyvinyl alcohol and polyvinyl acetate; polystyrene resins; mixtures and copolymers thereof. In this specification, "(meth)acrylic" means "at least one of acrylic and methacrylic". These resins may contain one or more additives such as lubricants, plasticizers, dispersants, heat stabilizers, UV absorbers, infrared absorbers, antistatic agents, antioxidants, and light diffusing agents such as fine particles.
　鎖状ポリオレフィン系樹脂としては、ポリエチレン樹脂、ポリプロピレン樹脂のような鎖状オレフィンの単独重合体のほか、２種以上の鎖状オレフィンからなる共重合体を挙げることができる。 Linear polyolefin resins include homopolymers of linear olefins such as polyethylene resin and polypropylene resin, as well as copolymers made of two or more types of linear olefins.
　環状ポリオレフィン系樹脂は、環状オレフィンを重合単位として重合される樹脂の総称である。環状ポリオレフィン系樹脂の具体例を挙げれば、環状オレフィンの開環（共）重合体、環状オレフィンの付加重合体、環状オレフィンとエチレン、プロピレンのような鎖状オレフィンとの共重合体（代表的にはランダム共重合体）、およびこれらを不飽和カルボン酸やその誘導体で変性したグラフト重合体、並びにそれらの水素化物等である。中でも、環状オレフィンとしてノルボルネンや多環ノルボルネン系モノマー等のノルボルネン系モノマーを用いたノルボルネン系樹脂が好ましく用いられる。 Cyclic polyolefin resin is a general term for resins polymerized using cyclic olefins as polymerization units. Specific examples of cyclic polyolefin resins include ring-opening (co)polymers of cyclic olefins, addition polymers of cyclic olefins, copolymers (typically random copolymers) of cyclic olefins with linear olefins such as ethylene and propylene, graft polymers modified with unsaturated carboxylic acids or their derivatives, and hydrogenated versions of these. Of these, norbornene resins using norbornene monomers such as norbornene or polycyclic norbornene monomers as the cyclic olefin are preferably used.
　セルロース系樹脂は、セルロースの部分または完全エステル化物であり、例えば、セルロースの酢酸エステル、プロピオン酸エステル、酪酸エステル、それらの混合エステル等が挙げられる。中でも、トリアセチルセルロース、ジアセチルセルロース、セルロースアセテートプロピオネート、セルロースアセテートブチレート等が好ましく用いられる。 Cellulosic resins are partial or complete esters of cellulose, such as cellulose acetate, propionate, butyrate, and mixed esters thereof. Among these, triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate, etc. are preferably used.
　ポリエステル系樹脂はエステル結合を有する、上記セルロース系樹脂以外の樹脂であり、多価カルボン酸またはその誘導体と多価アルコールとの重縮合体からなるものが一般的である。多価カルボン酸またはその誘導体としてはジカルボン酸またはその誘導体を用いることができ、例えばテレフタル酸、イソフタル酸、ジメチルテレフタレート、ナフタレンジカルボン酸ジメチル等が挙げられる。多価アルコールとしてはジオールを用いることができ、例えばエチレングリコール、プロパンジオール、ブタンジオール、ネオペンチルグリコール、シクロヘキサンジメタノール等が挙げられる。 　Polyester resins are resins other than the above-mentioned cellulose resins that have ester bonds, and are generally made of polycondensates of polycarboxylic acids or their derivatives with polyhydric alcohols. As the polycarboxylic acids or their derivatives, dicarboxylic acids or their derivatives can be used, such as terephthalic acid, isophthalic acid, dimethyl terephthalate, and dimethyl naphthalenedicarboxylate. As the polyhydric alcohols, diols can be used, such as ethylene glycol, propanediol, butanediol, neopentyl glycol, and cyclohexanedimethanol.
　ポリエステル系樹脂の具体例は、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート、ポリトリメチレンテレフタレート、ポリトリメチレンナフタレート、ポリシクロへキサンジメチルテレフタレート、ポリシクロヘキサンジメチルナフタレートを含む。 Specific examples of polyester resins include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polycyclohexane dimethyl terephthalate, and polycyclohexane dimethyl naphthalate.
　ポリカーボネート系樹脂は、カルボナート基を介してモノマー単位が結合された重合体からなる。ポリカーボネート系樹脂は、ポリマー骨格を修飾したような変性ポリカーボネートと呼ばれる樹脂や、共重合ポリカーボネート等であってもよい。 Polycarbonate-based resins consist of polymers in which monomer units are bonded via carbonate groups. Polycarbonate-based resins may be modified polycarbonates, which are resins in which the polymer backbone has been modified, or copolymer polycarbonates, etc.
　（メタ）アクリル系樹脂は、メタクリル酸エステルを主たるモノマーとする重合体であることができ、これに少量の他のコモノマー成分が共重合されている共重合体であることが好ましい。（メタ）アクリル系樹脂は、より好ましくはメタクリル酸メチルとアクリル酸メチルとの共重合体であり、第三の単官能モノマーをさらに共重合させてもよい。 The (meth)acrylic resin can be a polymer containing a methacrylic acid ester as the main monomer, and is preferably a copolymer in which a small amount of other comonomer components are copolymerized. The (meth)acrylic resin is more preferably a copolymer of methyl methacrylate and methyl acrylate, and may further be copolymerized with a third monofunctional monomer.
　第三の単官能モノマーとしては、例えば、メタクリル酸エチル、メタクリル酸ブチル、メタクリル酸シクロヘキシル、メタクリル酸フェニル、メタクリル酸ベンジル、メタクリル酸２－エチルヘキシル、メタクリル酸２－ヒドロキシエチルのようなメタクリル酸メチル以外のメタクリル酸エステル類；アクリル酸エチル、アクリル酸ブチル、アクリル酸シクロヘキシル、アクリル酸フェニル、アクリル酸ベンジル、アクリル酸２－エチルヘキシル、アクリル酸２－ヒドロキシエチルのようなアクリル酸エステル類；２－（ヒドロキシメチル）アクリル酸メチル、２－（１－ヒドロキシエチル）アクリル酸メチル、２－（ヒドロキシメチル）アクリル酸エチル、２－（ヒドロキシメチル）アクリル酸ブチルのようなヒドロキシアルキルアクリル酸エステル類；メタクリル酸、アクリル酸のような不飽和酸類；クロロスチレン、ブロモスチレンのようなハロゲン化スチレン類；ビニルトルエン、α－メチルスチレンのような置換スチレン類；アクリロニトリル、メタクリロニトリルのような不飽和ニトリル類；無水マレイン酸、無水シトラコン酸のような不飽和酸無水物類；フェニルマレイミド、シクロヘキシルマレイミドのような不飽和イミド類等を挙げることができる。第三の単官能モノマーは、１種のみを単独で用いてもよいし、２種以上を併用してもよい。 Examples of the third monofunctional monomer include methacrylic acid esters other than methyl methacrylate, such as ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, and 2-hydroxyethyl methacrylate; acrylic acid esters such as ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, and 2-hydroxyethyl acrylate; 2-(hydroxymethyl)methyl acrylate, 2-(1-hydroxy Examples of the third monofunctional monomer include hydroxyalkyl acrylates such as methyl 2-(ethyl)acrylate, ethyl 2-(hydroxymethyl)acrylate, and butyl 2-(hydroxymethyl)acrylate; unsaturated acids such as methacrylic acid and acrylic acid; halogenated styrenes such as chlorostyrene and bromostyrene; substituted styrenes such as vinyltoluene and α-methylstyrene; unsaturated nitriles such as acrylonitrile and methacrylonitrile; unsaturated acid anhydrides such as maleic anhydride and citraconic anhydride; and unsaturated imides such as phenylmaleimide and cyclohexylmaleimide. The third monofunctional monomer may be used alone or in combination of two or more kinds.
　（メタ）アクリル系樹脂には、多官能モノマーをさらに共重合させてもよい。多官能モノマーとしては、例えば、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ノナエチレングリコールジ（メタ）アクリレート、テトラデカエチレングリコールジ（メタ）アクリレートのようなエチレングリコールまたはそのオリゴマーの両末端水酸基をアクリル酸またはメタクリル酸でエステル化したもの；プロピレングリコールまたはそのオリゴマーの両末端水酸基をアクリル酸またはメタクリル酸でエステル化したもの；ネオペンチルグリコールジ（メタ）アクリレート、ヘキサンジオールジ（メタ）アクリレート、ブタンジオールジ（メタ）アクリレートのような２価アルコールの水酸基をアクリル酸またはメタクリル酸でエステル化したもの；ビスフェノールＡ、ビスフェノールＡのアルキレンオキサイド付加物、またはこれらのハロゲン置換体の両末端水酸基をアクリル酸またはメタクリル酸でエステル化したもの；トリメチロールプロパン、ペンタエリスリトールのような多価アルコールをアクリル酸またはメタクリル酸でエステル化したもの、並びにこれら末端水酸基にグリシジルアクリレートまたはグリシジルメタクリレートのエポキシ基を開環付加させたもの；コハク酸、アジピン酸、テレフタル酸、フタル酸、これらのハロゲン置換体等の二塩基酸、およびこれらのアルキレンオキサイド付加物等にグリシジルアクリレートまたはグリシジルメタクリレートのエポキシ基を開環付加させたもの；アリール（メタ）アクリレート；ジビニルベンゼンのような芳香族ジビニル化合物等が挙げられる。中でも、エチレングリコールジメタクリレート、テトラエチレングリコールジメタクリレート、ネオペンチルグリコールジメタクリレートが好ましく用いられる。 A polyfunctional monomer may be further copolymerized into the (meth)acrylic resin. Examples of polyfunctional monomers include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, and tetradecaethylene glycol di(meth)acrylate, which are esterified at both terminal hydroxyl groups of ethylene glycol or its oligomers with acrylic acid or methacrylic acid; propylene glycol or its oligomers with acrylic acid or methacrylic acid, which are esterified at both terminal hydroxyl groups of propylene glycol or its oligomers with acrylic acid or methacrylic acid; and dihydric alcohols such as neopentyl glycol di(meth)acrylate, hexanediol di(meth)acrylate, and butanediol di(meth)acrylate, which are esterified at both terminal hydroxyl groups of dihydric alcohols with acrylic acid or methacrylic acid. esterified with; bisphenol A, alkylene oxide adducts of bisphenol A, or both terminal hydroxyl groups of these halogen-substituted products esterified with acrylic acid or methacrylic acid; polyhydric alcohols such as trimethylolpropane and pentaerythritol esterified with acrylic acid or methacrylic acid, and products obtained by ring-opening addition of epoxy groups of glycidyl acrylate or glycidyl methacrylate to the terminal hydroxyl groups of these; dibasic acids such as succinic acid, adipic acid, terephthalic acid, phthalic acid, halogen-substituted products thereof, and alkylene oxide adducts thereof, etc., obtained by ring-opening addition of epoxy groups of glycidyl acrylate or glycidyl methacrylate; aryl (meth)acrylates; aromatic divinyl compounds such as divinylbenzene, etc. Among these, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and neopentyl glycol dimethacrylate are preferably used.
　（メタ）アクリル系樹脂は、さらに共重合体が有する官能基間の反応を行い、変性されたものであってもよい。その反応としては、例えば、アクリル酸メチルのメチルエステル基と２－（ヒドロキシメチル）アクリル酸メチルの水酸基との高分子鎖内脱メタノール縮合反応、アクリル酸のカルボキシル基と２－（ヒドロキシメチル）アクリル酸メチルの水酸基との高分子鎖内脱水縮合反応等が挙げられる。また（メタ）アクリル系樹脂は、グルタルイミド誘導体、グルタル酸無水物誘導体またはラクトン環構造のいずれかの構造を有してもよい。 The (meth)acrylic resin may be modified by further reacting the functional groups of the copolymer. Examples of such reactions include an intrapolymer chain demethanolization condensation reaction between the methyl ester group of methyl acrylate and the hydroxyl group of methyl 2-(hydroxymethyl)acrylate, and an intrapolymer chain dehydration condensation reaction between the carboxyl group of acrylic acid and the hydroxyl group of methyl 2-(hydroxymethyl)acrylate. The (meth)acrylic resin may also have any of the following structures: a glutarimide derivative, a glutaric anhydride derivative, or a lactone ring structure.
　（メタ）アクリル系樹脂のガラス転移温度は、好ましくは９０～１６０℃、より好ましくは１１０～１６０℃、さらに好ましくは１２０～１５０℃である。 The glass transition temperature of the (meth)acrylic resin is preferably 90 to 160°C, more preferably 110 to 160°C, and even more preferably 120 to 150°C.
　（メタ）アクリル系樹脂は、必要に応じて添加剤を含有していてもよい。添加剤としては例えば、滑剤、ブロッキング防止剤、熱安定剤、酸化防止剤、帯電防止剤、耐光剤、耐衝撃性改良剤、界面活性剤等を挙げることができる。 The (meth)acrylic resin may contain additives as necessary. Examples of additives include lubricants, antiblocking agents, heat stabilizers, antioxidants, antistatic agents, light resistance agents, impact resistance modifiers, surfactants, etc.
　（メタ）アクリル樹脂は、フィルムへの製膜性やフィルムの耐衝撃性等の観点から、衝撃性改良剤であるアクリル系ゴム粒子を含有していてもよい。アクリル系ゴム粒子とは、アクリル酸エステルを主体とする弾性重合体を必須成分とする粒子であり、実質的にこの弾性重合体のみからなる単層構造のものや、この弾性重合体を１つの層とする多層構造のものが挙げられる。この弾性重合体の例として、アクリル酸アルキルを主成分とし、これに共重合可能な他のビニルモノマーおよび架橋性モノマーを共重合させた架橋弾性共重合体が挙げられる。弾性重合体の主成分となるアクリル酸アルキルとしては、例えば、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸２－エチルへキシル等、アルキル基の炭素数が１～８程度のものが挙げられ、特に炭素数４以上のアルキル基を有するアクリル酸が好ましく用いられる。このアクリル酸アルキルに共重合可能な他のビニルモノマーとしては、分子内に重合性炭素－炭素二重結合を１個有する化合物を挙げることができ、より具体的には、メチルメタクリレートのようなメタクリル酸エステル、スチレンのような芳香族ビニル化合物、アクリロニトリルのようなビニルシアン化合物等が挙げられる。架橋性モノマーとしては、分子内に重合性炭素－炭素二重結合を少なくとも２個有する架橋性の化合物を挙げることができ、より具体的には、エチレングリコールジ（メタ）アクリレート、ブタンジオールジ（メタ）アクリレートのような多価アルコールの（メタ）アクリレート類、アリル（メタ）アクリレートのような（メタ）アクリル酸のアルケニルエステル、ジビニルベンゼン等が挙げられる。 　(Meth)acrylic resin may contain acrylic rubber particles as an impact modifier from the viewpoint of film formability and impact resistance of the film. Acrylic rubber particles are particles whose essential component is an elastic polymer mainly composed of acrylic acid ester, and examples thereof include a single-layer structure consisting essentially of this elastic polymer, and a multi-layer structure having this elastic polymer as one layer. An example of this elastic polymer is a cross-linked elastic copolymer in which alkyl acrylate is the main component and other copolymerizable vinyl monomers and cross-linkable monomers are copolymerized with this. Examples of alkyl acrylates that are the main component of elastic polymers include those with an alkyl group having 1 to 8 carbon atoms, such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, and acrylic acid having an alkyl group having 4 or more carbon atoms is particularly preferred. Examples of other vinyl monomers that can be copolymerized with this alkyl acrylate include compounds having one polymerizable carbon-carbon double bond in the molecule, and more specifically, methacrylic acid esters such as methyl methacrylate, aromatic vinyl compounds such as styrene, and vinyl cyan compounds such as acrylonitrile. Examples of crosslinkable monomers include crosslinkable compounds having at least two polymerizable carbon-carbon double bonds in the molecule, and more specifically, examples include (meth)acrylates of polyhydric alcohols such as ethylene glycol di(meth)acrylate and butanediol di(meth)acrylate, alkenyl esters of (meth)acrylic acid such as allyl (meth)acrylate, and divinylbenzene.
　ゴム粒子を含まないアクリル樹脂からなるフィルムと、ゴム粒子を含むアクリル樹脂からなるフィルムとの積層物を保護フィルムとすることもできる。 The protective film can also be a laminate of a film made of acrylic resin that does not contain rubber particles and a film made of acrylic resin that does contain rubber particles.
　位相差フィルムは、光学異方性を示す光学フィルムであり、上記保護フィルムに用いることができる樹脂のほか、例えば、ポリビニルアルコール系樹脂、ポリアリレート系樹脂、ポリイミド系樹脂、ポリエーテルサルホン系樹脂、ポリビニリデンフルオライド／ポリメチルメタクリレート系樹脂、液晶ポリエステル系樹脂、エチレン－酢酸ビニル共重合体ケン化物、ポリ塩化ビニル系樹脂等からなる樹脂フィルムを１．０１～６倍程度に延伸することにより得られる延伸フィルムであることができる。中でも、ポリカーボネート系樹脂フィルムやシクロオレフィン系樹脂フィルム、（メタ）アクリル系樹脂フィルムまたはセルロース系樹脂フィルムを一軸延伸または二軸延伸した延伸フィルムが好ましい。また本明細書においては、ゼロレタデーションフィルムも位相差フィルムに含まれる（ただし、保護フィルムとして用いることもできる。）。そのほか、一軸性位相差フィルム、広視野角位相差フィルム、低光弾性率位相差フィルム等と称されるフィルムも位相差フィルムとして適用可能である。 The retardation film is an optical film that exhibits optical anisotropy. In addition to the resins that can be used for the protective film, it can be a stretched film obtained by stretching a resin film made of, for example, polyvinyl alcohol resin, polyarylate resin, polyimide resin, polyethersulfone resin, polyvinylidene fluoride/polymethyl methacrylate resin, liquid crystal polyester resin, saponified ethylene-vinyl acetate copolymer, polyvinyl chloride resin, etc., by about 1.01 to 6 times. Among them, stretched films obtained by uniaxially or biaxially stretching a polycarbonate resin film, a cycloolefin resin film, a (meth)acrylic resin film, or a cellulose resin film are preferred. In this specification, zero retardation films are also included in the retardation film (however, they can also be used as protective films). In addition, films called uniaxial retardation films, wide viewing angle retardation films, low photoelasticity retardation films, etc. can also be used as retardation films.
　位相差フィルムは、基材上に重合性液晶化合物が配向した状態で重合した重合体からなる光学異方性層を有するフィルムであってもよい。基材は、上記保護フィルムに用いる熱可塑性樹脂フィルムであってよい。 The retardation film may be a film having an optically anisotropic layer made of a polymer formed by polymerizing a polymerizable liquid crystal compound in an oriented state on a substrate. The substrate may be the thermoplastic resin film used in the protective film.
　位相差フィルムは、例えば逆波長分散性の１／４波長位相差層、ポジティブＣプレート、正波長分散性の１／２波長位相差層、正波長分散性の１／４波長位相差層等であることができる。位相差フィルムは、２以上の位相差層から構成されてもよく、例えば逆波長分散性の１／４波長位相差層とポジティブＣプレートを組み合わせた構成、および、正波長分散性の１／２波長位相差層と正波長分散性の１／４波長位相差層を組み合わせた構成等を有していてもよい。 The retardation film can be, for example, a 1/4 wavelength retardation layer with reverse wavelength dispersion, a positive C plate, a 1/2 wavelength retardation layer with positive wavelength dispersion, a 1/4 wavelength retardation layer with positive wavelength dispersion, etc. The retardation film may be composed of two or more retardation layers, and may have, for example, a configuration in which a 1/4 wavelength retardation layer with reverse wavelength dispersion is combined with a positive C plate, or a configuration in which a 1/2 wavelength retardation layer with positive wavelength dispersion is combined with a 1/4 wavelength retardation layer with positive wavelength dispersion, etc.
　位相差フィルムや保護フィルムは、ＪＩＳ　Ｚ　０２０８に規定されるカップ法により、４０℃の温度および９０％の相対湿度で測定される透湿度が５００ｇ／（ｍ2・２４ｈｒ）以下であってよい。 The retardation film or protective film may have a moisture permeability of 500 g/(m 2 ·24 hr) or less, measured at a temperature of 40° C. and a relative humidity of 90% by the cup method specified in JIS Z 0208.
　表面保護フィルムは、被保護体である光学フィルム等の表面を傷や汚れから保護する目的で用いられるフィルムであり、例えば、液晶表示装置用の光学フィルムである偏光子、保護フィルム、位相差フィルム、光拡散シート、反射シート等の各種光学フィルムは通常、その表面（片面に粘着剤層を有する場合は、その粘着剤層と反対側の面）に表面保護フィルムを貼合した状態で流通している。表面保護フィルムは、上記光学フィルムを液晶セル等に貼合した後、剥離除去されるのが通例である。 A surface protective film is a film used for the purpose of protecting the surface of an object to be protected, such as an optical film, from scratches and dirt. For example, various optical films such as polarizers, protective films, retardation films, light diffusion sheets, and reflective sheets, which are optical films for liquid crystal display devices, are usually distributed with a surface protective film attached to their surface (the surface opposite the adhesive layer, if the optical film has an adhesive layer on one side). The surface protective film is usually peeled off and removed after the optical film is attached to a liquid crystal cell, etc.
　表面保護フィルムの基材としては、例えば、ポリエチレン、ポリプロピレン、ポリメチルペンテンのようなポリオレフィン系樹脂；ポリフッ化ビニル、ポリフッ化ビニリデン、ポリフッ化エチレンのようなフッ素化ポリオレフィン系樹脂；ポリエチレンナフタート、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンテレフタレート／イソフタレート共重合体のようなポリエステル系樹脂；ナイロン６、ナイロン６，６のようなポリアミド；ポリ塩化ビニル、塩化ビニル－酢酸ビニル共重合体、エチレン－酢酸ビニル共重合体、エチレン－ビニルアルコール共重合体、ポリビニルアルコール、ビニロンのようなビニル重合体；トリアセチルセルロース、ジアセチルセルロース、セロハンのようなセルロース系樹脂；ポリメタクリル酸メチル、ポリメタクリル酸エチル、ポリアクリル酸エチル、ポリアクリル酸ブチルのような（メタ）アクリル系樹脂；その他、ポリスチレン、ポリカーボネート、ポリアリレート、ポリイミド等が挙げられる。 　Examples of substrates for surface protection films include polyolefin resins such as polyethylene, polypropylene, and polymethylpentene; fluorinated polyolefin resins such as polyvinyl fluoride, polyvinylidene fluoride, and polyethylene fluoride; polyester resins such as polyethylene naphthalate, polyethylene terephthalate, polybutylene terephthalate, and polyethylene terephthalate/isophthalate copolymers; polyamides such as nylon 6 and nylon 6,6; vinyl polymers such as polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, and vinylon; cellulose resins such as triacetyl cellulose, diacetyl cellulose, and cellophane; (meth)acrylic resins such as polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, and polybutyl acrylate; and others such as polystyrene, polycarbonate, polyarylate, and polyimide.
　貼合層は、粘着剤層であってもよいし、接着剤層であってもよい。貼合層が粘着剤層である場合、貼合層には、上述の粘着剤層以外の粘着剤層を用いることができる。貼合層が粘着剤層である場合、粘着剤層は、（メタ）アクリル系樹脂、ゴム系樹脂、ウレタン系樹脂、エステル系樹脂、シリコーン系樹脂、ポリビニルエーテル系樹脂のような樹脂を主成分とする粘着剤組成物で構成することができる。中でも、透明性、耐候性、耐熱性等に優れる（メタ）アクリル系樹脂をベースポリマーとする粘着剤組成物が好適である。粘着剤組成物は、活性エネルギー線硬化型、熱硬化型であってもよい。 The lamination layer may be an adhesive layer or an adhesive layer. When the lamination layer is an adhesive layer, an adhesive layer other than the above-mentioned adhesive layer may be used for the lamination layer. When the lamination layer is an adhesive layer, the adhesive layer may be composed of an adhesive composition mainly composed of a resin such as a (meth)acrylic resin, a rubber resin, a urethane resin, an ester resin, a silicone resin, or a polyvinyl ether resin. Among them, an adhesive composition having a (meth)acrylic resin as a base polymer, which is excellent in transparency, weather resistance, heat resistance, etc., is preferable. The adhesive composition may be an active energy ray curable type or a heat curable type.
　粘着剤組成物に用いられる（メタ）アクリル系樹脂（ベースポリマー）としては、例えば、（メタ）アクリル酸ブチル、（メタ）アクリル酸エチル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸２－エチルヘキシルのような（メタ）アクリル酸エステルの１種または２種以上をモノマーとする重合体または共重合体が好適に用いられる。ベースポリマーには、極性モノマーを共重合させることが好ましい。極性モノマーとしては、例えば、（メタ）アクリル酸、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリルアミド、Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、グリシジル（メタ）アクリレートのような、カルボキシル基、水酸基、アミド基、アミノ基、エポキシ基等を有するモノマーを挙げることができる。 The (meth)acrylic resin (base polymer) used in the adhesive composition is preferably a polymer or copolymer having one or more monomers of (meth)acrylic acid esters such as butyl (meth)acrylate, ethyl (meth)acrylate, isooctyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. It is preferable to copolymerize a polar monomer into the base polymer. Examples of polar monomers include monomers having a carboxyl group, hydroxyl group, amide group, amino group, epoxy group, etc., such as (meth)acrylic acid, 2-hydroxypropyl (meth)acrylate, hydroxyethyl (meth)acrylate, (meth)acrylamide, N,N-dimethylaminoethyl (meth)acrylate, and glycidyl (meth)acrylate.
　粘着剤組成物は、上記ベースポリマーのみを含むものであってもよいが、通常は架橋剤をさらに含有する。架橋剤としては、２価以上の金属イオンであって、カルボキシル基との間でカルボン酸金属塩を形成するもの；ポリアミン化合物であって、カルボキシル基との間でアミド結合を形成するもの；ポリエポキシ化合物やポリオールであって、カルボキシル基との間でエステル結合を形成するもの；ポリイソシアネート化合物であって、カルボキシル基との間でアミド結合を形成するものが例示される。中でも、ポリイソシアネート化合物が好ましい。 The adhesive composition may contain only the base polymer, but usually also contains a crosslinking agent. Examples of crosslinking agents include divalent or higher metal ions that form metal carboxylates with carboxyl groups; polyamine compounds that form amide bonds with carboxyl groups; polyepoxy compounds or polyols that form ester bonds with carboxyl groups; and polyisocyanate compounds that form amide bonds with carboxyl groups. Of these, polyisocyanate compounds are preferred.
　貼合層が粘着剤層である場合、貼合層の厚みは、１μｍ以上２００μｍ以下が好ましく、２μｍ以上１００μｍ以下がより好ましく、２μｍ以上８０μｍ以下がさらに好ましく、３μｍ以上５０μｍ以下が特に好ましい。 When the attachment layer is an adhesive layer, the thickness of the attachment layer is preferably 1 μm or more and 200 μm or less, more preferably 2 μm or more and 100 μm or less, even more preferably 2 μm or more and 80 μm or less, and particularly preferably 3 μm or more and 50 μm or less.
　貼合層が接着剤層である場合、接着剤は、任意の適切な接着剤を用いることができる。接着剤は、水系接着剤、活性エネルギー線硬化型接着剤などを用いることができる。 When the lamination layer is an adhesive layer, any suitable adhesive can be used. The adhesive can be a water-based adhesive, an active energy ray curing adhesive, or the like.
　接着剤の塗布時の厚みは、任意の適切な値に設定され得る。例えば、硬化後または加熱（乾燥）後に、所望の厚みを有する接着剤層が得られるように設定する。接着剤層の厚みは、好ましくは０．０１μｍ以上７μｍ以下であり、より好ましくは０．０１μｍ以上５μｍ以下であり、さらに好ましくは０．０１μｍ以上２μｍ以下であり、最も好ましくは０．０１μｍ以上１μｍ以下である。 The thickness of the adhesive when applied can be set to any appropriate value. For example, it is set so that an adhesive layer having the desired thickness is obtained after curing or heating (drying). The thickness of the adhesive layer is preferably 0.01 μm or more and 7 μm or less, more preferably 0.01 μm or more and 5 μm or less, even more preferably 0.01 μm or more and 2 μm or less, and most preferably 0.01 μm or more and 1 μm or less.
　水系接着剤としては、例えばポリビニルアルコール系樹脂水溶液、水系二液型ウレタン系エマルジョン接着剤等を挙げることができる。 Examples of water-based adhesives include aqueous polyvinyl alcohol resin solutions and water-based two-component urethane emulsion adhesives.
　上記活性エネルギー線硬化性接着剤とは、紫外線、可視光、電子線、Ｘ線のような活性エネルギー線の照射によって硬化する硬化性化合物を含有する接着剤であり、好ましくは紫外線硬化性接着剤である。 The active energy ray-curable adhesive is an adhesive containing a curable compound that cures when exposed to active energy rays such as ultraviolet light, visible light, electron beams, and X-rays, and is preferably an ultraviolet ray-curable adhesive.
　上記硬化性化合物は、カチオン重合性の硬化性化合物やラジカル重合性の硬化性化合物であることができる。カチオン重合性の硬化性化合物としては、例えば、エポキシ系化合物（分子内に１個または２個以上のエポキシ基を有する化合物）や、オキセタン系化合物（分子内に１個または２個以上のオキセタン環を有する化合物）、またはこれらの組み合わせを挙げることができる。ラジカル重合性の硬化性化合物としては、例えば、（メタ）アクリル系化合物（分子内に１個または２個以上の（メタ）アクリロイルオキシ基を有する化合物）や、ラジカル重合性の二重結合を有するその他のビニル系化合物、またはこれらの組み合わせを挙げることができる。カチオン重合性の硬化性化合物とラジカル重合性の硬化性化合物とを併用してもよい。活性エネルギー線硬化性接着剤は通常、上記硬化性化合物の硬化反応を開始させるためのカチオン重合開始剤およびラジカル重合開始剤の少なくとも一方をさらに含む。 The curable compound may be a cationic polymerizable curable compound or a radical polymerizable curable compound. Examples of the cationic polymerizable curable compound include an epoxy compound (a compound having one or more epoxy groups in the molecule), an oxetane compound (a compound having one or more oxetane rings in the molecule), or a combination of these. Examples of the radical polymerizable curable compound include a (meth)acrylic compound (a compound having one or more (meth)acryloyloxy groups in the molecule), other vinyl compounds having a radical polymerizable double bond, or a combination of these. A cationic polymerizable curable compound and a radical polymerizable curable compound may be used in combination. An active energy ray curable adhesive usually further includes at least one of a cationic polymerization initiator and a radical polymerization initiator for initiating the curing reaction of the curable compound.
　接着性を高めるために、貼合層および光学フィルムの少なくともいずれか一方の貼合面に表面活性化処理を施してもよい。表面活性化処理としては、コロナ処理、プラズマ処理、放電処理（グロー放電処理等）、オゾン処理、ＵＶオゾン処理、電離活性線処理（紫外線処理、電子線処理等）のような乾式処理等を挙げることができる。これらの表面活性化処理は、単独で行ってもよいし、２つ以上を組み合わせてもよい。中でもコロナ処理が好ましい。コロナ処理は、例えば１ｋＪ／ｍ２以上５０ｋＪ／ｍ２以下の出力で行うことができる。コロナ処理を行う時間は、例えば１秒間以上１分以下であってよい。 In order to enhance adhesion, a surface activation treatment may be applied to at least one of the laminating surfaces of the laminating layer and the optical film. Examples of the surface activation treatment include dry treatments such as corona treatment, plasma treatment, discharge treatment (glow discharge treatment, etc.), ozone treatment, UV ozone treatment, and ionizing active ray treatment (ultraviolet ray treatment, electron beam treatment, etc.). These surface activation treatments may be performed alone or in combination of two or more. Among them, corona treatment is preferred. Corona treatment may be performed with an output of, for example, 1 kJ/m 2 or more and 50 kJ/m 2 or less. The time for performing corona treatment may be, for example, 1 second or more and 1 minute or less.
　本実施形態に係る粘着剤層付光学フィルムにおいて、その粘着剤層表面には、上述の剥離フィルムを貼着し、使用時まで仮着保護しておくことが好ましい。剥離フィルムが貼着された本実施形態に係る粘着剤層付光学フィルムは、剥離フィルムの上に粘着剤組成物を塗布して粘着剤層を形成し、得られた粘着剤層にさらに樹脂フィルムを積層する方法、樹脂フィルムの上に粘着剤組成物を塗布して粘着剤層を形成し、その粘着剤面に剥離フィルムを貼り合わせる方法によって製造できる。 In the optical film with an adhesive layer according to this embodiment, it is preferable to attach the above-mentioned release film to the surface of the adhesive layer and provide temporary protection until use. The optical film with an adhesive layer according to this embodiment with a release film attached can be manufactured by a method of applying an adhesive composition onto a release film to form an adhesive layer and further laminating a resin film onto the resulting adhesive layer, or a method of applying an adhesive composition onto a resin film to form an adhesive layer and laminating a release film onto the adhesive surface.
　粘着剤層付光学フィルムは、有機エレクトロルミネッセンス（有機ＥＬ）表示装置や液晶表示装置等の表示装置に用いることができ、この表示装置の画像表示素子の視認側に貼合して用いることができる。 The optical film with adhesive layer can be used in displays such as organic electroluminescence (organic EL) displays and liquid crystal displays, and can be attached to the viewing side of the image display element of these displays.
　粘着剤層付光学フィルムは、光学フィルムと、光学フィルム上に積層された粘着剤層とを含むものであれば、その積層構造は特に限定されない。 The laminated structure of the optical film with adhesive layer is not particularly limited as long as it includes an optical film and an adhesive layer laminated on the optical film.
　図１に示す粘着剤層付光学フィルム１０は、直線偏光板１１と、粘着剤層１２とを含む。直線偏光板１１は、第１保護フィルム１３、接着剤層１４、偏光子１５、接着剤層１６、第２保護フィルム１７をこの順に含む。粘着剤層１２は、液晶表示装置の画像表示素子である液晶セルに貼合するために用いられることができる。粘着剤層１２の直線偏光板１１とは反対側の面には、図示しないセパレータ（剥離フィルム）が設けられていてもよい。 The adhesive layer-attached optical film 10 shown in FIG. 1 includes a linear polarizer 11 and an adhesive layer 12. The linear polarizer 11 includes, in this order, a first protective film 13, an adhesive layer 14, a polarizer 15, an adhesive layer 16, and a second protective film 17. The adhesive layer 12 can be used to attach to a liquid crystal cell, which is an image display element of a liquid crystal display device. A separator (release film) (not shown) may be provided on the surface of the adhesive layer 12 opposite the linear polarizer 11.
　図２に示す粘着剤層付光学フィルム２０は、粘着剤層２１、位相差フィルム２２、貼合層２３、直線偏光板２４をこの順に含む。直線偏光板２４は、第１保護フィルム２５、接着剤層２６、偏光子２７、接着剤層２８、第２保護フィルム２９をこの順に含む。粘着剤層２１は、液晶表示装置の画像表示素子である液晶セルに貼合するために用いられることができる。粘着剤層２１の位相差フィルム２２とは反対側の面には、図示しないセパレータ（剥離フィルム）が設けられていてもよい。 The adhesive layer-attached optical film 20 shown in FIG. 2 includes, in this order, an adhesive layer 21, a retardation film 22, an attachment layer 23, and a linear polarizer 24. The linear polarizer 24 includes, in this order, a first protective film 25, an adhesive layer 26, a polarizer 27, an adhesive layer 28, and a second protective film 29. The adhesive layer 21 can be used to attach to a liquid crystal cell, which is an image display element of a liquid crystal display device. A separator (peeling film) (not shown) may be provided on the surface of the adhesive layer 21 opposite the retardation film 22.
　図１および図２に示す粘着剤層付光学フィルム１０および２０は一例にすぎず、上記以外の積層構造を有するものであってもよい。例えば保護フィルムはハードコートフィルムや防眩機能付きフィルム、表面反射防止機能付きフィルム等のさらなる層を有していてもよい。 The optical films 10 and 20 with adhesive layers shown in Figures 1 and 2 are merely examples, and may have a laminate structure other than that described above. For example, the protective film may have further layers such as a hard coat film, a film with anti-glare function, or a film with surface anti-reflection function.
　＜光学積層体＞
　本発明に係る光学積層体は、上述の粘着剤層付光学フィルムと金属層とを備える。図３は、光学積層体の層構成の例を示す概略断面図である。図３に示す光学積層体３０は、直線偏光板１１と粘着剤層１２とを備える粘着剤層付光学フィルム１０と、その粘着剤層１２に積層される金属層３１とを含む。図３に示す光学積層体３０において、粘着剤層付光学フィルム１０は、その粘着剤層１２が金属層３１に直接接するように金属層３１上に積層されている。本発明によれば、このように粘着剤層１２が金属層３１に直接接するような構成の光学積層体においても、金属層３１の腐食を効果的に抑制することができる。 <Optical laminate>
The optical laminate according to the present invention includes the above-mentioned pressure-sensitive adhesive layer-attached optical film and a metal layer. Fig. 3 is a schematic cross-sectional view showing an example of the layer structure of the optical laminate. The optical laminate 30 shown in Fig. 3 includes a pressure-sensitive adhesive layer-attached optical film 10 including a linear polarizing plate 11 and a pressure-sensitive adhesive layer 12, and a metal layer 31 laminated on the pressure-sensitive adhesive layer 12. In the optical laminate 30 shown in Fig. 3, the pressure-sensitive adhesive layer-attached optical film 10 is laminated on the metal layer 31 so that the pressure-sensitive adhesive layer 12 is in direct contact with the metal layer 31. According to the present invention, even in an optical laminate having such a configuration that the pressure-sensitive adhesive layer 12 is in direct contact with the metal layer 31, corrosion of the metal layer 31 can be effectively suppressed.
　図４は、本発明に係る光学積層体の層構成の他の一例を示す概略断面図である。図４に示す光学積層体４０のように、直線偏光板１１と粘着剤層１２とを備える粘着剤層付光学フィルム１０の粘着剤層１２が樹脂層４１を介して金属層４２に積層されている。粘着剤層１２は、樹脂層４１に直接接している。かかる光学積層体４０においても、金属層４２の腐食を効果的に抑制することができる。粘着剤層１２と金属層４２との間に配置される樹脂層４１は、例えば、硬化性樹脂の硬化物層であってもよい。樹脂層４１を形成し得る硬化性樹脂としては公知のものを用いることができ、例えば特開２００９－２１７０３７号公報に記載のものが挙げられる。 FIG. 4 is a schematic cross-sectional view showing another example of the layer structure of the optical laminate according to the present invention. As in the optical laminate 40 shown in FIG. 4, the adhesive layer 12 of the adhesive layer-attached optical film 10 including the linear polarizer 11 and the adhesive layer 12 is laminated to the metal layer 42 via the resin layer 41. The adhesive layer 12 is in direct contact with the resin layer 41. In this optical laminate 40, the corrosion of the metal layer 42 can also be effectively suppressed. The resin layer 41 disposed between the adhesive layer 12 and the metal layer 42 may be, for example, a cured layer of a curable resin. As the curable resin capable of forming the resin layer 41, a known one can be used, and examples thereof include those described in JP-A-2009-217037.
　金属層は、例えば、アルミニウム、銅、銀、金、鉄、スズ、亜鉛、ニッケル、モリブデン、クロム、タングステン、鉛及びこれらから選択される２種以上の金属を含む合金からなる群より選択される１種以上を含む層であることができ、導電性の観点から、好ましくはアルミニウム、銅、銀及び金からなる群より選択される金属元素を含む層であり、導電性及びコストの観点から、より好ましくはアルミニウム元素を含む層であり、さらに好ましくはアルミニウム元素を主成分として含む層である。主成分として含むとは、金属層を構成する金属成分が全金属成分の３０重量％以上、さらには５０重量％以上であることをいう。 The metal layer can be, for example, a layer containing one or more metals selected from the group consisting of aluminum, copper, silver, gold, iron, tin, zinc, nickel, molybdenum, chromium, tungsten, lead, and alloys containing two or more metals selected from these. From the viewpoint of electrical conductivity, it is preferably a layer containing a metal element selected from the group consisting of aluminum, copper, silver, and gold. From the viewpoint of electrical conductivity and cost, it is more preferably a layer containing aluminum element, and even more preferably a layer containing aluminum element as the main component. "Containing as the main component" means that the metal component constituting the metal layer is 30% by weight or more, and even more preferably 50% by weight or more of the total metal components.
　金属層は、例えばＩＴＯ等の金属酸化物層であってもよいが、本発明に係る粘着剤層付光学フィルムは、とりわけ金属単体や合金に対する耐腐食性が良好であることから、金属層は、上記の金属元素からなる金属単体及び／又は上記の金属元素の２種以上を含有する合金を含むことが好ましい。ただし、光学積層体は、このような金属層とともに、ＩＴＯ等の金属酸化物からなる透明電極層を有していてもよい。 The metal layer may be, for example, a metal oxide layer such as ITO, but since the pressure-sensitive adhesive layer-attached optical film according to the present invention has particularly good corrosion resistance against simple metals and alloys, it is preferable that the metal layer contains a simple metal composed of the above metal elements and/or an alloy containing two or more of the above metal elements. However, the optical laminate may have a transparent electrode layer composed of a metal oxide such as ITO in addition to such a metal layer.
　金属層の形態（例えば厚み等）や調製方法は特に限定されず、金属箔であることができるほか、真空蒸着法、スパッタリング法、イオンプレーティング法、インクジェット印刷法、グラビア印刷法により形成されたものでもよいが、好ましくはスパッタリング法、インクジェット印刷法、グラビア印刷法により形成された金属層であり、より好ましくスパッタリングにより形成された金属層である。スパッタリングで形成された金属層と金属箔とでは、前者の方が耐腐食性が悪い傾向にあるが、本発明に係る光学積層体によれば、スパッタリングで形成された金属層に対しても良好な耐金属腐食性を有する。金属層の厚みは、通常３μｍ以下であり、好ましくは１μｍ以下であり、より好ましくは０．８μｍ以下である。また金属層の厚みは、通常０．０１μｍ以上である。さらに、金属層が金属配線層の場合、その金属配線層が有する金属配線の線幅は通常１０μｍ以下であり、好ましくは５μｍ以下であり、さらに好ましくは３μｍ以下である。また金属配線の線幅は、通常０．０１μｍ以上であり、好ましくは０．１μｍ以上であり、さらに好ましくは０．５μｍ以上である。かかる薄膜の金属層や細線の金属配線からなる金属層に対しても、本発明に係る光学積層体は良好な耐金属腐食性を示す。特に、金属配線が、例えば厚み３μｍ以下であり線幅１０μｍ以下である場合や、厚み３μｍ以下であり線幅１０μｍ以下であり、スパッタリング法により形成された場合であっても、その腐食、特に孔食を抑えることができる。 The form (e.g., thickness, etc.) and preparation method of the metal layer are not particularly limited, and it can be a metal foil, or it may be formed by vacuum deposition, sputtering, ion plating, inkjet printing, or gravure printing. However, it is preferably a metal layer formed by sputtering, inkjet printing, or gravure printing, and more preferably a metal layer formed by sputtering. A metal layer formed by sputtering tends to have poorer corrosion resistance than a metal foil, but the optical laminate of the present invention has good metal corrosion resistance even against a metal layer formed by sputtering. The thickness of the metal layer is usually 3 μm or less, preferably 1 μm or less, and more preferably 0.8 μm or less. The thickness of the metal layer is usually 0.01 μm or more. Furthermore, when the metal layer is a metal wiring layer, the line width of the metal wiring of the metal wiring layer is usually 10 μm or less, preferably 5 μm or less, and more preferably 3 μm or less. The line width of the metal wiring is usually 0.01 μm or more, preferably 0.1 μm or more, and more preferably 0.5 μm or more. The optical laminate of the present invention exhibits good metal corrosion resistance even against such thin metal layers and metal layers consisting of fine metal wiring. In particular, even when the metal wiring has a thickness of 3 μm or less and a line width of 10 μm or less, or a thickness of 3 μm or less and a line width of 10 μm or less and is formed by a sputtering method, corrosion, particularly pitting corrosion, can be suppressed.
　金属層は、例えば、タッチ入力式液晶表示装置が有するタッチ入力素子の金属配線層（すなわち電極層）であることができる。この場合、金属層は、所定の形状にパターニングされているのが通常である。パターニングされた金属層上に粘着剤層を積層する場合、粘着剤は金属層に接触していない部分を有していてもよい。金属層は、上記金属又は合金を含む連続膜であってもよい。 The metal layer can be, for example, a metal wiring layer (i.e., an electrode layer) of a touch input element of a touch input type liquid crystal display device. In this case, the metal layer is usually patterned into a predetermined shape. When an adhesive layer is laminated on a patterned metal layer, the adhesive may have a portion that is not in contact with the metal layer. The metal layer may be a continuous film containing the above metal or alloy.
　また、金属層は単層構造であってもよいし、２層又は３層以上の多層構造であってもよい。多層構造の金属層としては、例えばモリブデン／アルミニウム／モリブデンで示される３層構造の金属含有層（メタルメッシュ等）が挙げられる。 The metal layer may have a single layer structure, or a multi-layer structure of two or more layers. An example of a multi-layer metal layer is a metal-containing layer (such as a metal mesh) with a three-layer structure represented by molybdenum/aluminum/molybdenum.
　例えば金属配線層である金属層は基板上に形成されていてもよく、この場合、本発明に係る光学積層体は、この基板を含むことができる。基板上への金属層の形成は、例えばスパッタリングにより行うことができる。基板は、タッチ入力素子に含まれる液晶セルを構成する透明基板であることができる。基板は、好ましくはガラス基板である。ガラス基板の材料としては、例えば、ソーダライムガラス、低アルカリガラス、無アルカリガラス等が挙げられる。金属層は、基板の全面に形成されていてもよいし、その一部に形成されていてもよい。基板上にパターニングされた金属層が形成される場合など、基板の表面の一部に金属層が形成される場合には、粘着剤層の一部は、例えばガラスからなる基板と直接接触することになるが、本発明に係る光学積層体における粘着剤層は、ガラスとの密着性にも優れているため、光学積層体、及びこれを備えた液晶表示装置は、そのような場合における耐熱耐久性にも優れる。 For example, a metal layer, which is a metal wiring layer, may be formed on a substrate, and in this case, the optical laminate according to the present invention may include this substrate. The metal layer may be formed on the substrate by, for example, sputtering. The substrate may be a transparent substrate that constitutes a liquid crystal cell included in a touch input element. The substrate is preferably a glass substrate. Examples of materials for the glass substrate include soda lime glass, low alkali glass, and non-alkali glass. The metal layer may be formed on the entire surface of the substrate, or may be formed on a part of it. When a metal layer is formed on a part of the surface of the substrate, such as when a patterned metal layer is formed on the substrate, a part of the adhesive layer will be in direct contact with the substrate made of, for example, glass. However, since the adhesive layer in the optical laminate according to the present invention has excellent adhesion to glass, the optical laminate and the liquid crystal display device including the same have excellent heat resistance and durability in such cases.
　＜表示装置＞
　本発明に係る表示装置は、上述の粘着剤層付光学フィルムを含む。上記した粘着剤層付光学フィルムは、有機ＥＬ表示装置、液晶表示装置、無機エレクトロルミネッセンス（無機ＥＬ）表示装置、電子放出表示装置等の表示装置に好適に用いることができる。 <Display Device>
The display device according to the present invention includes the pressure-sensitive adhesive layer-attached optical film described above. The pressure-sensitive adhesive layer-attached optical film described above can be suitably used in displays such as organic EL displays, liquid crystal displays, inorganic electroluminescence (inorganic EL) displays, and electron emission displays.
　図５に示す表示装置５０は、図１に示す粘着剤層付光学フィルム１０と、液晶表示素子５１とを含む液晶表示装置である。粘着剤層付光学フィルム１０は、粘着剤層１２を介して、液晶表示素子５１の視認側及び／又は背面側に配置することができる。 The display device 50 shown in FIG. 5 is a liquid crystal display device including the optical film 10 with adhesive layer shown in FIG. 1 and a liquid crystal display element 51. The optical film 10 with adhesive layer can be disposed on the viewing side and/or the back side of the liquid crystal display element 51 via the adhesive layer 12.
　以下、実施例及び比較例を示して本発明をさらに具体的に説明するが、本発明はこれらの例によって限定されるものではない。以下、使用量ないし含有量を表す部及び％は、特に断りのない限り質量基準である。 The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following, parts and percentages indicating amounts used or contents are based on mass unless otherwise specified.
　＜製造例１：粘着剤層用（メタ）アクリル系樹脂の製造＞
　冷却管、窒素導入管、温度計及び攪拌機を備えた反応容器に、酢酸エチル８６．４部、ブチルアクリレート６８．７部、メチルアクリレート２０．０部、メチルメタクリレート１０．０部、２－ヒドロキシエチルアクリレート１．０部、及びアクリル酸０．３部の混合溶液を仕込み、窒素ガスで装置内の空気を置換して酸素不含としながら内温を６０℃に上げた。その後、アゾビスイソブチロニトリル（重合開始剤）０．１５部を酢酸エチル１３．７部に溶かした溶液を全量添加した。開始剤の添加後４時間この濃度で保持した。最後に酢酸エチルを加えて（メタ）アクリル系樹脂の濃度が２０質量％となるように調節し、（メタ）アクリル系樹脂の酢酸エチル溶液を調製した。 <Production Example 1: Production of (meth)acrylic resin for pressure-sensitive adhesive layer>
A reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer was charged with a mixed solution of 86.4 parts of ethyl acetate, 68.7 parts of butyl acrylate, 20.0 parts of methyl acrylate, 10.0 parts of methyl methacrylate, 1.0 parts of 2-hydroxyethyl acrylate, and 0.3 parts of acrylic acid, and the air in the apparatus was replaced with nitrogen gas to make it oxygen-free, while the internal temperature was raised to 60 ° C. Then, a solution of 0.15 parts of azobisisobutyronitrile (polymerization initiator) dissolved in 13.7 parts of ethyl acetate was added in its entirety. After the addition of the initiator, this concentration was maintained for 4 hours. Finally, ethyl acetate was added to adjust the concentration of the (meth)acrylic resin to 20% by mass, and an ethyl acetate solution of the (meth)acrylic resin was prepared.
　得られた（メタ）アクリル系樹脂のガラス転移温度(Ｔｇ)を測定した。
　Ｔｇは、エスアイアイ・ナノテクノロジー（株）製の示差走査熱量計（ＤＳＣ）「ＥＸＳＴＡＲ　ＤＳＣ６０００」を用い、窒素雰囲気下、測定温度範囲－８０～５０℃、昇温速度１０℃／分の条件で測定した。 The glass transition temperature (Tg) of the resulting (meth)acrylic resin was measured.
The Tg was measured using a differential scanning calorimeter (DSC) "EXSTAR DSC6000" manufactured by SII NanoTechnology Co., Ltd. under conditions of a nitrogen atmosphere, a measurement temperature range of -80 to 50°C, and a heating rate of 10°C/min.
　得られた（メタ）アクリル系樹脂の重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）を測定した。
　Ｍｗ及びＭｎは、ＧＰＣ装置にカラムとして、東ソー（株）製の「ＴＳＫｇｅｌ　ｇｕａｒｄｃｏｌｕｍｎＨＨＲ－Ｈ（Ｓ）」を１本、「ＴＳＫｇｅｌ　ＧＭＨＨＲ－Ｈ」を２本の計３本を直列につないで配置し、溶出液としてテトラヒドロフランを用い、試料濃度２ｍｇ／ｍＬ、試料導入量１００μＬ、温度４０℃、流速１ｍＬ／分の条件で、標準ポリスチレン換算により測定した。
　用いたモノマー混合物のモノマー組成、並びに得られた（メタ）アクリル系樹脂のＴｇ、Ｍｗ及び分子量分布（Ｍｗ／Ｍｎ）を表１にまとめた。
　＜製造例２～１０＞
　モノマー組成を表１の通りにした以外は、製造例１と同様に（メタ）アクリル系樹脂の酢酸エチル溶液を調整した。 The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resulting (meth)acrylic resin were measured.
Mw and Mn were measured in terms of standard polystyrene using a GPC apparatus with three columns in series, one "TSKgel guard column HHR-H(S)" manufactured by Tosoh Corporation and two "TSKgel GMHHR-H", and tetrahydrofuran as an eluent under the conditions of a sample concentration of 2 mg/mL, a sample introduction amount of 100 μL, a temperature of 40° C., and a flow rate of 1 mL/min.
Table 1 shows the monomer composition of the monomer mixture used, as well as the Tg, Mw and molecular weight distribution (Mw/Mn) of the resulting (meth)acrylic resin.
<Production Examples 2 to 10>
An ethyl acetate solution of a (meth)acrylic resin was prepared in the same manner as in Production Example 1, except that the monomer composition was as shown in Table 1.
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
　表１の「モノマー組成」の欄にある略称は、次のモノマーを意味する。
　ＢＡ　　：ブチルアクリレート（ホモポリマーＴｇ：－５４℃）
　ＯＡ　　：オクチルメタクリレート（ホモポリマーＴｇ：－６５℃）
　ＭＡ　　：メチルアクリレート（ホモポリマーＴｇ：１０℃）
　ＭＭＡ　：メチルメタクリレート（ホモポリマーＴｇ：１０５℃）
　ＩＢＭＡ：イソボロニルメタクリレート（ホモポリマーＴｇ：１１０℃）
　ＴＢＭＡ：ｔｅｒｔ－ブチルメタクリレート（ホモポリマーＴｇ：１１８℃）
　ＣＨＭＡ：シクロヘキシルメタクリレート（ホモポリマーＴｇ：８３℃）
　ＥＭＡ　：エチルメタクリレート（ホモポリマーＴｇ：６５℃）
　ＨＥＡ　：２－ヒドロキシエチルアクリレート
　４ＨＢＡ：４－ヒドロキシブチルアクリレート
　ＡＡ　　：アクリル酸 The abbreviations in the "Monomer composition" column of Table 1 represent the following monomers.
BA: Butyl acrylate (homopolymer Tg: -54°C)
OA: Octyl methacrylate (homopolymer Tg: -65°C)
MA: methyl acrylate (homopolymer Tg: 10° C.)
MMA: methyl methacrylate (homopolymer Tg: 105°C)
IBMA: isobornyl methacrylate (homopolymer Tg: 110° C.)
TBMA: tert-butyl methacrylate (homopolymer Tg: 118° C.)
CHMA: cyclohexyl methacrylate (homopolymer Tg: 83° C.)
EMA: Ethyl methacrylate (homopolymer Tg: 65° C.)
HEA: 2-hydroxyethyl acrylate 4HBA: 4-hydroxybutyl acrylate AA: acrylic acid
　＜実施例１～１２、および比較例１および２＞
　（１）粘着剤組成物の調製
　上記製造例で得られた（メタ）アクリル系樹脂の酢酸エチル溶液（樹脂濃度：２０％）に、該溶液の固形分１００質量部に対し、架橋剤、シラン化合物及びイオン性化合物を表２に示す量（質量部）混合し、さらに固形分濃度が１４質量％となるように酢酸エチルを添加して粘着剤組成物の溶液を調製した。表２において、（メタ）アクリル系樹脂、架橋剤、シラン化合物及び帯電防止剤の配合量（質量部）は固形分換算量である。 <Examples 1 to 12, and Comparative Examples 1 and 2>
(1) Preparation of adhesive composition A crosslinker, a silane compound and an ionic compound were mixed in the ethyl acetate solution (resin concentration: 20%) of the (meth)acrylic resin obtained in the above Production Example in the amounts (parts by mass) shown in Table 2 relative to 100 parts by mass of the solid content of the solution, and ethyl acetate was further added so that the solid content concentration became 14% by mass to prepare a solution of the adhesive composition. In Table 2, the blending amounts (parts by mass) of the (meth)acrylic resin, the crosslinker, the silane compound and the antistatic agent are calculated as solid content.
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
　表２において略称で示される各配合成分の詳細は次のとおりである。
　［架橋剤］
　Ｂ：Ｄ－１０３（トリレンジイソシアネートのトリメチロールプロパンアダクト体の酢酸エチル溶液：固形分濃度７５質量％、三井化学(株)製）
　［シラン化合物］
　Ｃ－１：１，６－ビス（トリメトキシシリル）ヘキサン「ＫＢＭ－３０６６」、信越化学工業（株）製
　Ｃ－２：３－グリシドキシプロピルトリメトキシシラン「ＫＢＭ－４０３」、信越化学工業（株）製
　Ｃ－３：１，８－ビス（トリメトキシシリル）オクタン「ＫＢＭ－３０８６」、信越化学工業（株）製
　［イオン性化合物］
　Ｄ：メチルトリブチルアンモニウム=ビス(トリフルオロメチルスルホニル)イミド Details of each compounding component indicated by its abbreviation in Table 2 are as follows.
[Crosslinking agent]
B: D-103 (ethyl acetate solution of trimethylolpropane adduct of tolylene diisocyanate: solids concentration 75% by mass, manufactured by Mitsui Chemicals, Inc.)
[Silane Compound]
C-1: 1,6-bis(trimethoxysilyl)hexane "KBM-3066", manufactured by Shin-Etsu Chemical Co., Ltd. C-2: 3-glycidoxypropyltrimethoxysilane "KBM-403", manufactured by Shin-Etsu Chemical Co., Ltd. C-3: 1,8-bis(trimethoxysilyl)octane "KBM-3086", manufactured by Shin-Etsu Chemical Co., Ltd. [Ionic compounds]
D: Methyltributylammonium bis(trifluoromethylsulfonyl)imide
　（２）粘着剤層の作製
　上記（１）で調製した粘着剤組成物を、離型処理が施されたポリエチレンテレフタレートフィルムからなるセパレートフィルム〔三菱ケミカル(株)製の「ダイアホイルＭＲＶ３８（Ｖ０４）」〕の離型処理面に、アプリケーターを用いて乾燥後の厚みが２５μｍとなるように塗布し、１００℃で１分間乾燥して粘着剤層（粘着剤シート）を作製した。 (2) Preparation of Adhesive Layer The adhesive composition prepared in (1) above was applied to the release-treated surface of a separate film made of a release-treated polyethylene terephthalate film ["Diafoil MRV38 (V04)" manufactured by Mitsubishi Chemical Corporation] using an applicator so that the thickness after drying would be 25 μm, and the coating was dried at 100° C. for 1 minute to prepare an adhesive layer (adhesive sheet).
　（３）粘着剤層のゲル分率の測定
　（２）で作製した粘着剤層（粘着剤シート）を２３℃６０％で７日間保管した。保管後の粘着剤層（粘着剤シート）について、ゲル分率〔２３℃におけるゲル分率（Ｇ２３）〕を測定した。ゲル分率は、以下の〔ａ〕～〔ｄ〕に従って測定した。結果を表３に示す。
　〔ａ〕約８ｃｍ×約８ｃｍの面積の粘着剤層と、約１０ｃｍ×約１０ｃｍのＳＵＳ３０４からなる金属メッシュ（その質量をＷｍとする）とを貼合する。
　〔ｂ〕上記〔ａ〕で得られた貼合物を秤量して、その質量をＷｓとし、次に粘着剤層を包み込むように４回折りたたんでホッチキス（ステープラー）で留めた後に秤量して、その質量をＷｂとする。
　〔ｃ〕上記〔ｂ〕でホッチキス留めしたメッシュをガラス容器に入れ、酢酸エチル６０ｍＬを加えて浸漬した後、このガラス容器を室温で３日間保管する。
　〔ｄ〕ガラス容器からメッシュを取り出し、１２０℃で４時間乾燥した後に秤量して、その質量をＷａとし、下記式：
　ゲル分率（質量％）＝〔｛Ｗａ－（Ｗｂ－Ｗｓ）－Ｗｍ｝／（Ｗｓ－Ｗｍ）〕×１００に基づいてゲル分率を計算する。 (3) Measurement of gel fraction of pressure-sensitive adhesive layer The pressure-sensitive adhesive layer (pressure-sensitive adhesive sheet) prepared in (2) was stored at 23°C and 60% humidity for 7 days. After storage, the gel fraction [gel fraction at 23°C (G23)] of the pressure-sensitive adhesive layer (pressure-sensitive adhesive sheet) was measured. The gel fraction was measured according to the following [a] to [d]. The results are shown in Table 3.
[a] An adhesive layer having an area of about 8 cm x about 8 cm is bonded to a metal mesh made of SUS304 having an area of about 10 cm x about 10 cm (whose mass is represented as Wm).
[b] The laminate obtained in [a] above is weighed, and its mass is designated as Ws. Next, the laminate is folded four times so as to encase the adhesive layer and stapled, and then weighed, and its mass is designated as Wb.
[c] The mesh stapled in [b] above is placed in a glass container, 60 mL of ethyl acetate is added to soak it, and the glass container is then stored at room temperature for 3 days.
[d] The mesh is removed from the glass container, dried at 120° C. for 4 hours, and then weighed. The mass is designated as Wa, and the weight is calculated by the following formula:
The gel fraction is calculated based on the following formula: Gel fraction (mass %)=[(Wa-(Wb-Ws)-Wm)/(Ws-Wm)]×100.
　（４） 粘着剤層付光学フィルムの耐金属腐食性評価
　シクロオレフィン樹脂からなる厚み２３μｍのフィルム〔日本ゼオン(株)製の「ＺＦ－１４」〕にコロナ処理を施した後、上記（２）で作製した粘着剤層におけるセパレートフィルムとは反対側の面（粘着剤層面）をラミネーターにより貼り合わせて、粘着剤層付光学フィルムを得た。
　次いで、無アルカリガラスの表面に粘着剤を介してアルミ蒸着加工ポリエステルフィルムのポリエステルフィルム面を貼合し、金属層付ガラス基板を準備した。
　上記粘着剤層付光学フィルムを、５０ｍｍ×５０ｍｍの大きさの試験片に裁断し、金属層付ガラス基板の金属層側に粘着剤層を介して貼着した。得られた光学積層体を、温度８５℃ 、相対湿度８５％ のオーブン中で３６０時間保管した後、粘着剤層付光学フィルムが貼着された部分の金属層の状態をガラス基板の背面から光を当てて偏光板表面から拡大鏡（ルーペ）を通して観察し、孔食（直径０．１ｍｍ以上であり、光を透過することが可能な孔の発生）について、以下の基準で評価した。結果を表３に示す。
　Ａ：金属層表面の発生した孔食の数が１０個以下である。
　Ｂ：金属層表面に発生した孔食の数が１１個以上であり、一部白濁している。 (4) Evaluation of Metal Corrosion Resistance of Pressure-Sensitive Adhesive Layer-Attached Optical Film A 23 μm-thick film made of a cycloolefin resin ("ZF-14" manufactured by Zeon Corporation) was subjected to a corona treatment, and then the surface (pressure-sensitive adhesive layer surface) of the pressure-sensitive adhesive layer prepared in (2) above opposite to the separate film was bonded with a laminator to obtain a pressure-sensitive adhesive layer-attached optical film.
Next, the polyester film surface of the aluminum-deposited polyester film was attached to the surface of the alkali-free glass via an adhesive to prepare a glass substrate with a metal layer.
The pressure-sensitive adhesive layer-attached optical film was cut into a test piece measuring 50 mm x 50 mm, and attached to the metal layer side of a metal-layer-attached glass substrate via the pressure-sensitive adhesive layer. The obtained optical laminate was stored in an oven at a temperature of 85°C and a relative humidity of 85% for 360 hours, and then the state of the metal layer at the portion where the pressure-sensitive adhesive layer-attached optical film was attached was observed through a magnifying glass (loupe) from the polarizing plate surface by applying light from the back side of the glass substrate, and pitting corrosion (the occurrence of holes with a diameter of 0.1 mm or more that can transmit light) was evaluated according to the following criteria. The results are shown in Table 3.
A: The number of pits occurring on the metal layer surface is 10 or less.
B: The number of pitting corrosion that occurred on the metal layer surface was 11 or more, and some parts were cloudy.
　（５）偏光板の作製
　一軸延伸ポリビニルアルコールフィルムにヨウ素が吸着配向された厚み１２μｍの偏光子の両面にケン化処理を施したトリアセチルセルロース樹脂からなる厚み４０μｍの保護フィルムを、水系接着剤を介して貼合することにより偏光板を作製した。 (5) Preparation of Polarizing Plate A polarizing plate was prepared by laminating, via a water-based adhesive, 40 μm-thick protective films made of saponified triacetyl cellulose resin to both sides of a 12 μm-thick polarizer in which iodine was adsorbed and oriented on a uniaxially stretched polyvinyl alcohol film.
　（６）粘着剤層付偏光板の作製
　　上記（５）で作製した偏光板の一方の保護フィルムの外面に、上記（２）で作製した粘着剤層におけるセパレートフィルムとは反対側の面（粘着剤層面）をラミネーターにより貼り合わせた後、温度２３℃、相対湿度６０％の条件で７日間養生して、粘着剤層付偏光板を得た。 (6) Preparation of a polarizing plate with an adhesive layer The surface (adhesive layer surface) of the adhesive layer prepared in the above (2) opposite to the separate film was bonded to the outer surface of one of the protective films of the polarizing plate prepared in the above (5) using a laminator, and then cured for 7 days under conditions of a temperature of 23°C and a relative humidity of 60% to obtain a polarizing plate with an adhesive layer.
　（７）積層光学フィルムの耐熱耐久性評価
　上記（４）で作製した粘着剤層付偏光板からセパレートフィルムを剥がした後、その粘着剤層面を無アルカリガラス基板〔コーニング社製の「Ｅａｇｌｅ　ＸＧ」〕の両面にクロスニコルになるように貼着した。得られたガラス基板が貼り付けられた試験片（ガラス基板が貼り付けられた粘着剤層付偏光板）を、オートクレーブ中、温度５０℃、圧力５ｋｇ／ｃｍ2（４９０．３ｋＰａ）で、２０分間加圧し、評価用サンプルを作製した。このサンプルを用いて次の耐熱耐久性試験を実施した。
　〔耐熱耐久性試験〕
　温度１１０℃の乾燥条件下で７５０時間保持する耐熱性試験を行った。 (7) Evaluation of Heat Resistance and Durability of Laminated Optical Film After peeling off the separate film from the polarizing plate with adhesive layer prepared in (4) above, the adhesive layer surface was attached to both sides of an alkali-free glass substrate ["Eagle XG" manufactured by Corning] in a cross-Nicol configuration. The obtained test piece with the glass substrate attached (polarizing plate with adhesive layer attached to glass substrate) was pressurized in an autoclave at a temperature of 50°C and a pressure of 5 kg/cm 2 (490.3 kPa) for 20 minutes to prepare an evaluation sample. The following heat resistance and durability test was carried out using this sample.
[Heat resistance and durability test]
A heat resistance test was carried out by maintaining the sample at 110° C. for 750 hours under dry conditions.
　各試験後のサンプルについて、粘着剤層とガラス基板との界面での浮き及び剥がれの有無、並びに粘着剤層の発泡の有無を目視観察し、下記の評価基準に従って耐熱耐久性を評価した。結果を表３に示す。
　Ａ：浮き、剥れ、割れ、発泡等の外観変化が少し認められる。
　Ｂ：浮き、剥れ、割れ、発泡等の外観変化がやや大きく認められる。
　Ｃ：浮き、剥れ、割れ、発泡等の外観変化が大きく認められる。 After each test, the samples were visually observed for lifting or peeling at the interface between the adhesive layer and the glass substrate, and for foaming in the adhesive layer, and the heat resistance and durability were evaluated according to the following evaluation criteria. The results are shown in Table 3.
A: Slight changes in appearance such as lifting, peeling, cracking, and foaming are observed.
B: Somewhat significant changes in appearance such as lifting, peeling, cracking, and foaming are observed.
C: Significant changes in appearance such as lifting, peeling, cracking, and foaming are observed.
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
　１０，２０　粘着剤層付光学フィルム、１１，２４　直線偏光板、１２　粘着剤層、１３，２５　第１保護フィルム、１４，１６，２６，２８　接着剤層、１５，２７　偏光子、１７，２９　第２保護フィルム、２１　粘着剤層、２２　位相差フィルム、２３　貼合層、３０，４０　光学積層体、３１，４２　金属層、４１　樹脂層、５０　表示装置、５１　画像表示素子。 10, 20 Optical film with adhesive layer, 11, 24 Linear polarizing plate, 12 Adhesive layer, 13, 25 First protective film, 14, 16, 26, 28 Adhesive layer, 15, 27 Polarizer, 17, 29 Second protective film, 21 Adhesive layer, 22 Retardation film, 23 Lamination layer, 30, 40 Optical laminate, 31, 42 Metal layer, 41 Resin layer, 50 Display device, 51 Image display element.

Claims (16)

  1. 　（メタ）アクリル系樹脂（Ａ）と、架橋剤（Ｂ）と、シラン化合物（Ｃ）と、イオン性化合物（Ｄ）とを含有し、
    　前記（メタ）アクリル系樹脂（Ａ）は、ホモポリマーのガラス転移温度が３０℃以上であるアルキルメタクリレート（ａ）由来の構成単位と、ヒドロキシ基含有（メタ）アクリレート（ｂ）由来の構成単位と、カルボキシ基含有モノマー（ｃ）由来の構成単位とを含み、
    　前記シラン化合物（Ｃ）は、下記式（Ｉ）：
    Figure JPOXMLDOC01-appb-C000001
     ［式（Ｉ）中、
    　Ｌは、炭素数１～２０のアルカンジイル基または炭素数３～２０の２価の脂環式炭化水素基を表し、該アルカンジイル基および該脂環式炭化水素基を構成する－ＣＨ２－は、－Ｏ－または－Ｃ（＝Ｏ）－に置き換わっていてもよく、
    　Ａ１は、炭素数１～５のアルキル基を表し、
    　Ａ２、Ａ３、Ａ４、Ａ５およびＡ６は、互いに独立して、炭素数１～５のアルキル基または炭素数１～５のアルコキシ基を表す］
    で表される化合物を含む、粘着剤組成物。     The composition contains a (meth)acrylic resin (A), a crosslinking agent (B), a silane compound (C), and an ionic compound (D),
    The (meth)acrylic resin (A) contains a structural unit derived from an alkyl methacrylate (a) having a homopolymer glass transition temperature of 30° C. or higher, a structural unit derived from a hydroxyl group-containing (meth)acrylate (b), and a structural unit derived from a carboxyl group-containing monomer (c),
    The silane compound (C) is represented by the following formula (I):
    Figure JPOXMLDOC01-appb-C000001
     [In formula (I),
    L represents an alkanediyl group having 1 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and —CH 2 — constituting the alkanediyl group or the alicyclic hydrocarbon group may be replaced by —O— or —C(═O)—;
    A 1 represents an alkyl group having 1 to 5 carbon atoms;
    A 2 , A 3 , A 4 , A 5 and A 6 each independently represent an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.
    A pressure-sensitive adhesive composition comprising a compound represented by the formula:
  2. 　前記（メタ）アクリル系樹脂（Ａ）１００質量部に対して前記シラン化合物（Ｃ）を０．０１質量部以上２．０質量部以下含有する、請求項１に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1, which contains 0.01 parts by mass or more and 2.0 parts by mass or less of the silane compound (C) per 100 parts by mass of the (meth)acrylic resin (A).
  3. 　前記（メタ）アクリル系樹脂（Ａ）を構成する全構成単位１００質量部に対して、前記ホモポリマーのガラス転移温度が３０℃以上であるアルキルメタクリレート（ａ）由来の構成単位を１質量部以上１５質量部以下、前記ヒドロキシ基含有（メタ）アクリレート（ｂ）由来の構成単位を０．３質量部以上５．５質量部以下含有する、請求項１に記載の粘着剤組成物。 The adhesive composition according to claim 1, which contains 1 part by mass or more and 15 parts by mass or less of a structural unit derived from an alkyl methacrylate (a) having a homopolymer glass transition temperature of 30°C or higher, and 0.3 parts by mass or more and 5.5 parts by mass or less of a structural unit derived from a hydroxyl group-containing (meth)acrylate (b), relative to 100 parts by mass of all structural units constituting the (meth)acrylic resin (A).
  4. 　前記ヒドロキシ基含有（メタ）アクリレート（ｂ）由来の構成単位に対する前記カルボキシ基含有モノマー（ｃ）由来の構成単位の質量比（ｃ）／（ｂ）が０．０６以上１．０以下である、請求項１に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1, wherein the mass ratio (c)/(b) of the constituent units derived from the carboxyl group-containing monomer (c) to the constituent units derived from the hydroxyl group-containing (meth)acrylate (b) is 0.06 or more and 1.0 or less.
  5. 　前記ホモポリマーのガラス転移温度が３０℃以上であるアルキルメタクリレート（ａ）のホモポリマーのガラス転移温度が８０℃以上である、請求項１に記載の粘着剤組成物。 The adhesive composition according to claim 1, wherein the homopolymer of alkyl methacrylate (a) has a glass transition temperature of 30°C or higher and the homopolymer of alkyl methacrylate (a) has a glass transition temperature of 80°C or higher.
  6. 　前記ホモポリマーのガラス転移温度が３０℃以上であるアルキルメタクリレート（ａ）はメチルメタクリレート、ｔｅｒｔ－ブチルメタクリレート、イソボルニルメタクリレートおよびシクロヘキシルメタクリレートからなる群から選択される少なくとも１種を含む、請求項１～５のいずれか一項に記載の粘着剤組成物。 The adhesive composition according to any one of claims 1 to 5, wherein the alkyl methacrylate (a) having a homopolymer glass transition temperature of 30°C or higher includes at least one selected from the group consisting of methyl methacrylate, tert-butyl methacrylate, isobornyl methacrylate, and cyclohexyl methacrylate.
  7. 　前記（メタ）アクリル系樹脂（Ａ）の重量平均分子量が１００万以上３２０万以下である、請求項１～５のいずれか一項に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 5, wherein the weight-average molecular weight of the (meth)acrylic resin (A) is 1,000,000 or more and 3,200,000 or less.
  8. 　前記式（Ｉ）において、
    　Ｌは、炭素数２～１０のアルカンジイル基を表す、請求項１～５のいずれか一項に記載の粘着剤組成物。     In the formula (I),
    The pressure-sensitive adhesive composition according to any one of claims 1 to 5, wherein L represents an alkanediyl group having 2 to 10 carbon atoms.
  9. 　前記架橋剤（Ｂ）は芳香族系イソシアネート化合物を含み、前記（メタ）アクリル系樹脂（Ａ）１００質量部に対して前記架橋剤（Ｂ）を０．２質量部以上５．０質量部以下含有する、請求項１～５のいずれか一項に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 5, wherein the crosslinking agent (B) contains an aromatic isocyanate compound, and the crosslinking agent (B) is contained in an amount of 0.2 parts by mass or more and 5.0 parts by mass or less per 100 parts by mass of the (meth)acrylic resin (A).
  10. 　前記（メタ）アクリル系樹脂（Ａ）１００質量部に対して前記イオン性化合物（Ｄ）を０．１質量部以上１０．０質量部以下含有する、請求項１～５のいずれか一項に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 5, containing 0.1 parts by mass or more and 10.0 parts by mass or less of the ionic compound (D) per 100 parts by mass of the (meth)acrylic resin (A).
  11. 　前記イオン性化合物（Ｄ）は、下記式：
    Figure JPOXMLDOC01-appb-C000002
     で表される化合物からなる群から選択されるアニオンを含有する、請求項１～５のいずれか一項に記載の粘着剤組成物。     The ionic compound (D) is represented by the following formula:
    Figure JPOXMLDOC01-appb-C000002
     The pressure-sensitive adhesive composition according to any one of claims 1 to 5, comprising an anion selected from the group consisting of compounds represented by the following formula:
  12. 　請求項１～５のいずれか一項に記載の粘着剤組成物を含む粘着剤層。 An adhesive layer comprising the adhesive composition according to any one of claims 1 to 5.
  13. 　光学フィルムと、前記光学フィルム上に積層された請求項１２に記載の粘着剤層とを含む、粘着剤層付光学フィルム。 An optical film with a pressure-sensitive adhesive layer, comprising an optical film and the pressure-sensitive adhesive layer according to claim 12 laminated on the optical film.
  14. 　前記光学フィルムは偏光子を含む、請求項１３に記載の粘着剤層付光学フィルム。 The optical film with a pressure-sensitive adhesive layer according to claim 13, wherein the optical film includes a polarizer.
  15. 　請求項１３に記載の粘着剤層付光学フィルムを含む表示装置。 A display device comprising the pressure-sensitive adhesive layer-attached optical film according to claim 13.
  16. 　請求項１４に記載の粘着剤層付光学フィルムを含む表示装置。 A display device comprising the pressure-sensitive adhesive layer-attached optical film according to claim 14.
PCT/JP2024/000362 2023-01-13 2024-01-11 Adhesive composition, adhesive layer, optical film with adhesive layer, and display device WO2024150783A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2023-004049 2023-01-13
JP2023004049 2023-01-13

Publications (1)

Publication Number Publication Date
WO2024150783A1 true WO2024150783A1 (en) 2024-07-18

Family

ID=91897018

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2024/000362 WO2024150783A1 (en) 2023-01-13 2024-01-11 Adhesive composition, adhesive layer, optical film with adhesive layer, and display device

Country Status (2)

Country Link
JP (1) JP2024100729A (en)
WO (1) WO2024150783A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016101716A (en) * 2014-11-28 2016-06-02 住友化学株式会社 Optical laminate
JP2016193605A (en) * 2015-03-31 2016-11-17 住友化学株式会社 Optical laminate and liquid crystal display device
JP2016194071A (en) * 2015-03-31 2016-11-17 住友化学株式会社 Optical laminate having adhesive layer and liquid crystal display device
JP2018169612A (en) * 2017-03-29 2018-11-01 日東電工株式会社 Piece protection polarization film with adhesive layer, picture display unit and continuous manufacturing method thereof
JP2020003576A (en) * 2018-06-26 2020-01-09 日東電工株式会社 One-side protection polarization film having adhesive layer, picture display unit and continuous manufacturing method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016101716A (en) * 2014-11-28 2016-06-02 住友化学株式会社 Optical laminate
JP2016193605A (en) * 2015-03-31 2016-11-17 住友化学株式会社 Optical laminate and liquid crystal display device
JP2016194071A (en) * 2015-03-31 2016-11-17 住友化学株式会社 Optical laminate having adhesive layer and liquid crystal display device
JP2018169612A (en) * 2017-03-29 2018-11-01 日東電工株式会社 Piece protection polarization film with adhesive layer, picture display unit and continuous manufacturing method thereof
JP2020003576A (en) * 2018-06-26 2020-01-09 日東電工株式会社 One-side protection polarization film having adhesive layer, picture display unit and continuous manufacturing method thereof

Also Published As

Publication number Publication date
JP2024100729A (en) 2024-07-26

Similar Documents

Publication Publication Date Title
TWI553085B (en) Pressure sensitive adhesive sheet, optical film with pressure sensitive adhesive and optical laminate
TWI789372B (en) Adhesive composition
JP6745596B2 (en) Adhesive composition
JP6991860B2 (en) Adhesive composition
JP2007119667A5 (en)
TWI735489B (en) Adhesive composition
JP7184990B2 (en) adhesive composition
KR102666263B1 (en) Optical films and optical laminates with adhesive layer
KR20040045372A (en) Acrylic resin composition, adhesive comprising the composition, and optical laminate comprising the adhesive
WO2024150783A1 (en) Adhesive composition, adhesive layer, optical film with adhesive layer, and display device
WO2024150781A1 (en) Adhesive composition, adhesive layer, adhesive layer-attached optical film and display device
WO2024150784A1 (en) Adhesive composition, adhesive layer, optical film with adhesive layer, and display device
WO2024150782A1 (en) Adhesive composition, adhesive layer, optical film with adhesive layer, and display device
TWI728014B (en) Adhesive composition
TW202436570A (en) Adhesive composition, adhesive layer, optical film with an adhesive layer, and display device
TW202436549A (en) Adhesive composition, adhesive layer, optical film with an adhesive layer, and display device

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24741555

Country of ref document: EP

Kind code of ref document: A1