WO2018216645A1 - Adhesive composition - Google Patents

Adhesive composition Download PDF

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Publication number
WO2018216645A1
WO2018216645A1 PCT/JP2018/019451 JP2018019451W WO2018216645A1 WO 2018216645 A1 WO2018216645 A1 WO 2018216645A1 JP 2018019451 W JP2018019451 W JP 2018019451W WO 2018216645 A1 WO2018216645 A1 WO 2018216645A1
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WO
WIPO (PCT)
Prior art keywords
meth
sensitive adhesive
pressure
group
adhesive layer
Prior art date
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PCT/JP2018/019451
Other languages
French (fr)
Japanese (ja)
Inventor
悠司 淺津
亜依 小橋
明軒 薛
吉川　裕司
Original Assignee
住友化学株式会社
信越化学工業株式会社
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Publication date
Application filed by 住友化学株式会社, 信越化学工業株式会社 filed Critical 住友化学株式会社
Priority to KR1020197034440A priority Critical patent/KR102515307B1/en
Priority to CN201880033734.6A priority patent/CN110651017B/en
Publication of WO2018216645A1 publication Critical patent/WO2018216645A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • 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
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/14—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

Definitions

  • the present invention relates to a pressure-sensitive adhesive composition useful as an optical member utilized in a liquid crystal display device, a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition, an optical film with a pressure-sensitive adhesive layer containing the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer
  • the present invention relates to an optical laminate including an attached optical film and a siloxane compound for pressure-sensitive adhesive.
  • An optical film typified by a polarizing plate formed by laminating and laminating a transparent resin film on one or both surfaces of a polarizer is widely used as an optical member constituting an image display device such as a liquid crystal display device.
  • An optical film such as a polarizing plate is often used by being bonded to another member (for example, a liquid crystal cell in a liquid crystal display device) via an adhesive layer (see Patent Document 1). For this reason, the optical film with an adhesive layer by which the adhesive layer was previously provided in the one surface as an optical film is known.
  • liquid crystal display devices have been deployed in mobile device applications such as smartphones and tablet terminals and in-vehicle devices such as car navigation systems. In such an application, there is a possibility that it may be exposed to a harsh environment as compared with a conventional indoor TV application.
  • the pressure-sensitive adhesive layer incorporated in a liquid crystal display device or the like may be placed in a high temperature or high temperature and high humidity environment, or may be placed in an environment where high and low temperatures are repeated.
  • the optical film is required to be able to suppress problems such as floating and peeling at the interface between the pressure-sensitive adhesive layer and the optical member to which the optical film is bonded, foaming of the pressure-sensitive adhesive layer, and the like even under these circumstances. It is also required that the optical characteristics do not deteriorate.
  • an object of the present invention is to provide a pressure-sensitive adhesive composition capable of forming a pressure-sensitive adhesive layer exhibiting good durability under severe durability conditions even when applied to a transparent electrode layer such as ITO, and the pressure-sensitive adhesive composition
  • An object is to provide a pressure-sensitive adhesive layer comprising a product, an optical film with a pressure-sensitive adhesive layer including the pressure-sensitive adhesive layer, an optical laminate including the optical film with the pressure-sensitive adhesive layer, and a siloxane compound for pressure-sensitive adhesive.
  • the siloxane compound (A) is represented by the following formula (a1) (In the formula, B represents an alkanediyl group having 1 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and constitutes the alkanediyl group and the alicyclic hydrocarbon group.
  • a pressure-sensitive adhesive composition which is a hydrolysis-condensation product (a) of a hydrolysis-condensable silane compound represented by: [2]
  • the content of the alkoxy group contained in the siloxane compound (A) is 60 to 95 mol% with respect to 100 mol% of the total amount of alkoxy groups contained in the hydrolytic condensable silane compound (a1).
  • the pressure-sensitive adhesive composition according to 1. [3] The pressure-sensitive adhesive composition according to [1] or [2], wherein the siloxane compound (A) has a weight average molecular weight of 800 to 4000 in terms of polystyrene. [4] The pressure-sensitive adhesive composition according to any one of [1] to [3], further comprising a (meth) acrylic resin (B) and a crosslinking agent (C). [5] The pressure-sensitive adhesive composition according to [4], wherein the ratio of the siloxane compound (A) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin (B).
  • the (meth) acrylic resin (B) comprises a structural unit derived from an alkyl acrylate (b1) having a homopolymer glass transition temperature of less than 0 ° C., and an alkyl acrylate having a homopolymer glass transition temperature of 0 ° C. or more
  • the proportion of the structural unit derived from the carboxyl group-containing (meth) acrylate contained in the (meth) acrylic resin (B) is 100 parts by mass of all the structural units constituting the (meth) acrylic resin (B).
  • the ratio of the crosslinking agent (C) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin (B), according to any one of [4] to [9] Adhesive composition.
  • a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition according to any one of [1] to [10].
  • After the pressure-sensitive adhesive layer on the surface of the optical film with the pressure-sensitive adhesive layer not bonded to the optical film is bonded to a glass substrate and stored for 24 hours under conditions of a temperature of 23 ° C. and a relative humidity of 50%.
  • the adhesive film with an adhesive layer according to [12] which has an adhesive strength of 0.5 to 10 N / 25 mm at a peeling speed of 300 mm / min.
  • —CH 2 — may be substituted with —O— or —CO—
  • R 1 and R 2 each independently represents an alkyl group having 1 to 5 carbon atoms
  • R 3 , R 4 , R 5 and R 6 each independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms
  • the siloxane compound (A) for adhesives which is a hydrolysis-condensation product (a) of the hydrolytic condensable silane compound represented by these.
  • the pressure-sensitive adhesive composition of the present invention can form a pressure-sensitive adhesive layer exhibiting good durability under severe durability conditions even when applied to a transparent electrode layer such as ITO.
  • Pressure-sensitive adhesive composition contains a siloxane compound (A).
  • Siloxane compound (A) The siloxane compound (A) is represented by the following formula (a1) (In the formula, B represents an alkanediyl group having 1 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and constitutes the alkanediyl group and the alicyclic hydrocarbon group. —CH 2 — may be substituted with —O— or —CO—. R 1 and R 2 each independently represents an alkyl group having 1 to 5 carbon atoms.
  • formula (a1) In the formula, B represents an alkanediyl group having 1 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and constitutes the alkanediyl group and the alicyclic hydrocarbon group. —CH 2 — may be substituted with —O— or —CO—.
  • R 1 and R 2 each independently represents an alkyl group having 1 to 5 carbon atoms.
  • R 3 , R 4 , R 5 and R 6 each independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms) It is a hydrolysis-condensation product (a) of the hydrolytic condensable silane compound represented by these.
  • B represents an alkanediyl group having 1 to 20 carbon atoms such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group; a cyclobutylene group (for example, 1,2-cyclobutylene group), cyclopentylene group (for example, 1,2-cyclopentylene group), cyclohexylene group (for example, 1,2-cyclohexylene group), cyclooctylene group (for example, 1,2- A divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms such as a cyclooctylene group; or —CH 2 — constituting these alkanediyl groups and the alicyclic hydrocarbon group is —O— or A substituted group is represented by —CO—.
  • Preferred B is an alkanediyl group having 1 to 10 carbon atoms.
  • R 3 , R 4 , R 5 and R 6 each independently represents 1 carbon atom such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a s-butyl group, a t-butyl group, or a pentyl group.
  • an alkyl group having 1 to 5 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, an i-propoxy group, a butoxy group, an s-butoxy group, or a t-butoxy group.
  • R 3 , R 4 , R 5 and R 6 are preferably each independently an alkoxy group having 1 to 5 carbon atoms.
  • Examples of the alkyl group having 1 to 5 carbon atoms represented by R 1 and R 2 are the same as the alkyl group having 1 to 5 carbon atoms represented by R 3 , R 4 , R 5 and R 6 .
  • silane compound (a1) examples include bis (trimethoxysilyl) methane, 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, and 1,3-bis.
  • 1,2-bis (trimethoxysilyl) ethane 1,3-bis (trimethoxysilyl) propane, 1,4-bis (trimethoxysilyl) butane, 1,5-bis (trimethoxysilyl) Bis (triC 1-3 alkoxysilyl) C 1-10 alkanes such as pentane, 1,6-bis (trimethoxysilyl) hexane, 1,8-bis (trimethoxysilyl) octane are preferred, especially 1,6 -Bis (trimethoxysilyl) hexane and 1,8-bis (trimethoxysilyl) octane are preferred.
  • the hydrolytic condensate (a) of the hydrolytic condensable silane compound represented by the formula (a1) is the hydrolytic condensable silane compound.
  • the alkoxy group which is the hydrolyzable group in (a1) means a condensate obtained by hydrolysis and condensation, such as a dimer or oligomer.
  • the hydrolysis condensate (a) is a hydrolysis condensate obtained by partially hydrolyzing and condensing the alkoxy group of the hydrolyzable silane compound (a1) (sometimes referred to as a partial hydrolysis condensate).
  • it may be a condensate obtained by hydrolyzing and condensing all of the alkoxy groups.
  • the alkoxy group of the hydrolyzable silane compound (a1) is hydrolyzed to a hydroxyl group, and then the generated hydroxyl group is condensed, but a part of the hydroxyl group is not condensed, but the hydrolysis condensate (a) It may remain inside.
  • the hydrolysis-condensation product (a) has a structural unit derived from the hydrolytic condensable silane compound (a1) formed by Si—O—Si bond by partial or total, preferably partial hydrolysis and condensation of an alkoxy group. Having a repeated structure.
  • the hydrolysis condensate (a) may be linear or branched.
  • the pressure-sensitive adhesive composition of the present invention contains the siloxane compound (A), for example, even when a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition is applied (bonded or laminated) to the electrode layer, the durability of the pressure-sensitive adhesive layer The interface can be effectively prevented from peeling (or floating) and foaming even in a high temperature environment. Furthermore, the pressure-sensitive adhesive composition also has good reworkability (peelability). For this reason, the pressure-sensitive adhesive composition of the present invention can achieve both good durability and reworkability.
  • the term “durability” refers to the interface between the pressure-sensitive adhesive layer and the optical member adjacent thereto, for example, in a high temperature environment, a high temperature and high humidity environment, or an environment where high and low temperatures are repeated. It refers to a characteristic that can prevent floating and peeling (sometimes referred to as peeling resistance) and a characteristic that can suppress problems such as foaming of the pressure-sensitive adhesive layer (sometimes referred to as foaming resistance).
  • the cohesive failure resistance refers to a property capable of suppressing cohesive failure (or tearing) of the pressure-sensitive adhesive layer.
  • the hydrolysis condensate (a) is preferably a partial hydrolysis condensate of the hydrolytic condensable silane compound (a1).
  • the content of the alkoxy group contained in the siloxane compound (A) is preferably 60 mol% or more, more preferably 65 mol with respect to 100 mol% of the total amount of alkoxy groups contained in the hydrolytic condensable silane compound (a1).
  • it may be 60 to 95 mol%, preferably 65 to 90 mol%, more preferably 70 to 88 mol%.
  • the content of the alkoxy group contained in the siloxane compound (A) is not less than the above lower limit, the durability of the pressure-sensitive adhesive layer can be further improved, and when it is not more than the above upper limit, the reworkability of the pressure-sensitive adhesive layer can be further improved. it can.
  • the content of the alkoxy group contained in the siloxane compound (A) can be adjusted by the amount of hydrolyzed water. 1 mol of alkoxy group contained in the hydrolyzable condensable silane compound (a1) is hydrolyzed with 0.5 mol of hydrolyzed water. If the content of the alkoxy group contained in the siloxane compound (A) is 60 mol% with respect to the total amount of 100 mol% of the alkoxy groups contained in the hydrolytic condensable silane compound (a1), the hydrolyzable condensable silane compound This means that 40% of the alkoxy group of (a1) has been hydrolyzed, and the hydrolysis rate is 40%.
  • the weight average molecular weight of the siloxane compound (A) is preferably 600 or more, more preferably 700 or more, further preferably 800 or more, preferably 4000 or less, more preferably 4000 or less, in terms of polystyrene by gel permeation chromatography GPC. It is 3000 or less, more preferably 2000 or less, and any combination of these lower limit values and upper limit values may be used, for example, 600 to 4000, preferably 700 to 3000, and more preferably 800 to 2000. When the weight average molecular weight is in the above range, the durability and reworkability of the pressure-sensitive adhesive layer can be further improved.
  • the siloxane compound (A) may be a hydrolytic condensate (a) obtained by hydrolyzing and condensing the hydrolytic condensable silane compound (a1) alone or in combination.
  • the siloxane compound (A) may be referred to as a hydrolytic condensable silane compound (a1) and a hydrolytic condensable silane compound other than the hydrolytic condensable silane compound (a1) [hydrolytic condensable silane compound (a2). It may be a hydrolysis condensate (a).
  • the siloxane compound (A) is preferably 70 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol%, of the hydrolyzed silane compound (a1). As mentioned above, it is particularly preferable to contain 95 mol% or more.
  • the siloxane compound (A) may contain one or two or more non-condensed hydrolysis-condensable silane compounds (a1).
  • the silane compound (A) may contain an uncondensed hydrolyzable condensable silane compound (a2).
  • the non-condensed hydrolytic condensable silane compound (a1) or (a2) alkoxy group may be partially or wholly hydrolyzed (converted to a hydroxyl group) as long as it is not condensed.
  • hydrolytic condensable silane compound (a2) other than the hydrolytic condensable silane compound (a1) examples include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, and dimethyl.
  • the ratio of the siloxane compound (A) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more with respect to 100% by mass of the total amount of the pressure-sensitive adhesive composition. Particularly preferably 0.2% by mass or more, preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, particularly preferably 1% by mass or less, especially 0.5% by mass. Or any combination of these lower and upper limits, for example 0.01 to 10% by weight, preferably 0.01 to 5% by weight, more preferably 0.05 to 3% by weight, More preferably, it may be 0.1 to 1% by mass, and particularly preferably 0.2 to 0.5% by mass. When the proportion of the siloxane compound (A) is in the above range, the durability and reworkability of the pressure-sensitive adhesive layer can be further improved.
  • the content of the siloxane compound (A) is preferably 0.00 with respect to 100 parts by mass of the (meth) acrylic resin (B).
  • it is more preferably 3 parts by mass or less, particularly preferably 1 part by mass or less, especially 0.5 part by mass or less, and any combination of these lower limit values and upper limit values may be used.
  • Parts by weight preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, still more preferably 0.1 to 1 part by weight, particularly preferably 0.2 to 0.5 parts by weight. Also good.
  • the proportion of the siloxane compound (A) is in the above range, the durability and reworkability of the pressure-sensitive adhesive layer can be further improved.
  • the production method of the siloxane compound (A) is a conventional method, for example, in the presence of a solvent, a catalyst (for example, an acidic catalyst, a basic catalyst, etc.) is added if necessary, and the hydrolytic condensable silane compound (a1). And the method of mixing and stirring a hydrolytic condensable silane compound (a2) as needed.
  • a catalyst for example, an acidic catalyst, a basic catalyst, etc.
  • the (meth) acrylic resin (B) is preferably a structural unit derived from a (meth) acrylic monomer, preferably 50% with respect to 100% by mass of all the structural units constituting the (meth) acrylic resin (B). It is a polymer or copolymer containing at least mass%, more preferably at least 70 mass%, and even more preferably at least 90 mass%.
  • “(meth) acryl” means acryl or methacryl
  • “(meth) acrylate”, “(meth) acryloyl”, and the like are acrylate or methacrylate, acryloyl or methacryloyl, respectively. means.
  • the (meth) acrylic resin (B) is, for example, a structural unit derived from a polar functional group-containing (meth) acrylate, a structural unit derived from a (meth) acrylamide monomer, a structural unit derived from a styrene monomer, or vinyl.
  • These structural units can be used individually or in combination of 2 or more types.
  • Examples of the polar functional group-containing (meth) acrylate include a hydroxy group-containing (meth) acrylate, a heterocyclic group-containing (meth) acrylate such as an epoxy group, a substituted or unsubstituted amino group-containing (meth) acrylate, and a carboxyl group-containing (meta ) Acrylate and the like.
  • the hydroxy group-containing (meth) acrylate is preferably a hydroxy group-containing (meth) acrylate represented by the following formula (b1) or (b2).
  • n represents an integer of 1 to 4, A 1 represents a hydrogen atom or an alkyl group, X 1 represents an optionally substituted methylene group, and when n is 2 or more, The substituents may be the same or different)
  • m represents an integer of 5 or more
  • a 2 represents a hydrogen atom or an alkyl group
  • X 2 represents a methylene group which may have a substituent, and the substituents are the same or different. Also good
  • X 1 and X 2 represent a methylene group which may have a substituent.
  • substituents include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (eg, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an s-butyl group, a t-butyl group).
  • C 1-10 alkyl group such as butyl group, pentyl group, hexyl group, preferably C 1-6 alkyl group, more preferably C 1-3 alkyl group), cycloalkyl group (eg cyclopentyl group, cyclohexyl group, etc.) ), Aryl group [eg phenyl group, alkylphenyl group (tolyl group, xylyl group etc.)], aralkyl group (eg benzyl group etc.), alkoxy group (eg C 1-4 alkoxy group such as methoxy group, ethoxy group etc.) , Polyoxyalkylene groups (eg, dioxyethylene groups), cycloalkoxy groups (eg, cyclohexyl) C 5-10 cycloalkyloxy group such as ruoxy group), aryloxy group (eg phenoxy group etc.), aralkyloxy group (eg benzyloxy group etc.), alkylthi
  • halogen atom an alkyl group, an alkoxy group, an aryloxy group, and the like are preferable, and an alkyl group (for example, a methyl group, an ethyl group, and the like) is particularly preferable.
  • the alkyl group represented by A 1 and A 2 is a C 1-10 alkyl such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, s-butyl group, t-butyl group, pentyl group, and hexyl group. Group etc. are mentioned, Preferably a methyl group etc. may be sufficient.
  • n represents an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 2.
  • m represents an integer of 5 or more, and examples include an integer of 5 to 20, preferably an integer of 5 to 15, more preferably an integer of 5 to 9, and still more preferably. Is an integer from 5 to 7.
  • m is preferably an odd number.
  • hydroxy group-containing (meth) acrylate (b1) examples include 1-hydroxymethyl (meth) acrylate, 1-hydroxyethyl (meth) acrylate, 1-hydroxyheptyl (meth) acrylate, and (meth) acrylic.
  • 1-hydroxybutyl acid, 1-hydroxyC 1-8 alkyl (meth) acrylate such as 1-hydroxypentyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate (Meth) acrylic acid 2-hydroxybutyl, (meth) acrylic acid 2-hydroxypentyl, (meth) acrylic acid 2-hydroxyhexyl and the like (meth) acrylic acid 2-hydroxy C 2-9 alkyl; (meth) acrylic 3-hydroxypropyl acid, 3-hydroxybutyl (meth) acrylate, ( Data) acrylate, 3-hydroxypentyl, (meth) acrylate, 3-hydroxyhexyl, (meth) (meth) acrylic acid such as acrylic acid 3-hydroxy-heptyl 3-hydroxy C 3-10 alkyl; (meth) acrylic acid 4 -(Meth) acrylic acid such as hydroxybutyl, 4-hydroxypentyl (meth) acrylate, 4-hydroxyhexyl (meth) acrylate,
  • hydroxy group-containing (meth) acrylates in which n is 2 such as 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, etc.
  • Hydroxy group-containing (meth) acrylates where n is 3 such as 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 3-hydroxypentyl (meth) acrylate, and the like are preferable.
  • the hydroxy group-containing (meth) acrylate in which n is 2 is preferable, and among these, 2-hydroxyethyl (meth) acrylate is preferable.
  • hydroxy group-containing (meth) acrylate (b2) include 5-hydroxypentyl (meth) acrylate, 5-hydroxyhexyl (meth) acrylate, 5-hydroxyheptyl (meth) acrylate, and (meth) acrylic.
  • 5-hydroxyoctyl acid 5-hydroxy C 5-12 alkyl (meth) acrylate such as 5-hydroxynonyl (meth) acrylate; 6-hydroxyhexyl (meth) acrylate, 6-hydroxyheptyl (meth) acrylate (Meth) acrylic acid 6-hydroxyoctyl, (meth) acrylic acid 6-hydroxynonyl, (meth) acrylic acid 6-hydroxydecyl (meth) acrylic acid 6-hydroxy C 6-13 alkyl; (meth) acrylic Acid 7-hydroxyheptyl, (meth) acrylic acid 7-hydroxyo Chill, (meth) acrylic acid 7-hydroxy-nonyl, (meth) acrylic acid 7-hydroxy decyl (meth) (meth) acrylic acid such as acrylic acid 7-hydroxy undecyl 7-hydroxy C 7-14 alkyl; (meth ) 8-hydroxyoctyl acrylate, 8-hydroxynonyl (meth) acrylate, 8-hydroxydecyl (meth) acrylate, 8
  • the (meth) acrylic resin (B) comprises a structural unit derived from a hydroxy group-containing (meth) acrylate represented by the formula (b1), and a hydroxy group-containing formula (b2) ( And a structural unit derived from (meth) acrylate.
  • the (meth) acrylic resin (B) since the (meth) acrylic resin (B) has hydroxyalkyl groups with different carbon chain lengths (n and m) in the side chain, peeling (or floating) of the interface in a high temperature environment and foaming are more effective. And the durability of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition can be further improved.
  • the proportion of the structural unit derived from the hydroxy group-containing (meth) acrylate represented by the formula (b1) with respect to 100 parts by mass of all the structural units constituting the (meth) acrylic resin is preferably 1.5 to 5 masses. Parts, more preferably 2 to 4.5 parts by mass, and the proportion of the structural unit derived from the hydroxy group-containing (meth) acrylate represented by the formula (b2) is preferably 0.1 to 2 parts by mass, more preferably Is 0.25 to 1 part by mass.
  • heterocyclic group-containing (meth) acrylate examples include acryloylmorpholine, vinylcaprolactam, N-vinyl-2-pyrrolidone, vinylpyridine, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, and 3,4-epoxy.
  • examples include cyclohexylmethyl (meth) acrylate, glycidyl (meth) acrylate, and 2,5-dihydrofuran.
  • substituted or unsubstituted amino group-containing (meth) acrylate examples include aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and the like.
  • carboxyl group-containing (meth) acrylate examples include (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, carboxyalkyl (meth) acrylate (for example, carboxyethyl (meth) acrylate, carboxypentyl (meth) ) Acrylate) and the like. These carboxyl group-containing (meth) acrylates can be used alone or in combination of two or more.
  • it is preferable that the structural unit derived from the monomer which has an amino group is not included substantially from a viewpoint of preventing the fall of the peelability of the separate film which can be laminated
  • the proportion of the structural unit derived from the carboxyl group-containing (meth) acrylate is 1.0 part by mass or less with respect to 100 parts by mass of all the structural units constituting the (meth) acrylic resin.
  • the upper limit of the proportion of structural units derived from carboxyl group-containing (meth) acrylate is preferably 0.5 parts by mass, more preferably 0.3 parts by mass, still more preferably 0.2 parts by mass, and particularly preferably 0.15. Part by mass.
  • the lower limit of the proportion of the structural unit derived from the carboxyl group-containing (meth) acrylate is preferably 0 parts by mass, more preferably 0.001 parts by mass, still more preferably 0.005 parts by mass, particularly preferably 0.01 parts by mass. Especially 0.05 parts by mass.
  • the proportion of the structural unit derived from the carboxyl group-containing (meth) acrylate may be any combination of these upper limit value and lower limit value, for example, 0 to 1 part by mass, preferably 0 to 0.8 part by mass, more preferably Is 0.001 to 0.5 parts by mass, more preferably 0.005 to 0.3 parts by mass, particularly preferably 0.01 to 0.2 parts by mass, especially 0.05 to 0.15 parts by mass. Good.
  • the proportion of the structural unit derived from the carboxyl group-containing (meth) acrylate is at most the upper limit value, the corrosivity of the transparent electrode layer such as ITO can be suppressed, and when it is at least the lower limit value, the durability can be improved.
  • Examples of (meth) acrylamide monomers include N-methylolacrylamide, N- (2-hydroxyethyl) acrylamide, N- (3-hydroxypropyl) acrylamide, N- (4-hydroxybutyl) acrylamide, N- (5-hydroxypentyl) acrylamide, N- (6-hydroxyhexyl) acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, N- (3-dimethylaminopropyl) acrylamide, N- (1,1-dimethyl-3-oxobutyl) acrylamide, N- [2- (2-oxo-1-imidazolidinyl) ethyl] acrylamide, 2-acryloylamino-2-methyl-1-propanesulfonic acid, N- (methoxy Methyl) Luamide, N- (ethoxymethyl) acrylamide, N- (propoxymethyl) acrylamide, N- (1-methylethoxymethyl
  • the durability of the pressure-sensitive adhesive layer can be further improved.
  • N- (methoxymethyl) acrylamide, N- (ethoxymethyl) acrylamide, N- (propoxymethyl) acrylamide, N- (butoxymethyl) acrylamide, N- (2-methylpropoxymethyl) acrylamide, etc. preferable.
  • the proportion of the structural unit derived from the (meth) acrylamide monomer is preferably 5 parts by mass or less with respect to 100 parts by mass of all the structural units constituting the (meth) acrylic resin.
  • the upper limit of the proportion of the structural unit derived from the (meth) acrylamide monomer is preferably 3 parts by mass, more preferably 2 parts by mass, and even more preferably 1 part by mass.
  • the lower limit of the proportion of the structural unit derived from the (meth) acrylamide monomer is preferably 0 parts by mass, more preferably 0.001 parts by mass, still more preferably 0.01 parts by mass, particularly preferably 0.1 parts by mass. Part.
  • the proportion of the structural unit derived from the (meth) acrylamide monomer may be any combination of these upper limit value and lower limit value, for example, 0 to 5 parts by mass, preferably 0.001 to 3 parts by mass.
  • the amount may be preferably 0.01 to 2 parts by mass, more preferably 0.1 to 1 part by mass.
  • styrenic monomer examples include styrene; alkyl styrene such as methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, octyl styrene; fluoro Halogenated styrene such as styrene, chlorostyrene, bromostyrene, dibromostyrene, iodostyrene; nitrostyrene; acetylstyrene; methoxystyrene; divinylbenzene, and the like.
  • alkyl styrene such as methyl sty
  • vinyl monomers include 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 chloride And vinylidene halides such as vinyl pyridine, vinyl pyrrolidone, vinyl carbazole, and the like; conjugated diene monomers such as butadiene, isoprene, and chloroprene; and unsaturated nitriles such as acrylonitrile and methacrylonitrile.
  • 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 chloride And vinylidene halides such as vinyl pyridine, vinyl pyrrolidone, vinyl carbazole, and the like
  • conjugated diene monomers such
  • Examples of the monomer having a plurality of (meth) acryloyl groups in the molecule include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol.
  • (meth) acryloyl in the molecule such as di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate
  • a monomer having a group a monomer having three (meth) acryloyl groups in a molecule such as trimethylolpropane tri (meth) acrylate;
  • alkyl acrylate examples include an alkyl acrylate (b3) having a glass transition temperature (Tg) of the homopolymer of less than 0 ° C., and an alkyl acrylate (b4) having a Tg of the homopolymer of 0 ° C. or more.
  • Examples of the alkyl acrylate (b3) having a glass transition temperature (Tg) of the homopolymer of less than 0 ° C. include ethyl acrylate, n- and i-propyl acrylate, n- and i-butyl acrylate, n-pentyl acrylate, n- And alkyl such as 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 Examples thereof include linear or branched alkyl acrylates having a group having about 2 to 12 carbon atoms.
  • the alkyl acrylate (b3) may be an alkyl acrylate (cycloalkyl acrylate) having an alicyclic structure, but has a carbon number of 2 to 10 from the viewpoint of followability (or flexibility and adhesiveness) to the optical film.
  • Alkyl acrylates preferably alkyl acrylates having 3 to 8 carbon atoms, more preferably alkyl acrylates having 4 to 6 carbon atoms, particularly n-butyl alkyl acrylate.
  • n-butyl alkyl acrylate is used, the followability can be enhanced, and for example, it is advantageous in peeling resistance.
  • These alkyl acrylates (b3) can be used alone or in combination of two or more.
  • alkyl acrylate (b4) whose Tg of the homopolymer is 0 ° C. or higher include methyl acrylate, cycloalkyl acrylate (for example, cyclohexyl acrylate, isobornyl acrylate), stearyl acrylate, t-butyl acrylate, etc., particularly methyl acrylate Is particularly preferred.
  • methyl acrylate When methyl acrylate is used, the strength can be increased, which is advantageous for cohesive failure, for example.
  • These alkyl acrylates (b4) can be used alone or in combination of two or more.
  • Tg of the alkyl acrylate homopolymer reference values such as POLYMER HANDBOOK (Wiley-Interscience) can be referred to.
  • the (meth) acrylic resin (A) comprises a structural unit derived from an alkyl acrylate (b3) having a glass transition temperature of less than 0 ° C. and a homopolymer from the viewpoint of improving the durability of the pressure-sensitive adhesive layer. And a structural unit derived from alkyl acrylate (b4) having a glass transition temperature of 0 ° C. or higher.
  • an alkyl acrylate having a homopolymer Tg of less than 0 ° C and an alkyl acrylate having a homopolymer Tg of 0 ° C or higher are used in combination, both cohesive fracture resistance and follow-up properties (foaming resistance and peeling resistance) can be achieved.
  • the durability against dimensional changes of a film for example, a polarizing plate) can be improved.
  • the proportion of the structural units derived from the alkyl acrylate in the (meth) acrylic resin (B) is 100 masses of all structural units constituting the (meth) acrylic resin (B) from the viewpoints of durability and reworkability of the pressure-sensitive adhesive layer.
  • Part is preferably 40 parts by weight or more, more preferably 50 parts by weight or more, still more preferably 60 parts by weight or more, particularly preferably 70 parts by weight or more, especially 80 parts by weight or more, preferably 98 parts by weight or less.
  • the followability improves as the proportion of the structural unit derived from the alkyl acrylate (b3) having a glass transition temperature of less than 0 ° C. increases.
  • the proportion of the structural unit derived from the alkyl acrylate (b4) having a glass transition temperature of 0 ° C. or higher is increased, the cohesive fracture resistance is improved.
  • Examples of the substituent-containing alkyl acrylate include alkyl acrylate in which a substituent is introduced into the alkyl group in the alkyl acrylate (a hydrogen atom of the alkyl group is substituted with a substituent).
  • Examples of the substituent include an aryl group (such as a phenyl group), an aryloxy group (phenoxy group), an alkoxy group (such as a methoxy group and an ethoxy group), and the like.
  • substituent-containing alkyl acrylate examples include alkoxyalkyl acrylate (such as 2-methoxyethyl acrylate and ethoxymethyl acrylate), arylalkyl acrylate (such as benzyl acrylate), aryloxyalkyl acrylate (such as phenoxyethyl acrylate), and aryloxypolyacrylate.
  • alkoxyalkyl acrylate such as 2-methoxyethyl acrylate and ethoxymethyl acrylate
  • arylalkyl acrylate such as benzyl acrylate
  • aryloxyalkyl acrylate such as phenoxyethyl acrylate
  • aryloxypolyacrylate examples include alkylene glycol monoacrylate and polyalkylene glycol monoacrylate.
  • an alkyl acrylate containing an aromatic ring such as an aryl group, a benzyl group, or an aryloxy group
  • white spots of the polarizing plate during the durability test can be improved.
  • the antistatic property at the time of adding an antistatic agent to an adhesive layer can be improved by including an alkoxy group, an aryloxy group, etc.
  • the alkylene group of the aryloxy polyalkylene glycol monoacrylate and the polyalkylene glycol monoacrylate may be, for example, a C 1-6 alkylene group (preferably an ethylene group) such as a methylene group, an ethylene group or a propylene group.
  • the repeating unit of the alkylene group is, for example, 1 to 7, preferably 1 to 5, particularly 1 to 2 from the viewpoint of the balance between durability and antistatic property of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition.
  • Specific examples include phenoxy di to hepta C 1-3 alkylene glycol acrylate such as phenoxy diethylene glycol acrylate, di to hepta C 1-3 alkylene mono acrylate such as diethylene glycol monoacrylate, and the like.
  • the substituent-containing alkyl acrylate used in the present invention is particularly preferably phenoxyethyl acrylate or phenoxydiethylene glycol acrylate from the viewpoint of the balance of durability, white spot resistance, and antistatic properties.
  • the proportion of the structural unit derived from the substituent-containing alkyl acrylate is, for example, 0 to 30 parts by weight, preferably 1 to 25 parts by weight with respect to 100 parts by weight of all the structural units constituting the (meth) acrylic resin (B).
  • the amount is more preferably 3 to 20 parts by mass, still more preferably 5 to 15 parts by mass.
  • the weight average molecular weight (Mw) in terms of standard polystyrene by gel permeation chromatography GPC is preferably 1 million or more in order to further improve the durability of the pressure-sensitive adhesive layer.
  • the lower limit value of Mw is more preferably 1.1 million, still more preferably 1.2 million, and particularly 1.3 million.
  • the upper limit value of Mw is not particularly limited, but is preferably 2.5 million, more preferably 220, from the viewpoint of coatability when the pressure-sensitive adhesive composition is processed into a sheet (for example, coated on a substrate). Million, more preferably 2 million.
  • Mw may be an arbitrary combination of these upper limit value and lower limit value, and may be, for example, 1 to 2.5 million, more preferably 1.1 million to 2.2 million, and still more preferably 1.3 to 2 million.
  • the molecular weight distribution represented by the ratio of the weight average molecular weight Mw to the number average molecular weight Mn (Mw / Mn) is usually 2 to 10, preferably 3 to 8, and more preferably 4 to 6.
  • the (meth) acrylic resin (B) preferably has a single peak in the range of 1.0 ⁇ 10 3 to 2.5 ⁇ 10 6 of Mw on the GPC emission curve.
  • Use of the (meth) acrylic resin (B) having a peak number of 1 is advantageous for improving the durability of the pressure-sensitive adhesive layer.
  • “Having a single peak” in the above range of the obtained discharge curve means having only one maximum value in the range of Mw 1.0 ⁇ 10 3 to 2.5 ⁇ 10 6 .
  • a peak having an S / N ratio of 30 or more in the GPC emission curve is defined.
  • the number of peaks in the GPC discharge curve and the Mw and Mn of the (meth) acrylic resin (B) can be determined according to the GPC measurement conditions described in the Examples section.
  • the viscosity at 25 ° C. is preferably 20 Pa ⁇ s or less, preferably 0.1 to 7 Pa ⁇ s. It is more preferable that When the viscosity is within this range, it is advantageous from the viewpoint of coatability when the pressure-sensitive adhesive composition is applied to a substrate.
  • the viscosity can be measured with a Brookfield viscometer.
  • the glass transition temperature (Tg) of the (meth) acrylic resin (B) is, for example, ⁇ 60 to 0 ° C., preferably ⁇ 50 to ⁇ 10 ° C., more preferably ⁇ 50 to ⁇ 20 ° C., and further preferably ⁇ 40 to It may be ⁇ 20 ° C., in particular ⁇ 40 to ⁇ 25 ° C.
  • Tg is in the above range, it is advantageous for improving the durability of the pressure-sensitive adhesive layer.
  • the glass transition temperature can be measured with a differential scanning calorimeter (DSC).
  • the (meth) acrylic resin (B) can be produced by a known method such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, and the solution polymerization method is particularly preferable.
  • a solution polymerization method for example, a monomer and an organic solvent are mixed, a thermal polymerization initiator is added in a nitrogen atmosphere, and the temperature is about 40 to 90 ° C., preferably about 50 to 80 ° C. The method of stirring for about an hour is raised.
  • a monomer or a thermal polymerization initiator may be added continuously or intermittently during the polymerization.
  • the monomer or thermal initiator may be added to an organic solvent.
  • the polymerization initiator a thermal polymerization initiator, a photopolymerization initiator, or the like is used.
  • the photopolymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone.
  • the thermal polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile).
  • the ratio of the polymerization initiator is about 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of monomers constituting the (meth) acrylic resin.
  • a polymerization method using active energy rays for example, ultraviolet rays may be used.
  • organic solvent 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; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. And the like.
  • the pressure-sensitive adhesive composition can contain a crosslinking agent (C).
  • the crosslinking agent (C) reacts with a reactive group (for example, a hydroxyl group) in the (meth) acrylic resin (B).
  • the crosslinking agent (C) forms a crosslinked structure with a (meth) acrylic resin or the like, and forms a crosslinked structure advantageous for durability and reworkability.
  • crosslinking agent (C) examples include conventional crosslinking agents (for example, isocyanate compounds, epoxy compounds, aziridine compounds, metal chelate compounds, peroxides, etc.), and particularly the pot life of the pressure-sensitive adhesive composition and the pressure-sensitive adhesive layer. From the viewpoints of durability, crosslinking speed and the like, an isocyanate compound is preferable.
  • the isocyanate compound is preferably a compound having at least two isocyanato groups (—NCO) in the molecule.
  • an aliphatic isocyanate compound eg, hexamethylene diisocyanate
  • an alicyclic isocyanate compound eg, isophorone diisocyanate
  • aromatic isocyanate compounds for example, tolylene diisocyanate, xylylene diisocyanate diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, etc.
  • the crosslinking agent (C) is an adduct (adduct) of the isocyanate compound with a polyhydric alcohol compound [for example, an adduct with glycerol, trimethylolpropane or the like], an isocyanurate, a burette type compound, a polyether polyol, or a polyester. It may be a derivative such as a urethane prepolymer type isocyanate compound obtained by addition reaction with a polyol, an acrylic polyol, a polybutadiene polyol, a polyisoprene polyol or the like.
  • a crosslinking agent (C) can be used individually or in combination of 2 or more types.
  • aromatic isocyanate compounds for example, tolylene diisocyanate, xylylene diisocyanate
  • aliphatic isocyanate compounds for example, hexamethylene diisocyanate
  • their polyhydric alcohol compounds for example, glycerol, trimethylolpropane.
  • isocyanurate is an adduct of an aromatic isocyanate compound and / or a polyhydric alcohol compound thereof, or an isocyanurate.
  • it is advantageous for forming an optimal crosslinking density (or crosslinked structure) The durability of the pressure-sensitive adhesive layer can be improved.
  • durability can be improved even when, for example, the pressure-sensitive adhesive layer is applied to a transparent electrode.
  • the ratio of the crosslinking agent (C) is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and further preferably 0.1 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin (B).
  • Part by mass or more particularly preferably 0.2 part by mass or more, especially 0.3 part by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, particularly preferably.
  • Silane compound (D) The pressure-sensitive adhesive composition can contain a silane compound (D) other than the siloxane compound (A).
  • the silane compound (D) is a silane compound capable of binding to a reactive group (for example, a hydroxyl group) of the (meth) acrylic resin (B), preferably a silane compound having at least one alkoxy group in the molecule.
  • a reactive group for example, a hydroxyl group
  • the silane compound (D) is a silane compound capable of binding to a reactive group (for example, a hydroxyl group) of the (meth) acrylic resin (B), preferably a silane compound having at least one alkoxy group in the molecule.
  • a reactive group for example, a hydroxyl group
  • vinyltrimethoxysilane vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane
  • 3-glycidoxypropyltrimethoxysilane 3-glycidoxypropyltriethoxysilane
  • 3-glycidoxypropyl Methyldimethoxysilane 3-glycidoxypropylethoxy
  • the silane compound (D) may be a silicone oligomer type compound.
  • the silicone oligomer is represented by a combination of monomers, for example, 3-mercaptopropyldi or trimethoxysilane-tetramethoxysilane oligomer, 3 -Mercaptoalkyl group-containing oligomers such as mercaptomethyldi or trimethoxysilane-tetraethoxysilane oligomer, 3-mercaptopropyldi or triethoxysilane-tetramethoxysilane oligomer, 3-mercaptomethyldi or triethoxysilane-tetraethoxysilane oligomer
  • the mercaptoalkyl group of the mercaptoalkyl group-containing oligomer is substituted with other substituents [3-glycidoxypropyl group, (meth) acryloyloxypropyl group, vinyl group, amino group, etc.
  • the pressure-sensitive adhesive composition may further contain an antistatic agent.
  • an antistatic agent By including the antistatic agent, the antistatic property of the pressure-sensitive adhesive can be improved (for example, a problem caused by static electricity generated when a release film, a protective film, or the like is peeled off) can be suppressed.
  • the antistatic agent include conventional ones, and an ionic antistatic agent is preferable.
  • the cation component constituting the ionic antistatic agent include organic cations and inorganic cations. Examples of the organic cation include a pyridinium cation, an imidazolium cation, an ammonium cation, a sulfonium cation, and a phosphonium cation.
  • the inorganic cation examples include alkali metal cations such as lithium cation, potassium cation, sodium cation and cesium cation, and alkaline earth metal cations such as magnesium cation and calcium cation.
  • the anionic component constituting the ionic antistatic agent may be either an inorganic anion or an organic anion, but an anionic component containing a fluorine atom is preferred from the viewpoint of excellent antistatic performance.
  • anion component containing a fluorine atom examples include hexafluorophosphate anion (PF 6 ⁇ ), bis (trifluoromethanesulfonyl) imide anion [(CF 3 SO 2 ) 2 N ⁇ ], bis (fluorosulfonyl) imide anion [(FSO 2 ) 2 N ⁇ ], tetra (pentafluorophenyl) borate anion [(C 6 F 5 ) 4 B ⁇ ] and the like.
  • PF 6 ⁇ hexafluorophosphate anion
  • bis (trifluoromethanesulfonyl) imide anion (CF 3 SO 2 ) 2 N ⁇ ]
  • bis (fluorosulfonyl) imide anion (FSO 2 ) 2 N ⁇ ]
  • tetra (pentafluorophenyl) borate anion (C 6 F 5 ) 4 B ⁇ ] and the like.
  • bis (trifluoromethanesulfonyl) imide anion [(CF 3 SO 2 ) 2 N ⁇ ]
  • tetra (pentafluorophenyl) borate anion [(C 6 F 5 ) 4 B ⁇ ]
  • An ionic antistatic agent that is solid at room temperature is preferable in that the antistatic performance of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition is excellent over time.
  • the proportion of the antistatic agent is, for example, 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and more preferably 1 to 3 parts by weight with respect to 100 parts by weight of the (meth) acrylic resin (B). Part.
  • the pressure-sensitive adhesive composition of the present invention exhibits good durability in a high temperature environment even when it contains an antistatic agent. For this reason, it is possible to achieve both good durability and antistatic performance.
  • the pressure-sensitive adhesive composition comprises a solvent, a crosslinking catalyst, an ultraviolet absorber, a weathering stabilizer, a tackifier, a plasticizer, a softener, a dye, a pigment, an inorganic filler, light scattering fine particles, and the like.
  • An agent can be contained alone or in combination of two or more. It is also useful to blend an ultraviolet curable compound into the pressure-sensitive adhesive composition and form a pressure-sensitive adhesive layer and then cure it by irradiating with ultraviolet rays to form a harder pressure-sensitive adhesive layer.
  • crosslinking catalyst examples include amine compounds such as hexamethylenediamine, ethylenediamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, isophoronediamine, trimethylenediamine, polyamino resin, and melamine resin.
  • the pressure-sensitive adhesive composition can contain a rust preventive agent from the viewpoint of enhancing the metal corrosion resistance of the pressure-sensitive adhesive layer.
  • a rust preventive agent examples include triazole compounds such as benzotriazole compounds; thiazole compounds such as benzothiazole compounds; imidazole compounds such as benzylimidazole compounds; imidazoline compounds; quinoline compounds; pyridine compounds; Examples include pyrimidine compounds; indole compounds; amine compounds; urea compounds; sodium benzoates; benzyl mercapto compounds; di-sec-butyl sulfide; and diphenyl sulfoxide.
  • the pressure-sensitive adhesive composition of the present invention does not substantially contain a photopolymerization initiator and a decomposition product thereof. This is because the photopolymerization initiator and its decomposition product in the pressure-sensitive adhesive composition may inhibit formation of a pressure-sensitive adhesive layer having excellent durability.
  • substantially not containing means that it is 1.0 part by mass or less, preferably 0.1 part by mass or less, more preferably 0.01 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive composition. Most preferably, it is at most 0.001 part by mass, more preferably at most 0 part by mass.
  • the present invention includes a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition.
  • the pressure-sensitive adhesive layer is obtained by, for example, dissolving or dispersing the pressure-sensitive adhesive composition in a solvent to obtain a solvent-containing pressure-sensitive adhesive composition, and then applying and drying this onto the surface of an optical film or a release film. Can be formed.
  • the present invention also includes an optical film with an adhesive layer in which an adhesive layer is laminated on at least one surface of the optical film.
  • the pressure-sensitive adhesive layer of the present invention and the optical film with the pressure-sensitive adhesive layer are formed from the pressure-sensitive adhesive composition, even when applied (or laminated) to a transparent electrode layer such as ITO, under severe durability conditions, Excellent durability.
  • FIG. 1 is a schematic sectional view showing an example of an optical film with an adhesive layer of the present invention.
  • the optical film 1 with an adhesive layer shown in FIG. 1 is an optical film having an optical film 10 and an adhesive layer 20 laminated on one side of the optical film.
  • the pressure-sensitive adhesive layer 20 is usually laminated directly on the surface of the optical film 10.
  • the pressure-sensitive adhesive layer 20 may be laminated on both surfaces of the optical film 10.
  • a primer layer is formed on the bonding surface of the optical film 10 and / or the bonding surface of the pressure-sensitive adhesive layer 20, or the surface activation treatment (for example, plasma treatment, corona treatment and the like are preferably performed, and corona treatment is particularly preferable.
  • the pressure-sensitive adhesive layer 20 is usually laminated on the polarizer surface, that is, the surface of the polarizer 2 opposite to the first resin film 3. (Preferably directly laminated).
  • the pressure-sensitive adhesive layer 20 may be laminated on the outer surface of either the first or second resin film 3 or 4, and both outer surfaces May be laminated.
  • a separate antistatic layer may be provided between the optical film 10 and the pressure-sensitive adhesive layer 20.
  • silicon materials such as polysiloxane, inorganic metal materials such as tin-doped indium oxide and tin-doped antimony oxide, and organic polymer materials such as polythiophene, polystyrene sulfonic acid, and polyaniline can be used.
  • the optical film 1 with an adhesive layer may include a separate film (release film) laminated on the outer surface of the adhesive layer 20.
  • This separate film is usually peeled and removed when the pressure-sensitive adhesive layer 20 is used (for example, when laminated on a transparent electrode or a glass substrate).
  • the separate film is obtained by, for example, performing a release treatment such as a silicone treatment on the surface on which the adhesive layer 20 of a film made of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, and polyarate is formed. Good.
  • the optical film 1 with the pressure-sensitive adhesive layer is 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 and drying this onto the surface of the optical film 10. And can be obtained by forming the pressure-sensitive adhesive layer 20. Moreover, the optical film 1 with an adhesive layer forms the adhesive layer 20 on the mold release process surface of a separate film similarly to the above, and laminates
  • the thickness of the pressure-sensitive adhesive layer is usually 2 to 40 ⁇ m, and preferably 5 to 30 ⁇ m, more preferably 10 from the viewpoints of durability of the optical film with the pressure-sensitive adhesive layer and reworkability of the optical film with the pressure-sensitive adhesive layer. ⁇ 25 ⁇ m.
  • the thickness of the pressure-sensitive adhesive layer is not more than the above upper limit value, the reworkability is good, and when it is more than the above lower limit value, the followability of the pressure-sensitive adhesive layer with respect to the dimensional change of the optical film is good.
  • the pressure-sensitive adhesive layer preferably shows a storage elastic modulus of 0.001 to 10 MPa in a temperature range of 23 to 120 ° C. Thereby, durability of the optical film with an adhesive layer can be improved more effectively.
  • “Showing a storage elastic modulus of 0.001 to 10 MPa in a temperature range of 23 to 120 ° C.” means that the storage elastic modulus is a value within the above range at any temperature within this range. Since the storage elastic modulus usually decreases gradually as the temperature rises, if both the storage elastic modulus at 23 ° C. and 120 ° C. are within the above range, the storage elastic modulus within the above range is exhibited at the temperature within this range. Can be assumed.
  • the storage elastic modulus of the pressure-sensitive adhesive layer can be measured using a commercially available viscoelasticity measuring device, for example, a viscoelasticity measuring device “DYNAMIC ANALYZER RDA II” manufactured by REOMETRIC.
  • Gel fraction can be used as an index of crosslinking density. Since the pressure-sensitive adhesive layer of the present invention has a predetermined crosslinking density, it exhibits a predetermined gel fraction. That is, the gel fraction of the pressure-sensitive adhesive layer of the present invention may be, for example, 70 to 90% by mass, preferably 75 to 90% by mass, and more preferably 75 to 85% by mass. When the gel fraction is at least the lower limit value, it is advantageous for foaming resistance and reworkability of the pressure-sensitive adhesive layer, and when the gel fraction is at most the upper limit value, it is advantageous for peeling resistance. The gel fraction can be measured by the method described in the Examples section.
  • the optical film with a pressure-sensitive adhesive layer of the present invention has a predetermined adhesive strength and is excellent in reworkability. That is, after the pressure-sensitive adhesive layer on the surface not bonded to the optical film of the optical film with the pressure-sensitive adhesive layer is bonded to a glass substrate and stored for 24 hours under conditions of a temperature of 23 ° C. and a relative humidity of 50%.
  • the adhesive strength is preferably 0.5 to 10 N / 25 mm, more preferably 0.7 to 5 N / 25 mm at a peeling speed of 300 mm / min.
  • the adhesive strength is at least the lower limit, the adhesiveness (or adhesiveness) is improved, which is advantageous for peeling resistance, and when the adhesive strength is at most the upper limit, it is advantageous for reworkability.
  • adhesive force can be measured by the method as described in the term of an Example, for example.
  • the optical film 10 constituting the optical film 1 with a pressure-sensitive adhesive layer may be various optical films (films having optical characteristics) that can be incorporated in an image display device such as a liquid crystal display device.
  • the optical film 10 may have a single layer structure (for example, an optical functional film such as a polarizer, a retardation film, a brightness enhancement film, an antiglare film, an antireflection film, a diffusion film, a light collecting film, etc.)
  • a multilayer structure for example, a polarizing plate, a phase difference plate, etc. may be used.
  • the optical film 10 is preferably a polarizing plate, a polarizer, a retardation plate or a retardation film, and particularly preferably a polarizing plate or a polarizer.
  • the optical film means a film that functions for image display (display screen or the like) (for example, a film that functions for improving the visibility of an image).
  • the polarizing plate means that a resin film or a resin layer is laminated on at least one surface of a polarizer
  • the retardation plate means a resin film on at least one surface of the retardation film. Or the thing on which the resin layer was laminated
  • FIGS. 2 and 3 are schematic cross-sectional views showing examples of the layer structure of the polarizing plate.
  • the polarizing plate 10a shown in FIG. 2 is a single-sided protective polarizing plate in which the first resin film 3 is laminated (or laminated) on one surface of the polarizer 2, and the polarizing plate 10b shown in FIG. This is a double-sided protective polarizing plate in which the second resin film 4 is further laminated (or laminated) on the other surface of the polarizer 2.
  • the first and second resin films 3 and 4 can be bonded to the polarizer 2 via an adhesive layer and an adhesive layer (not shown).
  • the polarizing plates 10a and 10b may include other films and layers other than the first and second resin films 3 and 4.
  • the polarizer 2 is a film having a property of absorbing linearly polarized light having a vibration surface parallel to the absorption axis and transmitting linearly polarized light having a vibration surface orthogonal to the absorption axis (parallel to the transmission axis).
  • a film in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol-based resin film can be used.
  • the dichroic dye include iodine and dichroic organic dyes.
  • the polyvinyl alcohol resin can be obtained by saponifying a polyvinyl acetate resin.
  • the polyvinyl acetate resin include polyvinyl acetate which is a homopolymer of vinyl acetate, and a monomer copolymerizable with vinyl acetate (for example, unsaturated carboxylic acid, olefin, vinyl ether, unsaturated sulfonic acid, ammonium group). (Meth) acrylamide etc.) and vinyl acetate.
  • the saponification degree of the polyvinyl alcohol resin is usually 85 to 100 mol%, preferably 98 mol% or more.
  • the polyvinyl alcohol-based resin may be modified, for example, polyvinyl formal or polyvinyl acetal modified with aldehydes.
  • the average degree of polymerization of the polyvinyl alcohol-based resin is usually 1000 to 10000, preferably 1500 to 5000.
  • the average degree of polymerization of the polyvinyl alcohol resin can be determined according to JIS K 6726.
  • a film made of a polyvinyl alcohol resin is used as the original film of the polarizer 2.
  • a polyvinyl alcohol-type resin can be formed into a film by a well-known method.
  • the thickness of the raw film is usually 1 to 150 ⁇ m, and is preferably 10 ⁇ m or more in consideration of easiness of stretching.
  • the polarizer 2 is, for example, a step of uniaxially stretching the original film, a step of dyeing the film with a dichroic dye and adsorbing the dichroic dye, a step of treating the film with an aqueous boric acid solution, and The film is washed with water and finally dried.
  • the thickness of the polarizer 2 is usually 1 to 30 ⁇ m, and preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, and particularly 10 ⁇ m or less from the viewpoint of thinning the optical film 1 with an adhesive layer.
  • a polarizer 2 formed by adsorbing and orienting a dichroic dye on a polyvinyl alcohol-based resin film uses a single film of a polyvinyl alcohol-based resin film as a raw film, and the uniaxial stretching treatment and dichroic dye of this film are used.
  • a substrate having a polyvinyl alcohol resin layer by applying a coating liquid (such as an aqueous solution) containing a polyvinyl alcohol resin to a substrate film, followed by drying, in addition to a method for performing a dyeing process (method (1)).
  • the base film a film made of a thermoplastic resin similar to the thermoplastic resin that can constitute the first and second resin films 3 and 4 described later can be used, and preferably a polyester-based resin such as polyethylene terephthalate. , Polycarbonate resins, cellulose resins such as triacetyl cellulose, cyclic polyolefin resins such as norbornene resins, polystyrene resins, and the like.
  • the method (2) the thin film polarizer 2 can be easily manufactured.
  • the polarizer 2 having a thickness of 7 ⁇ m or less can be easily manufactured.
  • the first and second resin films 3 and 4 are each independently a translucent resin film.
  • the first and second resin films 3 and 4 are preferably optically transparent thermoplastic resins such as chain polyolefin resins (for example, polyethylene resins and polypropylene resins), cyclic polyolefin resins (for example, norbornene-based resins).
  • Polyolefin resins such as resins); cellulose resins (such as cellulose ester resins); polyester resins (such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate); polycarbonate resins (such as 2,2-bis) (Polycarbonate derived from bisphenol such as (4-hydroxyphenyl) propane); (meth) acrylic resin; polystyrene resin; polyetheretherketone resin; polysulfone resin, or a mixture or copolymer thereof Etc. may be a film made of.
  • the first and second resin films 3 and 4 are films composed of a cyclic polyolefin resin, a polycarbonate resin, a cellulose resin, a polyester resin, and a (meth) acrylic resin, respectively. It is particularly preferable that the film is composed of a cellulose resin and a cyclic polyolefin resin.
  • chain polyolefin resin examples include a homopolymer of a chain olefin such as a polyethylene resin and a polypropylene resin, and a copolymer composed of two or more chain olefins.
  • the cyclic polyolefin-based resin is a general term for resins containing, as polymerization units, cyclic olefins whose representative examples are norbornene, tetracyclododecene (also known as dimethanooctahydronaphthalene) or their derivatives.
  • Cyclic polyolefin resins include ring-opening (co) polymers of cyclic olefins and hydrogenated products thereof, addition polymers of cyclic olefins, cyclic olefins and chain olefins such as ethylene and propylene, and aromatic compounds having a vinyl group And a modified (co) polymer obtained by modifying these with an unsaturated carboxylic acid or a derivative thereof.
  • norbornene resins using norbornene monomers such as norbornene and polycyclic norbornene monomers as cyclic olefins are preferred.
  • the cellulose resin is preferably a cellulose ester resin, that is, a cellulose partial or completely esterified product, and examples thereof include cellulose acetate ester, propionate ester, butyrate ester, and mixed ester thereof. Of these, triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate and the like are preferable.
  • the polyester-based resin is a resin other than the cellulose ester-based resin having an ester bond, and is generally made of a polycondensate of a polyvalent carboxylic acid or a derivative thereof and a polyhydric alcohol.
  • the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polycyclohexanedimethyl terephthalate, and polycyclohexanedimethyl naphthalate.
  • Polycarbonate resin is a polyester formed from carbonic acid and glycol or bisphenol.
  • an aromatic polycarbonate having a diphenylalkane in the molecular chain is preferable.
  • the polycarbonate include 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, , 1-bis (4-hydroxyphenyl) isobutane, polycarbonates derived from bisphenols such as 1,1-bis (4-hydroxyphenyl) ethane and the like.
  • the (meth) acrylic resin that can constitute the first and second resin films 3 and 4 can be a polymer mainly composed of a structural unit derived from a methacrylic ester (for example, containing 50% by mass or more).
  • the copolymer is preferably a copolymer in which another copolymer component is copolymerized.
  • the (meth) acrylic resin may contain two or more structural units derived from methacrylic acid esters. Examples of methacrylic acid esters include C 1 -C 4 alkyl esters of methacrylic acid such as methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like.
  • Examples of the copolymer component that can be copolymerized with the methacrylic acid ester include acrylic acid esters.
  • the acrylic ester is preferably a C 1 -C 8 alkyl ester of acrylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like.
  • Specific examples of other copolymerization components include unsaturated acids such as (meth) acrylic acid; aromatic vinyl compounds such as styrene, halogenated styrene, ⁇ -methylstyrene, and vinyl toluene; vinylcyan such as (meth) acrylonitrile.
  • (Meth) acrylic resin may have a ring structure in the polymer main chain in that the durability of the film can be improved.
  • the ring structure is preferably a heterocyclic structure such as a cyclic acid anhydride structure, a cyclic imide structure, or a lactone ring structure.
  • Specific examples of the cyclic acid anhydride structure include a glutaric anhydride structure and a succinic anhydride structure
  • specific examples of the cyclic imide structure include a glutarimide structure and a succinimide structure. Examples include butyrolactone ring structure and valerolactone ring structure.
  • the (meth) acrylic resin may contain acrylic rubber particles from the viewpoints of film-formability on the film and impact resistance of the film.
  • Acrylic rubber particles are particles having an elastic polymer mainly composed of an acrylate ester as an essential component.
  • the acrylic rubber particles have a single-layer structure consisting essentially of this elastic polymer, or an elastic polymer in one layer. And a multilayer structure having Examples of the elastic polymer include a cross-linked elastic copolymer obtained by copolymerizing an alkyl acrylate as a main component with another vinyl monomer and a cross-linkable monomer copolymerizable therewith.
  • the number of carbon atoms of the alkyl group is preferably 4 or more.
  • Examples of other vinyl monomers that can be copolymerized with alkyl acrylate include compounds having one polymerizable carbon-carbon double bond in the molecule, and more specifically, methacrylic acid esters such as methyl methacrylate. And aromatic vinyl compounds such as styrene, vinylcyan compounds such as (meth) acrylonitrile, and the like.
  • crosslinkable monomer examples include a crosslinkable compound having at least two polymerizable carbon-carbon double bonds in the molecule, and more specifically, ethylene glycol di (meth) acrylate, butanediol di ( Examples include (meth) acrylates of polyhydric alcohols such as (meth) acrylate, alkenyl esters of (meth) acrylic acid such as allyl (meth) acrylate, and divinylbenzene.
  • the content of the acrylic rubber particles is preferably 5 parts by mass or more, more preferably 10 parts by mass or more with respect to 100 parts by mass of the (meth) acrylic resin.
  • the content of the acrylic rubber particles is usually 80 parts by mass or less, preferably 60 parts by mass or less with respect to 100 parts by mass of the (meth) acrylic resin.
  • the first and second resin films 3 and 4 can contain usual additives in the technical field of the present invention.
  • the additive include an ultraviolet absorber, an infrared absorber, an organic dye, a pigment, an inorganic dye, an antioxidant, an antistatic agent, a surfactant, a lubricant, a dispersant, and a heat stabilizer.
  • the ultraviolet absorber include salicylic acid ester compounds, benzophenone compounds, benzotriazole compounds, triazine compounds, cyano (meth) acrylate compounds, nickel complex salts, and the like.
  • Each of the first and second resin films 3 and 4 may be an unstretched film or a uniaxially or biaxially stretched film.
  • the first resin film 3 and / or the second resin film 4 may be a protective film that plays a role of protecting the polarizer 2, or may be a protective film having an optical function such as a retardation film described later. Good.
  • the first resin film 3 and the second resin film 4 may be the same or different films.
  • the first resin film 3 and / or the second resin film 4 has a hard coat layer, an antiglare layer, an antireflection layer, a light diffusion layer, and an antistatic layer on the outer surface (the surface opposite to the polarizer 2). Further, a surface treatment layer (coating layer) such as an antifouling layer or a conductive layer may be provided.
  • the thickness of each of the first resin film 3 and the second resin film 4 is usually 1 to 150 ⁇ m, preferably 5 to 100 ⁇ m, more preferably 5 to 60 ⁇ m, still more preferably 50 ⁇ m or less (eg 1 to 40 ⁇ m), particularly 30 ⁇ m or less (for example, 5 to 25 ⁇ m).
  • a polarizing plate for small and medium-sized devices such as smartphones and tablet terminals is often used as a thin film having a thickness of 30 ⁇ m or less as the first resin film 3 and / or the second resin film 4 because of the demand for thinning.
  • Such a polarizing plate has a weak force to suppress the contraction force of the polarizer 2 and tends to have insufficient durability.
  • the optical film 1 with the pressure-sensitive adhesive layer of the present invention has good durability.
  • the first and second resin films 3 and 4 can be bonded to the polarizer 2 via an adhesive layer or an adhesive layer.
  • an adhesive forming the adhesive layer a water-based adhesive or an active energy ray-curable adhesive can be used.
  • a conventional water-based adhesive for example, an adhesive comprising a polyvinyl alcohol resin aqueous solution, an aqueous two-component urethane emulsion adhesive, an aldehyde compound, an epoxy compound, a melamine compound, a methylol compound, an isocyanate compound, And crosslinking agents such as amine compounds and polyvalent metal salts.
  • a water-based adhesive made of a polyvinyl alcohol-based resin aqueous solution can be suitably used.
  • a curing step for curing at a temperature of about 20 to 45 ° C. may be provided.
  • the active energy ray-curable adhesive refers to an adhesive that cures when irradiated with active energy rays such as ultraviolet rays and electron beams.
  • a curable composition containing a polymerizable compound and a photopolymerization initiator light Examples thereof include a curable composition containing a reactive resin, a curable composition containing a binder resin and a photoreactive cross-linking agent, and preferably an ultraviolet curable adhesive.
  • an active energy ray-curable adhesive When an active energy ray-curable adhesive is used, after the polarizer 2 and the first and second resin films 3 and 4 are bonded, a drying process is performed as necessary, and then an active energy ray is irradiated. A curing step of curing the active energy ray-curable adhesive is performed.
  • the light source of the active energy ray is not particularly limited, but ultraviolet light having a light emission distribution at a wavelength of 400 nm or less is preferable.
  • the adhesive for bonding these resin films may be the same type of adhesive or a different type of adhesive.
  • the polarizing plates 10a and 10b can further include other films or layers. Specific examples thereof include a retardation film, a brightness enhancement film, an antiglare film, an antireflection film, a diffusion film, a condensing film, an adhesive layer other than the adhesive layer 20, a coating layer, a protective film, and the like.
  • the protective film is a film used for the purpose of protecting the surface of the optical film 10 such as a polarizing plate from scratches and dirt. After the optical film 1 with an adhesive layer is bonded onto, for example, a metal layer or a substrate, it is peeled off. It is customary to be removed.
  • the base film is composed of a thermoplastic resin, for example, a polyolefin resin such as polyethylene resin or polypropylene resin; a polyester resin such as polyethylene terephthalate or polyethylene naphthalate; a polycarbonate resin; a (meth) acrylic resin, or the like. be able to.
  • a thermoplastic resin for example, a polyolefin resin such as polyethylene resin or polypropylene resin; a polyester resin such as polyethylene terephthalate or polyethylene naphthalate; a polycarbonate resin; a (meth) acrylic resin, or the like.
  • phase difference plate The phase difference film contained in the phase difference plate is an optical film exhibiting optical anisotropy as described above, and can be used for the first and second resin films 3 and 4.
  • thermoplastic resins for example, polyvinyl alcohol resins, polyarylate resins, polyimide resins, polyether sulfone resins, polyvinylidene fluoride / polymethyl methacrylate resins, liquid crystal polyester resins, It can be a stretched film obtained by stretching a resin film made of an ethylene-vinyl acetate copolymer saponified product, a polyvinyl chloride resin or the like to about 1.01 to 6 times.
  • a polycarbonate film, a cyclic olefin resin film, a (meth) acrylic resin film or a cellulose resin film is preferably a uniaxially stretched or biaxially stretched film.
  • a zero retardation film is also included in the retardation film.
  • a zero retardation film can also be used as a protective film.
  • a film called a uniaxial retardation film, a wide viewing angle retardation film, a low photoelastic modulus retardation film, or the like is also applicable as the retardation film.
  • the zero retardation film refers to a film having both an in-plane retardation value Re and a thickness direction retardation value Rth of ⁇ 15 to 15 nm.
  • This retardation film is suitably used for an IPS mode liquid crystal display device.
  • the in-plane retardation value R e and the thickness direction retardation value R th are both preferably ⁇ 10 to 10 nm, and more preferably both ⁇ 5 to 5 nm.
  • the in-plane retardation value R e and the thickness direction retardation value R th here are values at a wavelength of 590 nm.
  • n x is a refractive index in a slow axis direction (x-axis direction) in the film plane
  • n y is the fast axis direction in the film plane of the (y-axis direction orthogonal to the x-axis in a plane)
  • nz is the refractive index in the film thickness direction (z-axis direction perpendicular to the film surface)
  • d is the thickness of the film.
  • a resin film made of a polyolefin resin such as a cellulose resin, a chain polyolefin resin, and a cyclic polyolefin resin, a polyethylene terephthalate resin, or a (meth) acrylic resin
  • a cellulose resin, a polyolefin resin, or a (meth) acrylic resin is preferably used because the retardation value is easily controlled and easily available.
  • a film that exhibits optical anisotropy by applying and orienting a liquid crystalline compound and a film that exhibits optical anisotropy by applying an inorganic layered compound can be used as the retardation film.
  • a so-called temperature compensation type retardation film, and a rod-like liquid crystal sold under the trade name “NH film” from JX Nippon Mining & Energy Co., Ltd. are tilted.
  • orientation type film examples include a biaxial orientation type film sold by Sumitomo Chemical Co., Ltd. under the trade name “new VAC film”.
  • stacked on the at least one surface of retardation film may be the above-mentioned protective film, for example.
  • optical laminated body contains the base material laminated
  • the substrate examples include conventional substrates such as glass substrates, plastic films, organic conductive films, metal layers, overcoat resin layers, and the like.
  • a transparent electrode layer such as ITO or a metal layer such as a metal mesh (metal wiring layer) is used as the base material. Even in harsh durability conditions, it has excellent durability.
  • 4 to 8 are schematic cross-sectional views showing examples of the optical layered body according to the present invention.
  • the optical layered body 5 shown in FIG. 4 is formed by laminating the electrode layer 30 laminated on the substrate 40 on the surface on the pressure-sensitive adhesive layer side of the optical film 1a with the pressure-sensitive adhesive layer (or the polarizing plate with pressure-sensitive adhesive layer 1a). It is the optical laminated body.
  • the optical film 1a with an adhesive layer is obtained by laminating an adhesive layer 20 on the surface of the polarizing plate 10a on the polarizer 2 side.
  • the optical film 1b with an adhesive layer is an optical film in which an adhesive layer 20 is laminated on the surface of the polarizing plate 10b on the second resin film 4 side.
  • the optical laminates 5 and 6 can be obtained by bonding the optical films with adhesive layer (1a, 1b) to the electrode layer 30 laminated on the substrate 40 via the adhesive layer 20.
  • Examples of a method for forming the electrode layer 30 on the substrate 40 include a sputtering method.
  • the substrate 40 may be a transparent substrate constituting a liquid crystal cell included in the touch input element, and is preferably a glass substrate.
  • soda lime glass, low alkali glass, non-alkali glass, or the like can be used.
  • the electrode layer 30 may be formed on the entire surface of the substrate 40 or a part thereof.
  • Examples of the electrode layer 30 include a transparent electrode layer and a metal layer.
  • Examples of the transparent electrode layer include a layer composed of tin oxide, indium oxide, zinc oxide, gallium oxide, aluminum oxide, and a mixture thereof. In view of conductivity and visible light transmittance, ITO is preferable.
  • the metal layer a layer containing at least one metal element selected from aluminum, copper, silver, iron, tin, zinc, nickel, molybdenum, chromium, tungsten, lead, and an alloy containing two or more of these metals Etc.
  • it is preferably a metal layer containing at least one metal element selected from aluminum, copper, silver and gold, more preferably at least one selected from aluminum, copper and silver. It is a layer containing a seed metal element.
  • the metal layer may be a layer obtained by adding a metal mesh, metal nanoparticles, or metal nanowires in which a fine metal wiring layer is disposed on a substrate to a binder.
  • the method for preparing the electrode layer 30 is not particularly limited, and the electrode layer 30 may be formed by a vacuum deposition method, a sputtering method, an ion plating method, an ink jet printing method, or a gravure printing method.
  • the electrode layer is preferably a transparent electrode layer and a metal layer formed by a sputtering method, an inkjet printing method or a gravure printing method, and more preferably a transparent electrode layer and a metal layer formed by sputtering.
  • the thickness of the electrode layer 30 is not particularly limited, but is usually 3 ⁇ m or less, preferably 1 ⁇ m or less, more preferably 0.8 ⁇ m or less, and usually 0.01 ⁇ m or more.
  • the line width of the metal wiring is usually 10 ⁇ m or less, preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, and usually 0.5 ⁇ m or more. It is.
  • the optical laminate 7 shown in FIG. 6 is an optical laminate in which the adhesive layer 20 of the optical film 1 with an adhesive layer is laminated on a substrate 40.
  • the optical layered body 8 shown in FIG. 7 has a resin layer 50 further laminated on the surface of the electrode layer 30 laminated on the substrate 40 (on the surface opposite to the substrate 40). It is an optical laminate laminated on the surface of the optical film 1 on the pressure-sensitive adhesive layer 20 side.
  • resin which forms the resin layer 50 resin etc. which comprise the 1st or 2nd resin film of the said illustration are mentioned, for example.
  • the metal layer 30 is, for example, a metal wiring layer (that is, an electrode layer) of a touch input element included in the touch input type liquid crystal display device. ).
  • the plurality of electrode layers 30 may or may not be in contact with the pressure-sensitive adhesive layer 20 in whole or in part.
  • the electrode layer 30 may be a continuous film containing the metal or alloy.
  • the resin layer 50 may be omitted.
  • optical film (1, 1a, 1b) with the adhesive layer and the substrate 40 (glass substrate, transparent substrate, etc.) or the electrode layer 30 are bonded to produce an optical laminate. May require a so-called rework operation in which the optical film with an adhesive layer is peeled off from the substrate 40 or the electrode layer 30 and another optical film 1 with an adhesive layer is reattached to the substrate 40 or the electrode layer 30.
  • the optical film 1 with a pressure-sensitive adhesive layer according to the present invention is less likely to cause fogging or adhesive residue on the surface of a glass substrate or electrode layer (for example, a transparent conductive layer such as ITO) after peeling, and is excellent in reworkability. .
  • the pressure-sensitive adhesive layer, the optical film with the pressure-sensitive adhesive layer, and the optical laminate of the present invention can be used in a liquid crystal display device, and the liquid crystal display device has good durability.
  • the liquid crystal display device may be a touch input type liquid crystal display device having a touch panel function.
  • the touch input type liquid crystal display device includes a touch input element including a liquid crystal cell and a backlight.
  • the configuration of the touch panel may be a known method (for example, an out-cell type, an on-cell type, an in-cell type, etc.), and the operation method of the touch panel may be a known method, for example, a resistive film type, a capacitance type (surface type static type). (Capacitance method, projection type capacitance method) or the like.
  • the optical film with an adhesive layer according to the present invention may be disposed on the viewing side of the touch input element (liquid crystal cell), may be disposed on the backlight side, or may be disposed on both.
  • the driving method of the liquid crystal cell may be any conventionally known method such as a TN method, a VA method, an IPS method, a multi-domain method, and an OCB method.
  • the substrate 40 included in the optical laminate may be a substrate (typically a glass substrate) included in the liquid crystal cell.
  • Siloxane compound (A) for pressure-sensitive adhesive This invention includes the siloxane compound (A) for adhesives.
  • the pressure-sensitive adhesive siloxane compound (A) is the same as the above-described siloxane compound (A), the proportion of the alkoxy group of the hydrolysis condensate (a), the weight average molecular weight of the hydrolysis condensate (a), and The preferable range is the same.
  • the pressure-sensitive adhesive layer to which the siloxane compound for pressure-sensitive adhesive (A) is applied is not particularly limited, but preferably includes a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition described in [1] above.
  • the weight average molecular weight Mw and the number average molecular weight Mn are 4 columns of “TSKgel XL” manufactured by Tosoh Corp. and “Shodex GPC KF-” manufactured by Showa Denko K.K. "802" is connected in series, a total of 5 are connected in series, tetrahydrofuran is used as the eluent, sample concentration is 5mg / mL, sample introduction amount is 100 ⁇ L, temperature is 40 ° C, flow rate is 1mL / min. It was measured by. The conditions for obtaining the GPC discharge curve were also the same.
  • the glass transition temperature Tg was measured using a differential scanning calorimeter (DSC) “EXSTAR DSC6000” manufactured by SII NanoTechnology Co., Ltd. under a nitrogen atmosphere, a measurement temperature range of ⁇ 80 to 50 ° C., and a temperature increase rate of 10 ° C./min. It measured on condition of this.
  • DSC differential scanning calorimeter
  • Table 1 shows the composition of the monomers in each production example (the numerical values in Table 1 are parts by mass).
  • BA normal butyl acrylate (glass transition temperature of homopolymer: ⁇ 54 ° C.)
  • MA methyl acrylate (glass transition temperature of homopolymer: 10 ° C.)
  • HEA 2-hydroxyethyl acrylate 5HPA: 5-hydroxypentyl acrylate
  • PEA phenoxyethyl acrylate AA: acrylic acid.
  • siloxane compound (A-1) The weight average molecular weight of the obtained siloxane compound (A-1) was 1300. From 1 H-NMR, it was confirmed that 20% of the alkoxy groups were hydrolyzed without contradiction to the amount of added water. That is, the content of alkoxy groups contained in the siloxane compound (A-1) is 80 mol% with respect to 100 mol% of the total amount of alkoxy groups contained in 1,6-bistrimethoxysilylhexane.
  • siloxane compound (A-2) had a weight average molecular weight of 920. From 1 H-NMR, it was confirmed that 15% of the alkoxy groups were hydrolyzed without contradicting the amount of added water. That is, the content of alkoxy groups contained in the siloxane compound (A-2) is 85 mol% with respect to 100 mol% of the total amount of alkoxy groups contained in 1,6-bistrimethoxysilylhexane.
  • Siloxane compound (A) A-1: Siloxane compound (A) obtained in Production Example 3 (hydrolysis condensate of 1,6-bis (trimethoxysilyl) hexane, hydrolysis rate 20%)
  • a transparent protective film [trade name “KC2UA” manufactured by Konica Minolta Opto Co., Ltd.] made of a 25 ⁇ m-thick triacetyl cellulose film is placed on one side of the obtained polarizer with an adhesive made of an aqueous solution of a polyvinyl alcohol resin. And pasted.
  • a zero retardation film [trade name “ZEONOR” manufactured by Nippon Zeon Co., Ltd.] made of a cyclic polyolefin resin having a thickness of 23 ⁇ m is formed on the surface opposite to the triacetyl cellulose film in the polarizer.
  • a bonded polarizing plate was produced through an adhesive made of an aqueous resin solution.
  • the optical film with pressure-sensitive adhesive layer (P-1) produced in the above (3) is 300 mm ⁇ 220 mm so that the stretching axis direction of the polarizing plate is the long side. It cut
  • the test piece (the optical film with the pressure-sensitive adhesive layer to which the glass substrate was attached) obtained by attaching the obtained glass substrate was placed in an autoclave at a temperature of 50 ° C. and a pressure of 5 kg / cm 2 (490.3 kPa) for 20 minutes. Pressurized.
  • a non-alkali glass product name “Eagle XG” manufactured by Corning was used for the glass substrate.
  • a non-alkali glass manufactured by Corning [trade name “Eagle XG”] having a 30 nm ITO layer formed by ITO deposition was used. The following durability test was implemented about the obtained optical laminated body.
  • the optical film with pressure-sensitive adhesive layer (P-1) produced in the above (3) was cut into a test piece having a size of 25 mm ⁇ 150 mm.
  • the separator was peeled off from the test piece, and the pressure-sensitive adhesive surface was attached to a glass substrate.
  • the test piece (the optical film with the pressure-sensitive adhesive layer to which the glass substrate was attached) obtained by attaching the obtained glass substrate was placed in an autoclave at a temperature of 50 ° C. and a pressure of 5 kg / cm 2 (490.3 kPa) for 20 minutes. Pressurized. After storing for 24 hours in an atmosphere having a temperature of 23 ° C.
  • the optical film was peeled from the test piece together with the pressure-sensitive adhesive layer in the direction of 180 ° at a speed of 300 mm / min.
  • Table 3 shows the average peeling force at the time of peeling as the adhesive strength. When the adhesive strength is 6N or less, the rework property is excellent, and when it is 0.5N or more, peeling hardly occurs even when an impact is applied from the end of the polarizing plate.
  • the gel fraction evaluation method of the adhesive sheet of this invention is shown.
  • the gel fraction is a value measured according to the following (a) to (d).
  • a pressure-sensitive adhesive sheet having an area of about 8 cm ⁇ about 8 cm and a metal mesh made of SUS304 (about 10 cm ⁇ about 10 cm) (with a mass of Wm) are bonded.
  • C) The mesh stapled in (II) above is placed in a glass container, and 60 mL of ethyl acetate is added and immersed, and then the glass container is stored at room temperature for 3 days.
  • optical films with pressure-sensitive adhesive layers obtained in Examples 1 to 9 showed good durability even under severe durability conditions. Even when applied to an ITO substrate, good durability was exhibited. Moreover, it has also confirmed that it has favorable reworkability and can make durability and reworkability compatible.
  • SYMBOLS 1,1a, 1b Optical film with an adhesive layer, 2 ... Polarizer, 3 ... 1st resin film, 4 ... 2nd resin film, 5, 6, 7, 8, 9 ... Optical laminated body, 10 ... Optical film DESCRIPTION OF SYMBOLS 10a, 10b ... Polarizing plate, 20 ... Adhesive layer, 30 ... Electrode layer, 40 ... Substrate, 50 ... Resin layer.

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Abstract

An adhesive composition containing a siloxane compound (A), said siloxane compound (A) being a hydrolysis condensate (a) of a hydrolytically condensable silane compound represented by formula (a1) [wherein: B represents an alkanediyl group having 1-20 carbon atoms or a divalent alicyclic hydrocarbon group having 3-20 carbon atoms, -CH2- constituting the alkanediyl group or the alicyclic hydrocarbon group optionally being substituted by -O- or -CO-; R1 and R2 independently represent an alkyl group having 1-5 carbon atoms; and R3, R4, R5 and R6 independently represent an alkyl group having 1-5 carbon atoms or an alkoxy group having 1-5 carbon atoms].

Description

粘着剤組成物Adhesive composition
　本特許出願は日本国特許出願第２０１７－１０３０１８号（出願日：２０１７年５月２４日）についてパリ条約上の優先権を主張するものであり、ここに参照することによって、その全体が本明細書中へ組み込まれるものとする。
　本発明は、液晶表示装置等に利用される光学部材として有用な粘着剤組成物、該粘着剤組成物からなる粘着剤層、該粘着剤層を含む粘着剤層付光学フィルム、該粘着剤層付光学フィルムを含む光学積層体、並びに粘着剤用シロキサン化合物に関する。 This patent application claims priority under the Paris Convention for Japanese Patent Application No. 2017-103018 (filing date: May 24, 2017), which is hereby incorporated by reference in its entirety. It shall be incorporated into the book.
The present invention relates to a pressure-sensitive adhesive composition useful as an optical member utilized in a liquid crystal display device, a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition, an optical film with a pressure-sensitive adhesive layer containing the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer The present invention relates to an optical laminate including an attached optical film and a siloxane compound for pressure-sensitive adhesive.
　偏光子の片面又は両面に透明樹脂フィルムを積層貼合してなる偏光板に代表される光学フィルムは、液晶表示装置等の画像表示装置を構成する光学部材として広く用いられている。偏光板のような光学フィルムは、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）に貼合して用いられることが多い（特許文献１参照）。このため、光学フィルムとして、その一方の面に予め粘着剤層が設けられた粘着剤層付光学フィルムが知られている。 An optical film typified by a polarizing plate formed by laminating and laminating a transparent resin film on one or both surfaces of a polarizer is widely used as an optical member constituting an image display device such as a liquid crystal display device. An optical film such as a polarizing plate is often used by being bonded to another member (for example, a liquid crystal cell in a liquid crystal display device) via an adhesive layer (see Patent Document 1). For this reason, the optical film with an adhesive layer by which the adhesive layer was previously provided in the one surface as an optical film is known.
特開２０１０－２２９３２１号公報JP 2010-229321 A
　近年、液晶表示装置は、スマートフォンやタブレット型端末に代表されるモバイル機器用途やカーナビゲーションシステムに代表される車載用機器用途に展開されている。このような用途においては、従来の屋内用ＴＶ用途に比べて苛酷な環境に曝される可能性があることから、装置の耐久性向上が課題となっている。 In recent years, liquid crystal display devices have been deployed in mobile device applications such as smartphones and tablet terminals and in-vehicle devices such as car navigation systems. In such an application, there is a possibility that it may be exposed to a harsh environment as compared with a conventional indoor TV application.
　液晶表示装置等を構成する粘着剤層付光学フィルムにおいても同様に耐久性が要求されている。すなわち、液晶表示装置等に組み込まれた粘着剤層は、高温又は高温高湿環境下に置かれたり、高温と低温とが繰り返される環境下に置かれたりすることがあるが、粘着剤層付光学フィルムには、これらの環境下においても、粘着剤層とこれが貼合される光学部材との界面での浮きや剥れ、粘着剤層の発泡等の不具合を抑制できることが求められ、また、光学特性が劣化しないことも求められる。とりわけ、粘着剤層付光学フィルムがＩＴＯ（錫ドープ酸化インジウム）等の透明電極に適用（貼合又は積層）されるタッチパネルなどでは、特に上記のような苛酷な耐久条件下で、高い耐久性の発現が困難な場合があり、かかる場合においても高い耐久性能が要求されている。 Similarly, durability is required for an optical film with an adhesive layer constituting a liquid crystal display device or the like. That is, the pressure-sensitive adhesive layer incorporated in a liquid crystal display device or the like may be placed in a high temperature or high temperature and high humidity environment, or may be placed in an environment where high and low temperatures are repeated. The optical film is required to be able to suppress problems such as floating and peeling at the interface between the pressure-sensitive adhesive layer and the optical member to which the optical film is bonded, foaming of the pressure-sensitive adhesive layer, and the like even under these circumstances. It is also required that the optical characteristics do not deteriorate. In particular, in a touch panel in which an optical film with an adhesive layer is applied (laminated or laminated) to a transparent electrode such as ITO (tin-doped indium oxide), it is highly durable particularly under the above severe durability conditions. In some cases, expression is difficult, and even in such a case, high durability performance is required.
　従って、本発明の目的は、ＩＴＯ等の透明電極層に適用した場合においても、苛酷な耐久条件下で、良好な耐久性を示す粘着剤層を形成可能な粘着剤組成物、該粘着剤組成物からなる粘着剤層、該粘着剤層を含む粘着剤層付光学フィルム、該粘着剤層付光学フィルムを含む光学積層体、並びに粘着剤用シロキサン化合物を提供することにある。 Accordingly, an object of the present invention is to provide a pressure-sensitive adhesive composition capable of forming a pressure-sensitive adhesive layer exhibiting good durability under severe durability conditions even when applied to a transparent electrode layer such as ITO, and the pressure-sensitive adhesive composition An object is to provide a pressure-sensitive adhesive layer comprising a product, an optical film with a pressure-sensitive adhesive layer including the pressure-sensitive adhesive layer, an optical laminate including the optical film with the pressure-sensitive adhesive layer, and a siloxane compound for pressure-sensitive adhesive.
　本発明者は、上記課題を解決するために鋭意検討した結果、本発明を完成するに至った。すなわち、本発明には、以下のものが含まれる。
［１］シロキサン化合物（Ａ）を含む粘着剤組成物であって、
シロキサン化合物（Ａ）は、下記式（ａ１）
Figure JPOXMLDOC01-appb-C000003
 （式中、Ｂは、炭素数１～２０のアルカンジイル基又は炭素数３～２０の二価の脂環式炭化水素基を示し、前記アルカンジイル基及び前記脂環式炭化水素基を構成する－ＣＨ２－は、－Ｏ－又は－ＣＯ－に置換されてもよく、Ｒ１及びＲ２はそれぞれ独立して炭素数１～５のアルキル基を示し、Ｒ３、Ｒ４、Ｒ５及びＲ６はそれぞれ独立して、炭素数１～５のアルキル基又は炭素数１～５のアルコキシ基を示す）
で表される加水分解縮合性シラン化合物の加水分解縮合物（ａ）である、粘着剤組成物。
［２］シロキサン化合物（Ａ）に含まれるアルコキシ基の含有量は、加水分解縮合性シラン化合物（ａ１）に含まれるアルコキシ基の総量１００モル％に対して、６０～９５モル％である、［１］に記載の粘着剤組成物。
［３］シロキサン化合物（Ａ）の重量平均分子量は、ポリスチレン換算で、８００～４０００である、［１］又は［２］に記載の粘着剤組成物。
［４］さらに（メタ）アクリル系樹脂（Ｂ）及び架橋剤（Ｃ）を含む、［１］～［３］のいずれかに記載の粘着剤組成物。
［５］シロキサン化合物（Ａ）の割合は、（メタ）アクリル系樹脂（Ｂ）１００質量部に対して、０．０１～１０質量部である、［４］に記載の粘着剤組成物。
［６］（メタ）アクリル系樹脂（Ｂ）は、ホモポリマーのガラス転移温度が０℃未満のアルキルアクリレート（ｂ１）由来の構成単位と、ホモポリマーのガラス転移温度が０℃以上のアルキルアクリレート（ｂ２）由来の構成単位とを含む、［４］又は［５］に記載の粘着剤組成物。
［７］（メタ）アクリル系樹脂（Ｂ）に含まれるカルボキシル基含有（メタ）アクリレート由来の構成単位の割合は、（メタ）アクリル系樹脂（Ｂ）を構成する全構成単位１００質量部に対して１．０質量部以下である、［４］～［６］のいずれかに記載の粘着剤組成物。
［８］（メタ）アクリル系樹脂（Ｂ）の重量平均分子量は、ポリスチレン換算で、１００～２５０万である、［４］～［７］のいずれかに記載の粘着剤組成物。
［９］架橋剤（Ｃ）はイソシアネート系化合物である、［４］～［８］のいずれかに記載の粘着剤組成物。
［１０］架橋剤（Ｃ）の割合は、（メタ）アクリル系樹脂（Ｂ）１００質量部に対して、０．０１～１０質量部である、［４］～［９］のいずれかに記載の粘着剤組成物。
［１１］［１］～［１０］のいずれかに記載の粘着剤組成物からなる粘着剤層。
［１２］［１１］に記載の粘着剤層を、光学フィルムの少なくとも一方の面に積層させた粘着剤層付光学フィルム。
［１３］前記粘着剤層付光学フィルムの、光学フィルムと貼合されていない面の粘着剤層をガラス基板に貼合し、温度２３℃、相対湿度５０％の条件下、２４時間保管した後の粘着力は、剥離速度３００ｍｍ／分において、０．５～１０Ｎ／２５ｍｍである、［１２］に記載の粘着剤層付光学フィルム。
［１４］［１２］又は［１３］に記載の粘着剤層付光学フィルムを含む、光学積層体。
［１５］下記式（ａ１）
Figure JPOXMLDOC01-appb-C000004
 （式中、Ｂは、炭素数１～２０のアルカンジイル基又は炭素数３～２０の二価の脂環式炭化水素基を示し、前記アルカンジイル基及び前記脂環式炭化水素基を構成する－ＣＨ２－は、－Ｏ－又は－ＣＯ－に置換されてもよく、Ｒ１及びＲ２はそれぞれ独立して炭素数１～５のアルキル基を示し、Ｒ３、Ｒ４、Ｒ５及びＲ６はそれぞれ独立して、炭素数１～５のアルキル基又は炭素数１～５のアルコキシ基を示す）
で表される加水分解縮合性シラン化合物の加水分解縮合物（ａ）である、粘着剤用シロキサン化合物（Ａ）。 As a result of intensive studies in order to solve the above problems, the present inventors have completed the present invention. That is, the present invention includes the following.
[1] A pressure-sensitive adhesive composition containing a siloxane compound (A),
The siloxane compound (A) is represented by the following formula (a1)
Figure JPOXMLDOC01-appb-C000003
 (In the formula, B represents an alkanediyl group having 1 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and constitutes the alkanediyl group and the alicyclic hydrocarbon group. —CH 2 — may be substituted with —O— or —CO—, R 1 and R 2 each independently represents an alkyl group having 1 to 5 carbon atoms, and R 3 , R 4 , R 5 and R 6 each independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms)
A pressure-sensitive adhesive composition, which is a hydrolysis-condensation product (a) of a hydrolysis-condensable silane compound represented by:
[2] The content of the alkoxy group contained in the siloxane compound (A) is 60 to 95 mol% with respect to 100 mol% of the total amount of alkoxy groups contained in the hydrolytic condensable silane compound (a1). 1] The pressure-sensitive adhesive composition according to 1.
[3] The pressure-sensitive adhesive composition according to [1] or [2], wherein the siloxane compound (A) has a weight average molecular weight of 800 to 4000 in terms of polystyrene.
[4] The pressure-sensitive adhesive composition according to any one of [1] to [3], further comprising a (meth) acrylic resin (B) and a crosslinking agent (C).
[5] The pressure-sensitive adhesive composition according to [4], wherein the ratio of the siloxane compound (A) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin (B).
[6] The (meth) acrylic resin (B) comprises a structural unit derived from an alkyl acrylate (b1) having a homopolymer glass transition temperature of less than 0 ° C., and an alkyl acrylate having a homopolymer glass transition temperature of 0 ° C. or more ( The pressure-sensitive adhesive composition according to [4] or [5], comprising a structural unit derived from b2).
[7] The proportion of the structural unit derived from the carboxyl group-containing (meth) acrylate contained in the (meth) acrylic resin (B) is 100 parts by mass of all the structural units constituting the (meth) acrylic resin (B). The pressure-sensitive adhesive composition according to any one of [4] to [6], which is 1.0 part by mass or less.
[8] The pressure-sensitive adhesive composition according to any one of [4] to [7], wherein the (meth) acrylic resin (B) has a weight average molecular weight of 1,000 to 2,500,000 in terms of polystyrene.
[9] The pressure-sensitive adhesive composition according to any one of [4] to [8], wherein the crosslinking agent (C) is an isocyanate compound.
[10] The ratio of the crosslinking agent (C) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin (B), according to any one of [4] to [9] Adhesive composition.
[11] A pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition according to any one of [1] to [10].
[12] An optical film with an adhesive layer in which the adhesive layer according to [11] is laminated on at least one surface of the optical film.
[13] After the pressure-sensitive adhesive layer on the surface of the optical film with the pressure-sensitive adhesive layer not bonded to the optical film is bonded to a glass substrate and stored for 24 hours under conditions of a temperature of 23 ° C. and a relative humidity of 50%. The adhesive film with an adhesive layer according to [12], which has an adhesive strength of 0.5 to 10 N / 25 mm at a peeling speed of 300 mm / min.
[14] An optical laminate comprising the optical film with the pressure-sensitive adhesive layer according to [12] or [13].
[15] The following formula (a1)
Figure JPOXMLDOC01-appb-C000004
 (In the formula, B represents an alkanediyl group having 1 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and constitutes the alkanediyl group and the alicyclic hydrocarbon group. —CH 2 — may be substituted with —O— or —CO—, R 1 and R 2 each independently represents an alkyl group having 1 to 5 carbon atoms, and R 3 , R 4 , R 5 and R 6 each independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms)
The siloxane compound (A) for adhesives which is a hydrolysis-condensation product (a) of the hydrolytic condensable silane compound represented by these.
　本発明の粘着剤組成物は、ＩＴＯ等の透明電極層に適用した場合においても、苛酷な耐久条件下で、良好な耐久性を示す粘着剤層を形成できる。 The pressure-sensitive adhesive composition of the present invention can form a pressure-sensitive adhesive layer exhibiting good durability under severe durability conditions even when applied to a transparent electrode layer such as ITO.
本発明に係る粘着剤組成物から形成された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。It is a schematic sectional drawing which shows an example of the optical film with an adhesive layer formed from the adhesive composition which concerns on this invention. 偏光板の層構成の一例を示す概略断面図である。It is a schematic sectional drawing which shows an example of the laminated constitution of a polarizing plate. 偏光板の層構成の他の例を示す概略断面図である。It is a schematic sectional drawing which shows the other example of the laminated constitution of a polarizing plate. 本発明に係る粘着剤組成物から形成された粘着剤層付光学フィルムを含む光学積層体の一例を示す概略断面図である。It is a schematic sectional drawing which shows an example of the optical laminated body containing the optical film with an adhesive layer formed from the adhesive composition which concerns on this invention. 本発明に係る粘着剤組成物から形成された粘着剤層付光学フィルムを含む光学積層体の他の例を示す概略断面図である。It is a schematic sectional drawing which shows the other example of the optical laminated body containing the optical film with an adhesive layer formed from the adhesive composition which concerns on this invention. 本発明に係る粘着剤組成物から形成された粘着剤層付光学フィルムを含む光学積層体のさらに他の例を示す概略断面図である。It is a schematic sectional drawing which shows the further another example of the optical laminated body containing the optical film with an adhesive layer formed from the adhesive composition which concerns on this invention. 本発明に係る粘着剤組成物から形成された粘着剤層付光学フィルムを含む光学積層体の別の例を示す概略断面図である。It is a schematic sectional drawing which shows another example of the optical laminated body containing the optical film with an adhesive layer formed from the adhesive composition which concerns on this invention. 本発明に係る粘着剤組成物から形成された粘着剤層付光学フィルムを含む光学積層体のさらに別の例を示す概略断面図である。It is a schematic sectional drawing which shows another example of the optical laminated body containing the optical film with an adhesive layer formed from the adhesive composition which concerns on this invention.
　［１］粘着剤組成物
　本発明の粘着剤組成物は、シロキサン化合物（Ａ）を含む。 [1] Pressure-sensitive adhesive composition The pressure-sensitive adhesive composition of the present invention contains a siloxane compound (A).
　［１－１］シロキサン化合物（Ａ）
　シロキサン化合物（Ａ）は、下記式（ａ１）
Figure JPOXMLDOC01-appb-C000005
 （式中、Ｂは、炭素数１～２０のアルカンジイル基又は炭素数３～２０の二価の脂環式炭化水素基を示し、前記アルカンジイル基及び前記脂環式炭化水素基を構成する－ＣＨ２－は、－Ｏ－又は－ＣＯ－に置換されてもよい。
　Ｒ１及びＲ２はそれぞれ独立して炭素数１～５のアルキル基を示す。
　Ｒ３、Ｒ４、Ｒ５及びＲ６はそれぞれ独立して、炭素数１～５のアルキル基又は炭素数１～５のアルコキシ基を示す）
で表される加水分解縮合性シラン化合物の加水分解縮合物（ａ）である。 [1-1] Siloxane compound (A)
The siloxane compound (A) is represented by the following formula (a1)
Figure JPOXMLDOC01-appb-C000005
 (In the formula, B represents an alkanediyl group having 1 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and constitutes the alkanediyl group and the alicyclic hydrocarbon group. —CH 2 — may be substituted with —O— or —CO—.
R 1 and R 2 each independently represents an alkyl group having 1 to 5 carbon atoms.
R 3 , R 4 , R 5 and R 6 each independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms)
It is a hydrolysis-condensation product (a) of the hydrolytic condensable silane compound represented by these.
　式（ａ１）において、Ｂは、メチレン基、エチレン基、トリメチレン基、テトラメチレン基、ヘキサメチレン基、ヘプタメチレン基、オクタメチレン基などの炭素数１～２０のアルカンジイル基；シクロブチレン基（例えば１，２－シクロブチレン基）、シクロペンチレン基（例えば１，２－シクロペンチレン基）、シクロヘキシレン基（例えば１，２－シクロへキシレン基）、シクロオクチレン基（例えば１，２－シクロオクチレン基）などの炭素数３～２０の二価の脂環式炭化水素基；又はこれらのアルカンジイル基及び前記脂環式炭化水素基を構成する－ＣＨ２－が、－Ｏ－又は－ＣＯ－に置換された基を示す。好ましいＢは、炭素数１～１０のアルカンジイル基である。
　Ｒ３、Ｒ４、Ｒ５及びＲ６は、それぞれ独立して、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、ｔ－ブチル基、ペンチル基などの炭素数１～５のアルキル基；又はメトキシ基、エトキシ基、プロポキシ基、ｉ－プロポキシ基、ブトキシ基、s－ブトキシ基、t－ブトキシ基などの炭素数１～５のアルコキシ基を示す。Ｒ３、Ｒ４、Ｒ５及びＲ６は、それぞれ独立して炭素数１～５のアルコキシ基であることが好ましい。
　Ｒ１及びＲ２で表される炭素数１～５のアルキル基は、Ｒ３、Ｒ４、Ｒ５及びＲ６で表される炭素数１～５のアルキル基と同じものが挙げられる。 In the formula (a1), B represents an alkanediyl group having 1 to 20 carbon atoms such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group; a cyclobutylene group (for example, 1,2-cyclobutylene group), cyclopentylene group (for example, 1,2-cyclopentylene group), cyclohexylene group (for example, 1,2-cyclohexylene group), cyclooctylene group (for example, 1,2- A divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms such as a cyclooctylene group; or —CH 2 — constituting these alkanediyl groups and the alicyclic hydrocarbon group is —O— or A substituted group is represented by —CO—. Preferred B is an alkanediyl group having 1 to 10 carbon atoms.
R 3 , R 4 , R 5 and R 6 each independently represents 1 carbon atom such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a s-butyl group, a t-butyl group, or a pentyl group. Or an alkyl group having 1 to 5 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, an i-propoxy group, a butoxy group, an s-butoxy group, or a t-butoxy group. R 3 , R 4 , R 5 and R 6 are preferably each independently an alkoxy group having 1 to 5 carbon atoms.
Examples of the alkyl group having 1 to 5 carbon atoms represented by R 1 and R 2 are the same as the alkyl group having 1 to 5 carbon atoms represented by R 3 , R 4 , R 5 and R 6 .
　具体的なシラン化合物（ａ１）としては、例えば、ビス（トリメトキシシリル）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、１，３－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、１，４－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、１，５－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、１，６－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、１，８－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、１，８－ビス（トリプロポキシシリル）オクタンなどのビス（トリＣ１－５アルコキシシリル）Ｃ１－１０アルカン；ビス（ジメトキシメチルシリル）メタン、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、１，４－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、１，６－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、１，８－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）オクタンなどのビス（ジＣ１－５アルコキシＣ１－５アルキルシリル）Ｃ１－１０アルカン；１，６－ビス（メトキシジメチルシリル）ヘキサン、１，８－ビス（メトキシジメチルシリル）オクタンなどのビス（モノＣ１－５アルコキシ－ジＣ１－５アルキルシリル）Ｃ１－１０アルカンなどが挙げられる。これらのうち、１，２－ビス（トリメトキシシリル）エタン、１，３－ビス（トリメトキシシリル）プロパン、１，４－ビス（トリメトキシシリル）ブタン、１，５－ビス（トリメトキシシリル）ペンタン、１，６－ビス（トリメトキシシリル）ヘキサン、１，８－ビス（トリメトキシシリル）オクタンなどのビス（トリＣ１－３アルコキシシリル）Ｃ１－１０アルカンが好ましく、特に、１，６－ビス（トリメトキシシリル）ヘキサン、１，８－ビス（トリメトキシシリル）オクタンが好ましい。 Specific examples of the silane compound (a1) include bis (trimethoxysilyl) methane, 1,2-bis (trimethoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, and 1,3-bis. (Trimethoxysilyl) propane, 1,3-bis (triethoxysilyl) propane, 1,4-bis (trimethoxysilyl) butane, 1,4-bis (triethoxysilyl) butane, 1,5-bis (tri Methoxysilyl) pentane, 1,5-bis (triethoxysilyl) pentane, 1,6-bis (trimethoxysilyl) hexane, 1,6-bis (triethoxysilyl) hexane, 1,6-bis (tripropoxysilyl) ) Hexane, 1,8-bis (trimethoxysilyl) octane, 1,8-bis (triethoxysilyl) octane, 1,8-bis (triple) Pokishishiriru) bis octane (tri C 1-5 alkoxysilyl) C 1-10 alkanes, bis (dimethoxymethylsilyl) methane, 1,2-bis (dimethoxymethylsilyl) ethane, 1,2-bis (dimethoxy ethyl silyl ) Ethane, 1,4-bis (dimethoxymethylsilyl) butane, 1,4-bis (dimethoxyethylsilyl) butane, 1,6-bis (dimethoxymethylsilyl) hexane, 1,6-bis (dimethoxyethylsilyl) hexane Bis (diC 1-5 alkoxyC 1-5 alkylsilyl) C 1-10 alkane such as 1,8-bis (dimethoxymethylsilyl) octane, 1,8-bis (dimethoxyethylsilyl) octane; -Bis (methoxydimethylsilyl) hexane, 1,8-bis (methoxydimethylsilyl) octane And bis (mono C 1-5 alkoxy-diC 1-5 alkylsilyl) C 1-10 alkane such as tan. Of these, 1,2-bis (trimethoxysilyl) ethane, 1,3-bis (trimethoxysilyl) propane, 1,4-bis (trimethoxysilyl) butane, 1,5-bis (trimethoxysilyl) Bis (triC 1-3 alkoxysilyl) C 1-10 alkanes such as pentane, 1,6-bis (trimethoxysilyl) hexane, 1,8-bis (trimethoxysilyl) octane are preferred, especially 1,6 -Bis (trimethoxysilyl) hexane and 1,8-bis (trimethoxysilyl) octane are preferred.
　前記式（ａ１）で表される加水分解縮合性シラン化合物（以下、加水分解縮合性シラン化合物（ａ１）と称する場合がある）の加水分解縮合物（ａ）とは、加水分解縮合性シラン化合物（ａ１）中の加水分解性基であるアルコキシ基が、加水分解及び縮合されて得られた縮合物、例えばダイマーやオリゴマーなどを意味する。また、加水分解縮合物（ａ）は、加水分解縮合性シラン化合物（ａ１）のアルコキシ基が、部分的に加水分解及び縮合された加水分解縮合物（部分加水分解縮合物と称する場合がある）であっても、該アルコキシ基の全部が加水分解及び縮合された縮合物であってもよい。また、加水分解性シラン化合物（ａ１）のアルコキシ基がヒドロキシル基に加水分解され、次いで生成したヒドロキシル基が縮合されるが、ヒドロキシル基の一部が縮合されずに、加水分解縮合物（ａ）中に残存していてもよい。 The hydrolytic condensate (a) of the hydrolytic condensable silane compound represented by the formula (a1) (hereinafter sometimes referred to as hydrolytic condensable silane compound (a1)) is the hydrolytic condensable silane compound. The alkoxy group which is the hydrolyzable group in (a1) means a condensate obtained by hydrolysis and condensation, such as a dimer or oligomer. The hydrolysis condensate (a) is a hydrolysis condensate obtained by partially hydrolyzing and condensing the alkoxy group of the hydrolyzable silane compound (a1) (sometimes referred to as a partial hydrolysis condensate). Alternatively, it may be a condensate obtained by hydrolyzing and condensing all of the alkoxy groups. In addition, the alkoxy group of the hydrolyzable silane compound (a1) is hydrolyzed to a hydroxyl group, and then the generated hydroxyl group is condensed, but a part of the hydroxyl group is not condensed, but the hydrolysis condensate (a) It may remain inside.
　加水分解縮合物（ａ）は、部分的又は全体的、好ましくは部分的なアルコキシ基の加水分解及び縮合により、加水分解縮合性シラン化合物（ａ１）由来の構成単位が、Ｓｉ－Ｏ－Ｓｉ結合を介して繰り返された構造を有する。加水分解縮合物（ａ）は、直鎖状であっても分岐鎖状であってもよい。 The hydrolysis-condensation product (a) has a structural unit derived from the hydrolytic condensable silane compound (a1) formed by Si—O—Si bond by partial or total, preferably partial hydrolysis and condensation of an alkoxy group. Having a repeated structure. The hydrolysis condensate (a) may be linear or branched.
　本発明の粘着剤組成物は、シロキサン化合物（Ａ）を含むため、例えば粘着剤組成物からなる粘着剤層を電極層に適用（貼合又は積層）した場合においても、粘着剤層の耐久性を向上でき、高温環境下でも、界面の剥がれ（又は浮き）及び発泡を有効に抑制できる。さらに、該粘着剤組成物は良好なリワーク性（剥離性）も有する。このため、本発明の粘着剤組成物は、良好な耐久性とリワーク性とを両立することができる。 Since the pressure-sensitive adhesive composition of the present invention contains the siloxane compound (A), for example, even when a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition is applied (bonded or laminated) to the electrode layer, the durability of the pressure-sensitive adhesive layer The interface can be effectively prevented from peeling (or floating) and foaming even in a high temperature environment. Furthermore, the pressure-sensitive adhesive composition also has good reworkability (peelability). For this reason, the pressure-sensitive adhesive composition of the present invention can achieve both good durability and reworkability.
　なお、本明細書において、耐久性とは、例えば高温環境下、高温高湿環境下、高温と低温とが繰り返される環境下などにおいて、粘着剤層とこれに隣接する光学部材との界面での浮きや剥れを抑制できる特性（耐剥がれ性という場合がある）、及び粘着剤層の発泡等の不具合を抑制できる特性（耐発泡性という場合がある）をいう。さらに、本明細書において、耐凝集破壊性とは、粘着剤層の凝集破壊（又は破れ）を抑制できる特性をいう。 In the present specification, the term “durability” refers to the interface between the pressure-sensitive adhesive layer and the optical member adjacent thereto, for example, in a high temperature environment, a high temperature and high humidity environment, or an environment where high and low temperatures are repeated. It refers to a characteristic that can prevent floating and peeling (sometimes referred to as peeling resistance) and a characteristic that can suppress problems such as foaming of the pressure-sensitive adhesive layer (sometimes referred to as foaming resistance). Furthermore, in this specification, the cohesive failure resistance refers to a property capable of suppressing cohesive failure (or tearing) of the pressure-sensitive adhesive layer.
　加水分解縮合物（ａ）は、好ましくは加水分解縮合性シラン化合物（ａ１）の部分加水分解縮合物である。シロキサン化合物（Ａ）に含まれるアルコキシ基の含有量は、加水分解縮合性シラン化合物（ａ１）に含まれるアルコキシ基の総量１００モル％に対して、好ましくは６０モル％以上、より好ましくは６５モル％以上、さらに好ましくは７０モル％以上であり、好ましくは９５モル％以下、より好ましくは９０モル％以下、さらに好ましくは８８モル％以下であり、これらの下限値と上限値の任意の組合せであってよく、例えば６０～９５モル％、好ましくは６５～９０モル％、より好ましくは７０～８８モル％であってもよい。シロキサン化合物（Ａ）に含まれるアルコキシ基の含有量が上記下限値以上であると、粘着剤層の耐久性をより向上でき、上記上限値以下であると、粘着剤層のリワーク性をより向上できる。 The hydrolysis condensate (a) is preferably a partial hydrolysis condensate of the hydrolytic condensable silane compound (a1). The content of the alkoxy group contained in the siloxane compound (A) is preferably 60 mol% or more, more preferably 65 mol with respect to 100 mol% of the total amount of alkoxy groups contained in the hydrolytic condensable silane compound (a1). % Or more, more preferably 70 mol% or more, preferably 95 mol% or less, more preferably 90 mol% or less, still more preferably 88 mol% or less, and any combination of these lower and upper limits. For example, it may be 60 to 95 mol%, preferably 65 to 90 mol%, more preferably 70 to 88 mol%. When the content of the alkoxy group contained in the siloxane compound (A) is not less than the above lower limit, the durability of the pressure-sensitive adhesive layer can be further improved, and when it is not more than the above upper limit, the reworkability of the pressure-sensitive adhesive layer can be further improved. it can.
　シロキサン化合物（Ａ）に含まれるアルコキシ基の含有量は、加水分解水の配合量によって調整できる。加水分解縮合性シラン化合物（ａ１）に含まれる１モルのアルコキシ基は、０．５モルの加水分解水で加水分解される。加水分解縮合性シラン化合物（ａ１）に含まれるアルコキシ基の総量１００モル％に対して、シロキサン化合物（Ａ）に含まれるアルコキシ基の含有量が６０モル％であれば、加水分解縮合性シラン化合物（ａ１）の４０％のアルコキシ基を加水分解したこととなり、加水分解率は４０％となる。シロキサン化合物（Ａ）に含まれるアルコキシ基の含有量が９５モル％であれば、加水分解縮合性シラン化合物（ａ１）の５モル％のアルコキシ基を加水分解したこととなり加水分解率は５％となる。 The content of the alkoxy group contained in the siloxane compound (A) can be adjusted by the amount of hydrolyzed water. 1 mol of alkoxy group contained in the hydrolyzable condensable silane compound (a1) is hydrolyzed with 0.5 mol of hydrolyzed water. If the content of the alkoxy group contained in the siloxane compound (A) is 60 mol% with respect to the total amount of 100 mol% of the alkoxy groups contained in the hydrolytic condensable silane compound (a1), the hydrolyzable condensable silane compound This means that 40% of the alkoxy group of (a1) has been hydrolyzed, and the hydrolysis rate is 40%. If the content of the alkoxy group contained in the siloxane compound (A) is 95 mol%, 5 mol% of the alkoxy group of the hydrolytic condensable silane compound (a1) is hydrolyzed, and the hydrolysis rate is 5%. Become.
　シロキサン化合物（Ａ）の重量平均分子量は、ゲルパーミエイションクロマトグラフィーＧＰＣによるポリスチレン換算で、好ましくは６００以上、より好ましくは７００以上、さらに好ましくは８００以上であり、好ましくは４０００以下、より好ましくは３０００以下、さらに好ましくは２０００以下であり、これらの下限値と上限値の任意の組合せであってよく、例えば６００～４０００、好ましくは７００～３０００、より好ましくは８００～２０００であってもよい。重量平均分子量が上記範囲であると、粘着剤層の耐久性及びリワーク性をより向上することができる。 The weight average molecular weight of the siloxane compound (A) is preferably 600 or more, more preferably 700 or more, further preferably 800 or more, preferably 4000 or less, more preferably 4000 or less, in terms of polystyrene by gel permeation chromatography GPC. It is 3000 or less, more preferably 2000 or less, and any combination of these lower limit values and upper limit values may be used, for example, 600 to 4000, preferably 700 to 3000, and more preferably 800 to 2000. When the weight average molecular weight is in the above range, the durability and reworkability of the pressure-sensitive adhesive layer can be further improved.
　シロキサン化合物（Ａ）は、加水分解縮合性シラン化合物（ａ１）が、単独又は二種以上加水分解及び縮合した加水分解縮合物（ａ）であってよい。また、シロキサン化合物（Ａ）は、加水分解縮合性シラン化合物（ａ１）と、加水分解縮合性シラン化合物（ａ１）以外の加水分解縮合性シラン化合物［加水分解縮合性シラン化合物（ａ２）という場合がある］との加水分解縮合物（ａ）であってよい。加水分解縮合性シラン化合物（ａ２）を併用する場合、シロキサン化合物（Ａ）は、加水分解シラン化合物（ａ１）を好ましくは７０モル％以上、より好ましくは８０モル％以上、さらに好ましくは９０モル％以上、特に好ましくは９５モル％以上含有することが好ましい。 The siloxane compound (A) may be a hydrolytic condensate (a) obtained by hydrolyzing and condensing the hydrolytic condensable silane compound (a1) alone or in combination. The siloxane compound (A) may be referred to as a hydrolytic condensable silane compound (a1) and a hydrolytic condensable silane compound other than the hydrolytic condensable silane compound (a1) [hydrolytic condensable silane compound (a2). It may be a hydrolysis condensate (a). When the hydrolytic condensable silane compound (a2) is used in combination, the siloxane compound (A) is preferably 70 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol%, of the hydrolyzed silane compound (a1). As mentioned above, it is particularly preferable to contain 95 mol% or more.
　シロキサン化合物（Ａ）には、加水分解縮合物（ａ）に加え、単独又は二種以上の縮合されていない加水分解縮合性シラン化合物（ａ１）を含んでいてもよい。また、加水分解縮合性シラン化合物（ａ２）を併用する場合、シラン化合物（Ａ）には、縮合されていない加水分解縮合性シラン化合物（ａ２）を含んでいてもよい。縮合されていない加水分解縮合性シラン化合物（ａ１）又は（ａ２）のアルコキシ基は、縮合されていない限り、部分的又は全体的に加水分解（ヒドロキシル基に変換）されていてよい。 In addition to the hydrolysis-condensation product (a), the siloxane compound (A) may contain one or two or more non-condensed hydrolysis-condensable silane compounds (a1). When the hydrolyzable condensable silane compound (a2) is used in combination, the silane compound (A) may contain an uncondensed hydrolyzable condensable silane compound (a2). The non-condensed hydrolytic condensable silane compound (a1) or (a2) alkoxy group may be partially or wholly hydrolyzed (converted to a hydroxyl group) as long as it is not condensed.
　加水分解縮合性シラン化合物（ａ１）以外の加水分解縮合性シラン化合物（ａ２）としては、例えば、メチルトリメトキシシラン、メチルトリエトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジフェニルジメトキシシラン、ジフェニルジエトキシシラン、トリメチルメトキシシラン、トリメチルエトキシシラン、ビニルトリジメトキシシラン、ビニルトリジエトキシシラン、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メチルジエトキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルトリエトキシシラン、３－メタクリロキシプロピルメチルジメトキシシラン、３－メタクリロキシプロピルメチルジエトキシシラン、３－アクリロキシプロピルトリメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、３－メルカプトプロピルメチルジメトキシシラン及び３－メルカプトプロピルメトキシシラン等が挙げられる。 Examples of the hydrolytic condensable silane compound (a2) other than the hydrolytic condensable silane compound (a1) include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, and dimethyl. Diethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, vinyltridimethoxysilane, vinyltridiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane 3-glycidpropylpropyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypro Lutriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N -2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethoxysilane and the like .
　シロキサン化合物（Ａ）の割合は、粘着剤組成物の総量１００質量％に対して、好ましくは０．０１質量％以上、より好ましくは０．０５質量％以上、さらに好ましくは０．１質量％以上、特に好ましくは０．２質量％以上であり、好ましくは１０質量％以下、より好ましくは５質量％以下、さらに好ましくは３質量％以下、特に好ましくは１質量％以下、とりわけ０．５質量％以下であり、これらの下限値と上限値の任意の組合せであってよく、例えば０．０１～１０質量％、好ましくは０．０１～５質量％、より好ましくは０．０５～３質量％、さらに好ましくは０．１～１質量％、特に好ましくは０．２～０．５質量％であってもよい。シロキサン化合物（Ａ）の割合が上記範囲であると、粘着剤層の耐久性及びリワーク性をより向上することができる。 The ratio of the siloxane compound (A) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more with respect to 100% by mass of the total amount of the pressure-sensitive adhesive composition. Particularly preferably 0.2% by mass or more, preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, particularly preferably 1% by mass or less, especially 0.5% by mass. Or any combination of these lower and upper limits, for example 0.01 to 10% by weight, preferably 0.01 to 5% by weight, more preferably 0.05 to 3% by weight, More preferably, it may be 0.1 to 1% by mass, and particularly preferably 0.2 to 0.5% by mass. When the proportion of the siloxane compound (A) is in the above range, the durability and reworkability of the pressure-sensitive adhesive layer can be further improved.
　粘着剤組成物に後述の（メタ）アクリル系樹脂（Ｂ）を含む場合、シロキサン化合物（Ａ）の含有量は、（メタ）アクリル系樹脂（Ｂ）１００質量部に対して、好ましくは０．０１質量部以上、より好ましくは０．０５質量部以上、さらに好ましくは０．１質量部以上、特に好ましくは０．２質量部以上であり、好ましくは１０質量部以下、より好ましくは５質量部以下、さらに好ましくは３質量部以下、特に好ましくは１質量部以下、とりわけ０．５質量部以下であり、これらの下限値と上限値の任意の組合せであってよく、例えば０．０１～１０質量部、好ましくは０．０１～５質量部、より好ましくは０．０５～３質量部、さらに好ましくは０．１～１質量部、特に好ましくは０．２～０．５質量部であってもよい。シロキサン化合物（Ａ）の割合が上記範囲であると、粘着剤層の耐久性及びリワーク性をより向上することができる。 When the (meth) acrylic resin (B) described later is included in the pressure-sensitive adhesive composition, the content of the siloxane compound (A) is preferably 0.00 with respect to 100 parts by mass of the (meth) acrylic resin (B). 01 parts by mass or more, more preferably 0.05 parts by mass or more, further preferably 0.1 parts by mass or more, particularly preferably 0.2 parts by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass. In the following, it is more preferably 3 parts by mass or less, particularly preferably 1 part by mass or less, especially 0.5 part by mass or less, and any combination of these lower limit values and upper limit values may be used. Parts by weight, preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, still more preferably 0.1 to 1 part by weight, particularly preferably 0.2 to 0.5 parts by weight. Also good. When the proportion of the siloxane compound (A) is in the above range, the durability and reworkability of the pressure-sensitive adhesive layer can be further improved.
　シロキサン化合物（Ａ）の製造方法としては、慣用の方法、例えば溶媒の存在下、必要に応じて触媒（例えば、酸性触媒、塩基性触媒等）を加えて、加水分解縮合性シラン化合物（ａ１）及び必要に応じて加水分解縮合性シラン化合物（ａ２）を混合撹拌する方法などが挙げられる。 The production method of the siloxane compound (A) is a conventional method, for example, in the presence of a solvent, a catalyst (for example, an acidic catalyst, a basic catalyst, etc.) is added if necessary, and the hydrolytic condensable silane compound (a1). And the method of mixing and stirring a hydrolytic condensable silane compound (a2) as needed.
　［１－２］（メタ）アクリル系樹脂（Ｂ）
　（メタ）アクリル系樹脂（Ｂ）は、（メタ）アクリル系樹脂（Ｂ）を構成する全構成単位１００質量％に対して、（メタ）アクリル系単量体由来の構成単位を、好ましくは５０質量％以上、より好ましくは７０質量％以上、さらに好ましくは９０質量％以上含む重合体又は共重合体である。なお、本明細書において、「（メタ）アクリル」は、アクリル又はメタクリルを意味し、「（メタ）アクリレート」や「（メタ）アクリロイル」などについても同様に、それぞれアクリレート又はメタクリレート、アクリロイル又はメタクリロイルを意味する。 [1-2] (Meth) acrylic resin (B)
The (meth) acrylic resin (B) is preferably a structural unit derived from a (meth) acrylic monomer, preferably 50% with respect to 100% by mass of all the structural units constituting the (meth) acrylic resin (B). It is a polymer or copolymer containing at least mass%, more preferably at least 70 mass%, and even more preferably at least 90 mass%. In the present specification, “(meth) acryl” means acryl or methacryl, and “(meth) acrylate”, “(meth) acryloyl”, and the like are acrylate or methacrylate, acryloyl or methacryloyl, respectively. means.
　（メタ）アクリル系樹脂（Ｂ）は、例えば、極性官能基含有（メタ）アクリレート由来の構成単位、（メタ）アクリルアミド系単量体由来の構成単位、スチレン系単量体由来の構成単位、ビニル系単量体由来の構成単位、分子内に複数の（メタ）アクリロイル基を有する単量体由来の構成単位、アルキルアクリレート由来の構成単位、置換基含有アルキルアクリレート由来の構成単位等を含んでいてよい。これらの構成単位は単独又は二種以上組み合わせて使用できる。 The (meth) acrylic resin (B) is, for example, a structural unit derived from a polar functional group-containing (meth) acrylate, a structural unit derived from a (meth) acrylamide monomer, a structural unit derived from a styrene monomer, or vinyl. A structural unit derived from a monomer, a structural unit derived from a monomer having a plurality of (meth) acryloyl groups in the molecule, a structural unit derived from an alkyl acrylate, a structural unit derived from a substituent-containing alkyl acrylate, etc. Good. These structural units can be used individually or in combination of 2 or more types.
　極性官能基含有（メタ）アクリレートとしては、例えばヒドロキシ基含有（メタ）アクリレート、エポキシ基等の複素環基含有（メタ）アクリレート、置換若しくは無置換アミノ基含有（メタ）アクリレート、カルボキシル基含有（メタ）アクリレート等が挙げられる。 Examples of the polar functional group-containing (meth) acrylate include a hydroxy group-containing (meth) acrylate, a heterocyclic group-containing (meth) acrylate such as an epoxy group, a substituted or unsubstituted amino group-containing (meth) acrylate, and a carboxyl group-containing (meta ) Acrylate and the like.
　ヒドロキシ基含有（メタ）アクリレートとしては、好ましくは下記式（ｂ１）又は（ｂ２）に示されるヒドロキシ基含有（メタ）アクリレートなどが挙げられる。
Figure JPOXMLDOC01-appb-C000006
 （式中、ｎは１～４の整数を示し、Ａ１は水素原子又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し、ｎが２以上のとき、前記置換基は同一又は異なっていてもよい）
Figure JPOXMLDOC01-appb-C000007
 （式中、ｍは５以上の整数を示し、Ａ２は水素原子又はアルキル基を示し、Ｘ２は置換基を有していてもよいメチレン基を示し、前記置換基は同一又は異なっていてもよい） The hydroxy group-containing (meth) acrylate is preferably a hydroxy group-containing (meth) acrylate represented by the following formula (b1) or (b2).
Figure JPOXMLDOC01-appb-C000006
 (Wherein n represents an integer of 1 to 4, A 1 represents a hydrogen atom or an alkyl group, X 1 represents an optionally substituted methylene group, and when n is 2 or more, The substituents may be the same or different)
Figure JPOXMLDOC01-appb-C000007
 (In the formula, m represents an integer of 5 or more, A 2 represents a hydrogen atom or an alkyl group, X 2 represents a methylene group which may have a substituent, and the substituents are the same or different. Also good)
　式（ｂ１）及び式（ｂ２）において、Ｘ１及びＸ２は置換基を有していてもよいメチレン基を示す。該置換基としては、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、ｔ－ブチル基、ペンチル基、ヘキシル基などのＣ１－１０アルキル基、好ましくはＣ１－６アルキル基、さらに好ましくはＣ１－３アルキル基）、シクロアルキル基（例えばシクロペンチル基、シクロへキシル基など）、アリール基［例えばフェニル基、アルキルフェニル基（トリル基、キシリル基など）］、アラルキル基（例えばベンジル基など）、アルコキシ基（例えば、メトキシ基、エトキシ基などのＣ１－４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など）、シクロアルコキシ基（例えば、シクロへキシルオキシ基などのＣ５－１０シクロアルキルオキシ基など）、アリールオキシ基（例えば、フェノキシ基など）、アラルキルオキシ基（例えば、ベンジルオキシ基など）、アルキルチオ基（例えば、メチルチオ基、エチルチオ基などのＣ１－４アルキルチオ基など）、シクロアルキルチオ基（例えば、シクロへキシルチオ基など）、アリールチオ基（例えば、チオフェノキシ基など）、アラルキルチオ基（例えば、ベンジルチオ基など）、アシル基（例えば、アセチル基など）、ニトロ基、シアノ基などが挙げられる。これらのうち、ハロゲン原子、アルキル基、アルコキシ基、アリールオキシ基などが好ましく、特にアルキル基（例えばメチル基、エチル基など）が好ましい。 In Formula (b1) and Formula (b2), X 1 and X 2 represent a methylene group which may have a substituent. Examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (eg, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an s-butyl group, a t-butyl group). C 1-10 alkyl group such as butyl group, pentyl group, hexyl group, preferably C 1-6 alkyl group, more preferably C 1-3 alkyl group), cycloalkyl group (eg cyclopentyl group, cyclohexyl group, etc.) ), Aryl group [eg phenyl group, alkylphenyl group (tolyl group, xylyl group etc.)], aralkyl group (eg benzyl group etc.), alkoxy group (eg C 1-4 alkoxy group such as methoxy group, ethoxy group etc.) , Polyoxyalkylene groups (eg, dioxyethylene groups), cycloalkoxy groups (eg, cyclohexyl) C 5-10 cycloalkyloxy group such as ruoxy group), aryloxy group (eg phenoxy group etc.), aralkyloxy group (eg benzyloxy group etc.), alkylthio group (eg methylthio group, ethylthio group etc.) C 1-4 alkylthio group), cycloalkylthio group (eg, cyclohexylthio group), arylthio group (eg, thiophenoxy group), aralkylthio group (eg, benzylthio group), acyl group (eg, acetyl) Group), nitro group, cyano group and the like. Among these, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, and the like are preferable, and an alkyl group (for example, a methyl group, an ethyl group, and the like) is particularly preferable.
　Ａ１及びＡ２で表されるアルキル基は、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、ｔ－ブチル基、ペンチル基、ヘキシル基などのＣ１－１０アルキル基等が挙げられ、好ましくはメチル基などであってもよい。
　式（ｂ１）において、ｎは１～４の整数を示し、好ましくは１～３の整数、さらに好ましくは２である。また、式（ｂ２）において、ｍは５以上の整数を示し、例えば５～２０の整数が挙げられ、好ましくは５～１５の整数であり、より好ましくは５～９の整数であり、さらに好ましくは５～７の整数である。ｍは、奇数であることが好ましい。 The alkyl group represented by A 1 and A 2 is a C 1-10 alkyl such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, s-butyl group, t-butyl group, pentyl group, and hexyl group. Group etc. are mentioned, Preferably a methyl group etc. may be sufficient.
In the formula (b1), n represents an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 2. In the formula (b2), m represents an integer of 5 or more, and examples include an integer of 5 to 20, preferably an integer of 5 to 15, more preferably an integer of 5 to 9, and still more preferably. Is an integer from 5 to 7. m is preferably an odd number.
　ヒドロキシ基含有（メタ）アクリレート（ｂ１）の具体例としては、（メタ）アクリル酸１－ヒドロキシメチル、（メタ）アクリル酸１－ヒドロキシエチル、（メタ）アクリル酸１－ヒドロキシヘプチル、（メタ）アクリル酸１－ヒドロキシブチル、（メタ）アクリル酸１－ヒドロキシペンチルなどの（メタ）アクリル酸１－ヒドロキシＣ１－８アルキル；（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシブチル、（メタ）アクリル酸２－ヒドロキシペンチル、（メタ）アクリル酸２－ヒドロキシヘキシルなどの（メタ）アクリル酸２－ヒドロキシＣ２－９アルキル；（メタ）アクリル酸３－ヒドロキシプロピル、（メタ）アクリル酸３－ヒドロキシブチル、（メタ）アクリル酸３－ヒドロキシペンチル、（メタ）アクリル酸３－ヒドロキシヘキシル、（メタ）アクリル酸３－ヒドロキシヘプチルなどの（メタ）アクリル酸３－ヒドロキシＣ３－１０アルキル；（メタ）アクリル酸４－ヒドロキシブチル、（メタ）アクリル酸４－ヒドロキシペンチル、（メタ）アクリル酸４－ヒドロキシヘキシル、（メタ）アクリル酸４－ヒドロキシヘプチル、（メタ）アクリル酸４－ヒドロキシオクチルなどの（メタ）アクリル酸４－ヒドロキシＣ４－１１アルキル；（メタ）アクリル酸２－クロロ－２－ヒドロキシプロピル、（メタ）アクリル酸３－クロロ－２－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシー３－フェノキシプロピルなどが挙げられる。これらのうち、耐久性の観点から、アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸２－ヒドロキシブチルなどのｎが２であるヒドロキシ基含有（メタ）アクリレート；（メタ）アクリル酸３－ヒドロキシプロピル、（メタ）アクリル酸３－ヒドロキシブチル、（メタ）アクリル酸３－ヒドロキシペンチルなどのｎが３であるヒドロキシ基含有（メタ）アクリレートが好ましい。特に、該ｎが２であるヒドロキシ基含有（メタ）アクリレートが好ましく、これらの中でも（メタ）アクリル酸２－ヒドロキシエチルが好ましい。 Specific examples of the hydroxy group-containing (meth) acrylate (b1) include 1-hydroxymethyl (meth) acrylate, 1-hydroxyethyl (meth) acrylate, 1-hydroxyheptyl (meth) acrylate, and (meth) acrylic. 1-hydroxybutyl acid, 1-hydroxyC 1-8 alkyl (meth) acrylate such as 1-hydroxypentyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate (Meth) acrylic acid 2-hydroxybutyl, (meth) acrylic acid 2-hydroxypentyl, (meth) acrylic acid 2-hydroxyhexyl and the like (meth) acrylic acid 2-hydroxy C 2-9 alkyl; (meth) acrylic 3-hydroxypropyl acid, 3-hydroxybutyl (meth) acrylate, ( Data) acrylate, 3-hydroxypentyl, (meth) acrylate, 3-hydroxyhexyl, (meth) (meth) acrylic acid such as acrylic acid 3-hydroxy-heptyl 3-hydroxy C 3-10 alkyl; (meth) acrylic acid 4 -(Meth) acrylic acid such as hydroxybutyl, 4-hydroxypentyl (meth) acrylate, 4-hydroxyhexyl (meth) acrylate, 4-hydroxyheptyl (meth) acrylate, 4-hydroxyoctyl (meth) acrylate 4-hydroxy C 4-11 alkyl; (meth) acrylic acid 2-chloro-2-hydroxypropyl, (meth) acrylic acid 3-chloro-2-hydroxypropyl, (meth) acrylic acid 2-hydroxy-3-phenoxypropyl, etc. Is mentioned. Among these, from the viewpoint of durability, hydroxy group-containing (meth) acrylates in which n is 2, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, etc. Hydroxy group-containing (meth) acrylates where n is 3 such as 3-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 3-hydroxypentyl (meth) acrylate, and the like are preferable. In particular, the hydroxy group-containing (meth) acrylate in which n is 2 is preferable, and among these, 2-hydroxyethyl (meth) acrylate is preferable.
　ヒドロキシ基含有（メタ）アクリレート（ｂ２）の具体例としては、（メタ）アクリル酸５－ヒドロキシペンチル、（メタ）アクリル酸５－ヒドロキシヘキシル、（メタ）アクリル酸５－ヒドロキシヘプチル、（メタ）アクリル酸５－ヒドロキシオクチル、（メタ）アクリル酸５－ヒドロキシノニルなどの（メタ）アクリル酸５－ヒドロキシＣ５－１２アルキル；（メタ）アクリル酸６－ヒドロキシヘキシル、（メタ）アクリル酸６－ヒドロキシヘプチル、（メタ）アクリル酸６－ヒドロキシオクチル、（メタ）アクリル酸６－ヒドロキシノニル、（メタ）アクリル酸６－ヒドロキシデシルなどの（メタ）アクリル酸６－ヒドロキシＣ６－１３アルキル；（メタ）アクリル酸７－ヒドロキシヘプチル、（メタ）アクリル酸７－ヒドロキシオクチル、（メタ）アクリル酸７－ヒドロキシノニル、（メタ）アクリル酸７－ヒドロキシデシル、（メタ）アクリル酸７－ヒドロキシウンデシルなどの（メタ）アクリル酸７－ヒドロキシＣ７－１４アルキル；（メタ）アクリル酸８－ヒドロキシオクチル、（メタ）アクリル酸８－ヒドロキシノニル、（メタ）アクリル酸８－ヒドロキシデシル、（メタ）アクリル酸８－ヒドロキシウンデシル、（メタ）アクリル酸８－ヒドロキシドデシルなどの（メタ）アクリル酸８－ヒドロキシＣ８－１５アルキル；（メタ）アクリル酸９－ヒドロキシノニル、（メタ）アクリル酸９－ヒドロキシデシル、（メタ）アクリル酸９－ヒドロキシウンデシル、（メタ）アクリル酸９－ヒドロキシドデシル、（メタ）アクリル酸９－ヒドロキシトリデシルなどの（メタ）アクリル酸９－ヒドロキシＣ９－１６アルキル；（メタ）アクリル酸１０－ヒドロキシデシル、（メタ）アクリル酸１０－ヒドロキシウンデシル、（メタ）アクリル酸１０－ヒドロキシドデシル、アクリル酸１０－ヒドロキシトリデシル、（メタ）アクリル酸１０－ヒドロキシテトラデシルなどの（メタ）アクリル酸１０－ヒドロキシＣ１０－１７アルキル；（メタ）アクリル酸１１－ヒドロキシウンデシル、（メタ）アクリル酸１１－ヒドロキシドデシル、（メタ）アクリル酸１１－ヒドロキシトリデシル、（メタ）アクリル酸１１－ヒドロキシテトラデシル、（メタ）アクリル酸１１－ヒドロキシペンタデシルなどの（メタ）アクリル酸１０－ヒドロキシＣ１１－１８アルキル；（メタ）アクリル酸１２－ヒドロキシドデシル、（メタ）アクリル酸１２－ヒドロキシトリデシル、（メタ）アクリル酸１２－ヒドロキシテトラデシルなどのなどの（メタ）アクリル酸１２－ヒドロキシＣ１２－１９アルキル；（メタ）アクリル酸１３－ヒドロキシペンタデシル、（メタ）アクリル酸１３－ヒドロキシテトラデシル、（メタ）アクリル酸１３－ヒドロキシペンタデシルなどの（メタ）アクリル酸１３－ヒドロキシＣ１３－２０アルキル；（メタ）アクリル酸１４－ヒドロキシテトラデシル、（メタ）アクリル酸１４－ヒドロキシペンタデシルなどの（メタ）アクリル酸１４－ヒドロキシＣ１４－２１アルキル；（メタ）アクリル酸１５－ヒドロキシペンタデシル、（メタ）アクリル酸１５－ヒドロキシヘプタデシルなどの（メタ）アクリル酸１５－ヒドロキシＣ１５－２２アルキルなどが挙げられる。これらのうち、耐久性の観点から、（メタ）アクリル酸５－ヒドロキシペンチル、（メタ）アクリル酸５－ヒドロキシヘキシル、（メタ）アクリル酸５－ヒドロキシヘプチル、（メタ）アクリル酸５－ヒドロキシオクチル、（メタ）アクリル酸５－ヒドロキシノニルなどのｎが５であるヒドロキシ基含有（メタ）アクリルレートが好ましく、特に（メタ）アクリル酸５－ヒドロキシペンチルが好ましい。 Specific examples of the hydroxy group-containing (meth) acrylate (b2) include 5-hydroxypentyl (meth) acrylate, 5-hydroxyhexyl (meth) acrylate, 5-hydroxyheptyl (meth) acrylate, and (meth) acrylic. 5-hydroxyoctyl acid, 5-hydroxy C 5-12 alkyl (meth) acrylate such as 5-hydroxynonyl (meth) acrylate; 6-hydroxyhexyl (meth) acrylate, 6-hydroxyheptyl (meth) acrylate (Meth) acrylic acid 6-hydroxyoctyl, (meth) acrylic acid 6-hydroxynonyl, (meth) acrylic acid 6-hydroxydecyl (meth) acrylic acid 6-hydroxy C 6-13 alkyl; (meth) acrylic Acid 7-hydroxyheptyl, (meth) acrylic acid 7-hydroxyo Chill, (meth) acrylic acid 7-hydroxy-nonyl, (meth) acrylic acid 7-hydroxy decyl (meth) (meth) acrylic acid such as acrylic acid 7-hydroxy undecyl 7-hydroxy C 7-14 alkyl; (meth ) 8-hydroxyoctyl acrylate, 8-hydroxynonyl (meth) acrylate, 8-hydroxydecyl (meth) acrylate, 8-hydroxyundecyl (meth) acrylate, 8-hydroxydodecyl (meth) acrylate, etc. (Meth) acrylic acid 8-hydroxy C 8-15 alkyl; (meth) acrylic acid 9-hydroxynonyl, (meth) acrylic acid 9-hydroxydecyl, (meth) acrylic acid 9-hydroxyundecyl, (meth) acrylic acid Such as 9-hydroxydodecyl and 9-hydroxytridecyl (meth) acrylate Meth) acrylic acid 9-hydroxy C 9-16 alkyl; (meth) acrylate, 12-hydroxylauryl (meth) acrylate, 12-hydroxy undecyl, (meth) acrylic acid 10-hydroxy dodecyl, acrylic acid 10-hydroxy-tri Decyl, 10-hydroxy C 10-17 alkyl (meth) acrylate such as 10-hydroxytetradecyl (meth) acrylate; 11-hydroxyundecyl (meth) acrylate, 11-hydroxydodecyl (meth) acrylate, ( (Meth) acrylic acid 11-hydroxytridecyl, (meth) acrylic acid 11-hydroxytetradecyl, (meth) acrylic acid 11-hydroxypentadecyl and the like (meth) acrylic acid 10-hydroxy C 11-18 alkyl; 12-hydroxydodecyl acrylate (Meth) acrylic acid 12-hydroxy tridecyl, (meth) such as such as acrylic acid 12-hydroxy-tetradecyl (meth) acrylic acid 12-hydroxy C 12-19 alkyl; (meth) acrylic acid 13-hydroxy-pentadecyl, (Meth) acrylic acid 13-hydroxytetradecyl, (meth) acrylic acid 13-hydroxypentadecyl and the like (meth) acrylic acid 13-hydroxy C 13-20 alkyl; (meth) acrylic acid 14-hydroxytetradecyl, (meta ) 14-hydroxy C 14-21 alkyl (meth) acrylate such as 14-hydroxypentadecyl acrylate; (meth) such as 15-hydroxypentadecyl (meth) acrylate, 15-hydroxyheptadecyl (meth) acrylate acrylic acid 15-hydroxy C 15 Such as 2 alkyl. Among these, from the viewpoint of durability, 5-hydroxypentyl (meth) acrylate, 5-hydroxyhexyl (meth) acrylate, 5-hydroxyheptyl (meth) acrylate, 5-hydroxyoctyl (meth) acrylate, Hydroxyl group-containing (meth) acrylates such as 5-hydroxynonyl (meth) acrylate with n = 5 are preferred, and 5-hydroxypentyl (meth) acrylate is particularly preferred.
　好ましい態様では、（メタ）アクリル系樹脂（Ｂ）は、前記式（ｂ１）で表されるヒドロキシ基含有（メタ）アクリレート由来の構成単位と、前記式（ｂ２）で表されるヒドロキシ基含有（メタ）アクリレート由来の構成単位とを含む。この態様では、（メタ）アクリル系樹脂（Ｂ）が、異なる炭素鎖長（ｎ及びｍ）のヒドロキシアルキル基を側鎖に有するため、高温環境における界面の剥がれ（又は浮き）及び発泡をより有効に抑制でき、粘着剤組成物から形成される粘着剤層の耐久性をより向上することが可能となる。さらに、ＩＴＯ等の透明電極層に粘着剤組成物を適用した場合であっても、高温環境下における耐久性をより向上することができる。これは、（メタ）アクリル系樹脂（Ａ）を粘着剤組成物に含有すると、良好な耐久性の発現に最適な架橋構造や架橋密度を有する粘着剤層を形成できるからだと推定される。 In a preferred embodiment, the (meth) acrylic resin (B) comprises a structural unit derived from a hydroxy group-containing (meth) acrylate represented by the formula (b1), and a hydroxy group-containing formula (b2) ( And a structural unit derived from (meth) acrylate. In this aspect, since the (meth) acrylic resin (B) has hydroxyalkyl groups with different carbon chain lengths (n and m) in the side chain, peeling (or floating) of the interface in a high temperature environment and foaming are more effective. And the durability of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition can be further improved. Furthermore, even if it is a case where an adhesive composition is applied to transparent electrode layers, such as ITO, durability in a high temperature environment can be improved more. This is presumed to be because, when the (meth) acrylic resin (A) is contained in the pressure-sensitive adhesive composition, it is possible to form a pressure-sensitive adhesive layer having a cross-linked structure and a cross-linking density optimal for the development of good durability.
　（メタ）アクリル系樹脂を構成する全構成単位１００質量部に対して、前記式（ｂ１）で表されるヒドロキシ基含有（メタ）アクリレート由来の構成単位の割合は好ましくは１．５～５質量部、より好ましくは２～４．５質量部であり、前記式（ｂ２）で表されるヒドロキシ基含有（メタ）アクリレート由来の構成単位の割合は好ましくは０．１～２質量部、より好ましくは０．２５～１質量部である。また、式（ｂ１）で表されるヒドロキシ基含有（メタ）アクリレート由来の構成単位と、式（ｂ２）で表されるヒドロキシ基含有（メタ）アクリレート由来の構成単位との割合（質量比）は、上記範囲であれば特に限定されないが、好ましくは（ｂ１）／（ｂ２）＝１３／１～３／１、より好ましくは１１／１～３／１、さらに好ましくは９／１～４／１、特に７／１～５／１であってもよい。上記範囲であると、粘着剤層の耐久性をより向上できる。 The proportion of the structural unit derived from the hydroxy group-containing (meth) acrylate represented by the formula (b1) with respect to 100 parts by mass of all the structural units constituting the (meth) acrylic resin is preferably 1.5 to 5 masses. Parts, more preferably 2 to 4.5 parts by mass, and the proportion of the structural unit derived from the hydroxy group-containing (meth) acrylate represented by the formula (b2) is preferably 0.1 to 2 parts by mass, more preferably Is 0.25 to 1 part by mass. Moreover, the ratio (mass ratio) of the structural unit derived from the hydroxy group-containing (meth) acrylate represented by the formula (b1) and the structural unit derived from the hydroxy group-containing (meth) acrylate represented by the formula (b2) is The above range is not particularly limited, but preferably (b1) / (b2) = 13/1 to 3/1, more preferably 11/1 to 3/1, still more preferably 9/1 to 4/1. In particular, it may be 7/1 to 5/1. Within the above range, the durability of the pressure-sensitive adhesive layer can be further improved.
　複素環基含有（メタ）アクリレートとしては、例えば、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－ジヒドロフランなどが挙げられる。 Examples of the heterocyclic group-containing (meth) acrylate include acryloylmorpholine, vinylcaprolactam, N-vinyl-2-pyrrolidone, vinylpyridine, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl acrylate, and 3,4-epoxy. Examples include cyclohexylmethyl (meth) acrylate, glycidyl (meth) acrylate, and 2,5-dihydrofuran.
　置換若しくは無置換アミノ基含有（メタ）アクリレートとしては、例えばアミノエチル（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）アクリレートなどが挙げられる。 Examples of the substituted or unsubstituted amino group-containing (meth) acrylate include aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and the like.
　カルボキシル基含有（メタ）アクリレートとしては、例えば（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）などが挙げられる。これらのカルボキシル基含有（メタ）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。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。実質的に含まないとは、（メタ）アクリル系樹脂（Ｂ）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。 Examples of the carboxyl group-containing (meth) acrylate include (meth) acrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, carboxyalkyl (meth) acrylate (for example, carboxyethyl (meth) acrylate, carboxypentyl (meth) ) Acrylate) and the like. These carboxyl group-containing (meth) acrylates can be used alone or in combination of two or more. In addition, it is preferable that the structural unit derived from the monomer which has an amino group is not included substantially from a viewpoint of preventing the fall of the peelability of the separate film which can be laminated | stacked on an adhesive layer. “Substantially not contained” means less than 1.0 part by mass with respect to 100 parts by mass of all the structural units constituting the (meth) acrylic resin (B).
　カルボキシル基含有（メタ）アクリレート由来の構成単位の割合は、（メタ）アクリル系樹脂を構成する全構成単位１００質量部に対して、１．０質量部以下である。カルボキシル基含有（メタ）アクリレート由来の構成単位の割合の上限値は、好ましくは０．５質量部、より好ましくは０．３質量部、さらに好ましくは０．２質量部、特に好ましくは０．１５質量部である。カルボキシル基含有（メタ）アクリレート由来の構成単位の割合の下限値は、好ましくは０質量部、より好ましくは０．００１質量部、さらに好ましくは０．００５質量部、特に好ましくは０．０１質量部、とりわけ０．０５質量部である。カルボキシル基含有（メタ）アクリレート由来の構成単位の割合は、これらの上限値と下限値の任意の組み合わせであってよく、例えば０～１質量部、好ましくは０～０．８質量部、より好ましくは０．００１～０．５質量部、さらに好ましくは０．００５～０．３質量部、特に好ましくは０．０１～０．２質量部、とりわけ０．０５～０．１５質量部であってよい。カルボキシル基含有（メタ）アクリレート由来の構成単位の割合が上限値以下であるとＩＴＯ等の透明電極層の腐食性を抑制でき、下限値以上であると耐久性を向上できる。 The proportion of the structural unit derived from the carboxyl group-containing (meth) acrylate is 1.0 part by mass or less with respect to 100 parts by mass of all the structural units constituting the (meth) acrylic resin. The upper limit of the proportion of structural units derived from carboxyl group-containing (meth) acrylate is preferably 0.5 parts by mass, more preferably 0.3 parts by mass, still more preferably 0.2 parts by mass, and particularly preferably 0.15. Part by mass. The lower limit of the proportion of the structural unit derived from the carboxyl group-containing (meth) acrylate is preferably 0 parts by mass, more preferably 0.001 parts by mass, still more preferably 0.005 parts by mass, particularly preferably 0.01 parts by mass. Especially 0.05 parts by mass. The proportion of the structural unit derived from the carboxyl group-containing (meth) acrylate may be any combination of these upper limit value and lower limit value, for example, 0 to 1 part by mass, preferably 0 to 0.8 part by mass, more preferably Is 0.001 to 0.5 parts by mass, more preferably 0.005 to 0.3 parts by mass, particularly preferably 0.01 to 0.2 parts by mass, especially 0.05 to 0.15 parts by mass. Good. When the proportion of the structural unit derived from the carboxyl group-containing (meth) acrylate is at most the upper limit value, the corrosivity of the transparent electrode layer such as ITO can be suppressed, and when it is at least the lower limit value, the durability can be improved.
　（メタ）アクリルアミド系単量体としては、例えば、Ｎ－メチロールアクリルアミド、Ｎ－（２－ヒドロキシエチル）アクリルアミド、Ｎ－（３－ヒドロキシプロピル）アクリルアミド、Ｎ－（４－ヒドロキシブチル）アクリルアミド、Ｎ－（５－ヒドロキシペンチル）アクリルアミド、Ｎ－（６－ヒドロキシヘキシル）アクリルアミド、Ｎ，Ｎ－ジメチルアクリルアミド、Ｎ，Ｎ－ジエチルアクリルアミド、Ｎ－イソプロピルアクリルアミド、Ｎ－（３－ジメチルアミノプロピル）アクリルアミド、Ｎ－（１，１－ジメチル－３－オキソブチル）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〕アクリルアミド、２－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）アクリルアミド、Ｎ－（エトキシメチル）アクリルアミド、Ｎ－（プロポキシメチル）アクリルアミド、Ｎ－（１－メチルエトキシメチル）アクリルアミド、Ｎ－（１－メチルプロポキシメチル）アクリルアミド、Ｎ－（２－メチルプロポキシメチル）アクリルアミド〔別名：Ｎ－（イソブトキシメチル）アクリルアミド〕、Ｎ－（ブトキシメチル）アクリルアミド、Ｎ－（１，１－ジメチルエトキシメチル）アクリルアミド、Ｎ－（２－メトキシエチル）アクリルアミド、Ｎ－（２－エトキシエチル）アクリルアミド、Ｎ－（２－プロポキシエチル）アクリルアミド、Ｎ－〔２－（１－メチルエトキシ）エチル〕アクリルアミド、Ｎ－〔２－（１－メチルプロポキシ）エチル〕アクリルアミド、Ｎ－〔２－（２－メチルプロポキシ）エチル〕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）アクリルアミド、Ｎ－〔２－（１，１－ジメチルエトキシ）エチル〕アクリルアミドなどが挙げられる。（メタ）アクリルアミド系単量体由来の構造単位を含むことで粘着剤層の耐久性をさらに向上させることができる。特に、これらのうち、Ｎ－（メトキシメチル）アクリルアミド、Ｎ－（エトキシメチル）アクリルアミド、Ｎ－（プロポキシメチル）アクリルアミド、Ｎ－（ブトキシメチル）アクリルアミド、Ｎ－（２－メチルプロポキシメチル）アクリルアミドなどが好ましい。 Examples of (meth) acrylamide monomers include N-methylolacrylamide, N- (2-hydroxyethyl) acrylamide, N- (3-hydroxypropyl) acrylamide, N- (4-hydroxybutyl) acrylamide, N- (5-hydroxypentyl) acrylamide, N- (6-hydroxyhexyl) acrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, N- (3-dimethylaminopropyl) acrylamide, N- (1,1-dimethyl-3-oxobutyl) acrylamide, N- [2- (2-oxo-1-imidazolidinyl) ethyl] acrylamide, 2-acryloylamino-2-methyl-1-propanesulfonic acid, N- (methoxy Methyl) Luamide, N- (ethoxymethyl) acrylamide, N- (propoxymethyl) acrylamide, N- (1-methylethoxymethyl) acrylamide, N- (1-methylpropoxymethyl) acrylamide, N- (2-methylpropoxymethyl) acrylamide [Also known as: N- (isobutoxymethyl) acrylamide], N- (butoxymethyl) acrylamide, N- (1,1-dimethylethoxymethyl) acrylamide, N- (2-methoxyethyl) acrylamide, N- (2-ethoxy Ethyl) acrylamide, N- (2-propoxyethyl) acrylamide, N- [2- (1-methylethoxy) ethyl] acrylamide, N- [2- (1-methylpropoxy) ethyl] acrylamide, N- [2- ( 2-methylpropoxy) ethyl] Riruamido [alias: N- (2-isobutoxy-ethyl) acrylamide], N- (2-butoxyethyl) acrylamide, such as N- [2- (1,1-dimethylethoxy) ethyl] acrylamide. By including a structural unit derived from a (meth) acrylamide monomer, the durability of the pressure-sensitive adhesive layer can be further improved. In particular, among these, N- (methoxymethyl) acrylamide, N- (ethoxymethyl) acrylamide, N- (propoxymethyl) acrylamide, N- (butoxymethyl) acrylamide, N- (2-methylpropoxymethyl) acrylamide, etc. preferable.
　（メタ）アクリルアミド系単量体由来の構成単位の割合は、（メタ）アクリル系樹脂を構成する全構成単位１００質量部に対して、好ましくは５質量部以下である。（メタ）アクリルアミド系単量体由来の構成単位の割合の上限値は、好ましくは３質量部、より好ましくは２質量部、さらに好ましくは１質量部である。（メタ）アクリルアミド系単量体由来の構成単位の割合の下限値は、好ましくは０質量部、より好ましくは０．００１質量部、さらに好ましくは０．０１質量部、特に好ましくは０．１質量部である。（メタ）アクリルアミド系単量体由来の構成単位の割合は、これらの上限値と下限値の任意の組み合わせであってよく、例えば０～５質量部、好ましくは０．００１～３質量部、より好ましくは０．０１～２質量部、さらに好ましくは０．１～１質量部であってよい。（メタ）アクリルアミド系単量体由来の構成単位の割合が上記範囲であると、粘着剤層の耐久性をさらに向上できる。 The proportion of the structural unit derived from the (meth) acrylamide monomer is preferably 5 parts by mass or less with respect to 100 parts by mass of all the structural units constituting the (meth) acrylic resin. The upper limit of the proportion of the structural unit derived from the (meth) acrylamide monomer is preferably 3 parts by mass, more preferably 2 parts by mass, and even more preferably 1 part by mass. The lower limit of the proportion of the structural unit derived from the (meth) acrylamide monomer is preferably 0 parts by mass, more preferably 0.001 parts by mass, still more preferably 0.01 parts by mass, particularly preferably 0.1 parts by mass. Part. The proportion of the structural unit derived from the (meth) acrylamide monomer may be any combination of these upper limit value and lower limit value, for example, 0 to 5 parts by mass, preferably 0.001 to 3 parts by mass. The amount may be preferably 0.01 to 2 parts by mass, more preferably 0.1 to 1 part by mass. When the proportion of the structural unit derived from the (meth) acrylamide monomer is within the above range, the durability of the pressure-sensitive adhesive layer can be further improved.
　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、オクチルスチレンなど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、ヨードスチレンなど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；ジビニルベンゼンなどが挙げられる。 Examples of the styrenic monomer include styrene; alkyl styrene such as methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, octyl styrene; fluoro Halogenated styrene such as styrene, chlorostyrene, bromostyrene, dibromostyrene, iodostyrene; nitrostyrene; acetylstyrene; methoxystyrene; divinylbenzene, and the like.
　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、ラウリン酸ビニルなどの脂肪酸ビニルエステル；塩化ビニル、臭化ビニルなどのハロゲン化ビニル；塩化ビニリデンなど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などの含窒素芳香族ビニル；ブタジエン、イソプレン、クロロプレンなどの共役ジエン単量体；アクリロニトリル、メタクリロニトリルなどの不飽和ニトリルなどが挙げられる。 Examples of vinyl monomers include 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 chloride And vinylidene halides such as vinyl pyridine, vinyl pyrrolidone, vinyl carbazole, and the like; conjugated diene monomers such as butadiene, isoprene, and chloroprene; and unsaturated nitriles such as acrylonitrile and methacrylonitrile.
　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）アクリレートなどの分子内に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）アクリレートなどの分子内に３個の（メタ）アクリロイル基を有する単量体などが挙げられる。 Examples of the monomer having a plurality of (meth) acryloyl groups in the molecule include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol. 2 (meth) acryloyl in the molecule such as di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate A monomer having a group; a monomer having three (meth) acryloyl groups in a molecule such as trimethylolpropane tri (meth) acrylate;
　アルキルアクリレートとしては、例えばホモポリマーのガラス転移温度（Ｔｇ）が０℃未満のアルキルアクリレート（ｂ３）、ホモポリマーのＴｇが０℃以上であるアルキルアクリレート（ｂ４）等が挙げられる。 Examples of the alkyl acrylate include an alkyl acrylate (b3) having a glass transition temperature (Tg) of the homopolymer of less than 0 ° C., and an alkyl acrylate (b4) having a Tg of the homopolymer of 0 ° C. or more.
　ホモポリマーのガラス転移温度（Ｔｇ）が０℃未満のアルキルアクリレート（ｂ３）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。アルキルアクリレート（ｂ３）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、特にｎ－ブチルアルキルアクリレートが好ましい。ｎ－ブチル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（ｂ３）は単独又は二種以上組み合わせて使用できる。 Examples of the alkyl acrylate (b3) having a glass transition temperature (Tg) of the homopolymer of less than 0 ° C. include ethyl acrylate, n- and i-propyl acrylate, n- and i-butyl acrylate, n-pentyl acrylate, n- And alkyl such as 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 Examples thereof include linear or branched alkyl acrylates having a group having about 2 to 12 carbon atoms. The alkyl acrylate (b3) may be an alkyl acrylate (cycloalkyl acrylate) having an alicyclic structure, but has a carbon number of 2 to 10 from the viewpoint of followability (or flexibility and adhesiveness) to the optical film. Alkyl acrylates, preferably alkyl acrylates having 3 to 8 carbon atoms, more preferably alkyl acrylates having 4 to 6 carbon atoms, particularly n-butyl alkyl acrylate. When n-butyl alkyl acrylate is used, the followability can be enhanced, and for example, it is advantageous in peeling resistance. These alkyl acrylates (b3) can be used alone or in combination of two or more.
　ホモポリマーのＴｇが０℃以上であるアルキルアクリレート（ｂ４）としては、メチルアクリレート、シクロアルキルアクリレート（例えばシクロヘキシルアクリレート、イソボロニルアクリレート）、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、特にメチルアクリレートが特に好ましい。メチルアクリレートを用いると、強度を高くでき、例えば凝集破壊に対して有利である。これらのアルキルアクリレート（ｂ４）は単独又は二種以上組み合わせて使用できる。なお、アルキルアクリレートのホモポリマーのＴｇは、例えばＰＯＬＹＭＥＲ　ＨＡＮＤＢＯＯＫ（Ｗｉｌｅｙ－Ｉｎｔｅｒｓｃｉｅｎｃｅ）などの文献値を参照できる。 Examples of the alkyl acrylate (b4) whose Tg of the homopolymer is 0 ° C. or higher include methyl acrylate, cycloalkyl acrylate (for example, cyclohexyl acrylate, isobornyl acrylate), stearyl acrylate, t-butyl acrylate, etc., particularly methyl acrylate Is particularly preferred. When methyl acrylate is used, the strength can be increased, which is advantageous for cohesive failure, for example. These alkyl acrylates (b4) can be used alone or in combination of two or more. For the Tg of the alkyl acrylate homopolymer, reference values such as POLYMER HANDBOOK (Wiley-Interscience) can be referred to.
　好ましい態様では、（メタ）アクリル系樹脂（Ａ）は、粘着剤層の耐久性向上の観点から、ホモポリマーのガラス転移温度が０℃未満のアルキルアクリレート（ｂ３）由来の構成単位と、ホモポリマーのガラス転移温度が０℃以上のアルキルアクリレート（ｂ４）由来の構成単位とを含む。ホモポリマーのＴｇが０℃未満であるアルキルアクリレートと、ホモポリマーのＴｇが０℃以上のアルキルアクリレートを併用すると、耐凝集破壊性及び追従性（耐発泡性及び耐剥がれ性）を両立でき、光学フィルム（例えば偏光板）の寸法変化に対する耐久性を向上できる。 In a preferred embodiment, the (meth) acrylic resin (A) comprises a structural unit derived from an alkyl acrylate (b3) having a glass transition temperature of less than 0 ° C. and a homopolymer from the viewpoint of improving the durability of the pressure-sensitive adhesive layer. And a structural unit derived from alkyl acrylate (b4) having a glass transition temperature of 0 ° C. or higher. When an alkyl acrylate having a homopolymer Tg of less than 0 ° C and an alkyl acrylate having a homopolymer Tg of 0 ° C or higher are used in combination, both cohesive fracture resistance and follow-up properties (foaming resistance and peeling resistance) can be achieved. The durability against dimensional changes of a film (for example, a polarizing plate) can be improved.
　（メタ）アクリル系樹脂（Ｂ）におけるアルキルアクリレート由来の構成単位の割合は、粘着剤層の耐久性及びリワーク性の観点から、（メタ）アクリル系樹脂（Ｂ）を構成する全構成単位１００質量部に対して、好ましくは４０質量部以上、より好ましくは５０質量部以上、さらに好ましくは６０質量部以上、特に好ましくは７０質量部以上、とりわけ８０質量部以上であり、好ましくは９８質量部以下、より好ましくは９５質量部以下、さらに好ましくは９０質量部以下であり、これらの下限値と上限値の任意の組み合わせであってよく、例えば５０～９８質量部、好ましくは７０～９５質量部、さらに好ましくは８０～９０質量部であってもよい。 The proportion of the structural units derived from the alkyl acrylate in the (meth) acrylic resin (B) is 100 masses of all structural units constituting the (meth) acrylic resin (B) from the viewpoints of durability and reworkability of the pressure-sensitive adhesive layer. Part is preferably 40 parts by weight or more, more preferably 50 parts by weight or more, still more preferably 60 parts by weight or more, particularly preferably 70 parts by weight or more, especially 80 parts by weight or more, preferably 98 parts by weight or less. More preferably 95 parts by mass or less, and still more preferably 90 parts by mass or less, and any combination of these lower limit value and upper limit value, for example, 50 to 98 parts by mass, preferably 70 to 95 parts by mass, More preferably, it may be 80 to 90 parts by mass.
　ホモポリマーのガラス転移温度が０℃未満のアルキルアクリレート（ｂ３）由来の構成単位と、ガラス転移温度が０℃以上のアルキルアクリレート（ｂ４）由来の構成単位との割合（質量比）は、好ましくは（ｂ３）／（ｂ４）＝２０／８０～９５／５、より好ましくは３０／７０～９０／１０、さらに好ましくは３０／７０～８５／１５、特に３０／７０～７０／３０である。上記範囲であると、耐久性をさらに向上できる。ガラス転移温度が０℃未満のアルキルアクリレート（ｂ３）由来の構成単位の割合が大きくなるほど、追従性が向上する。ガラス転移温度が０℃以上のアルキルアクリレート（ｂ４）由来の構成単位の割合が大きくなるほど、耐凝集破壊性が向上する。 The ratio (mass ratio) between the structural unit derived from the alkyl acrylate (b3) having a glass transition temperature of less than 0 ° C. and the structural unit derived from the alkyl acrylate (b4) having a glass transition temperature of 0 ° C. or higher is preferably (B3) / (b4) = 20/80 to 95/5, more preferably 30/70 to 90/10, still more preferably 30/70 to 85/15, particularly 30/70 to 70/30. When it is in the above range, the durability can be further improved. The followability improves as the proportion of the structural unit derived from the alkyl acrylate (b3) having a glass transition temperature of less than 0 ° C. increases. As the proportion of the structural unit derived from the alkyl acrylate (b4) having a glass transition temperature of 0 ° C. or higher is increased, the cohesive fracture resistance is improved.
　置換基含有アルキルアクリレートとしては、例えば、前記アルキル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）アルキルアクリレートが挙げられる。該置換基は、例えば、アリール基（フェニル基など）、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、エトキシ基など）等が挙げられる。置換基含有アルキルアクリレートとしては、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）、アリールアルキルアクリレート（例えばベンジ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。これらの置換基含有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、ベンジル基、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、アルコキシ基、アリールオキシ基などを含むことで粘着剤層に帯電防止剤を添加した際の帯電防止性を向上させることができる。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Ｃ１－６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と帯電防止性とのバランスの観点から、例えば１～７、好ましくは１～５、特に１～２である。具体的には、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Ｃ１－３アルキレングリコールアクリレート、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Ｃ１－３アルキレンモノアクリレートなどが挙げられる。本発明で用いる置換基含有アルキルアクリレートとしては、耐久性、耐白抜け性、帯電防止性のバランスの観点から、フェノキシエチルアクリレート、フェノキシジエチレングリコールアクリレートであることが特に好ましい。 Examples of the substituent-containing alkyl acrylate include alkyl acrylate in which a substituent is introduced into the alkyl group in the alkyl acrylate (a hydrogen atom of the alkyl group is substituted with a substituent). Examples of the substituent include an aryl group (such as a phenyl group), an aryloxy group (phenoxy group), an alkoxy group (such as a methoxy group and an ethoxy group), and the like. Examples of the substituent-containing alkyl acrylate include alkoxyalkyl acrylate (such as 2-methoxyethyl acrylate and ethoxymethyl acrylate), arylalkyl acrylate (such as benzyl acrylate), aryloxyalkyl acrylate (such as phenoxyethyl acrylate), and aryloxypolyacrylate. Examples include alkylene glycol monoacrylate and polyalkylene glycol monoacrylate. These substituent-containing alkyl acrylates can be used alone or in combination of two or more. By including an alkyl acrylate containing an aromatic ring such as an aryl group, a benzyl group, or an aryloxy group, white spots of the polarizing plate during the durability test can be improved. Moreover, the antistatic property at the time of adding an antistatic agent to an adhesive layer can be improved by including an alkoxy group, an aryloxy group, etc. The alkylene group of the aryloxy polyalkylene glycol monoacrylate and the polyalkylene glycol monoacrylate may be, for example, a C 1-6 alkylene group (preferably an ethylene group) such as a methylene group, an ethylene group or a propylene group. The repeating unit of the alkylene group is, for example, 1 to 7, preferably 1 to 5, particularly 1 to 2 from the viewpoint of the balance between durability and antistatic property of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition. Specific examples include phenoxy di to hepta C 1-3 alkylene glycol acrylate such as phenoxy diethylene glycol acrylate, di to hepta C 1-3 alkylene mono acrylate such as diethylene glycol monoacrylate, and the like. The substituent-containing alkyl acrylate used in the present invention is particularly preferably phenoxyethyl acrylate or phenoxydiethylene glycol acrylate from the viewpoint of the balance of durability, white spot resistance, and antistatic properties.
　置換基含有アルキルアクリレート由来の構成単位の割合は、（メタ）アクリル系樹脂（Ｂ）を構成する全構成単位１００質量部に対して、例えば０～３０質量部、好ましくは１～２５質量部、より好ましくは３～２０質量部、さらに好ましくは５～１５質量部である。 The proportion of the structural unit derived from the substituent-containing alkyl acrylate is, for example, 0 to 30 parts by weight, preferably 1 to 25 parts by weight with respect to 100 parts by weight of all the structural units constituting the (meth) acrylic resin (B). The amount is more preferably 3 to 20 parts by mass, still more preferably 5 to 15 parts by mass.
　（メタ）アクリル系樹脂（Ｂ）は、ゲルパーミエイションクロマトグラフィーＧＰＣによる標準ポリスチレン換算の重量平均分子量（Ｍｗ）は、粘着剤層の耐久性をより高めるために１００万以上であることが好ましい。Ｍｗの下限値はより好ましくは１１０万、さらに好ましくは１２０万、特に１３０万である。また、Ｍｗの上限値については特に制限されないが、粘着剤組成物を例えばシート状に加工する（基材に塗工する）際の塗工性の観点から、好ましくは２５０万、より好ましくは２２０万、さらに好ましくは２００万である。Ｍｗは、これらの上限値と下限値の任意の組み合わせであってよく、例えば１００～２５０万、より好ましくは１１０万～２２０万、さらに好ましくは１３０～２００万であってよい。また、重量平均分子量Ｍｗと数平均分子量Ｍｎとの比（Ｍｗ／Ｍｎ）で表される分子量分布は、通常２～１０、好ましくは３～８、さらに好ましくは４～６である。 In the (meth) acrylic resin (B), the weight average molecular weight (Mw) in terms of standard polystyrene by gel permeation chromatography GPC is preferably 1 million or more in order to further improve the durability of the pressure-sensitive adhesive layer. . The lower limit value of Mw is more preferably 1.1 million, still more preferably 1.2 million, and particularly 1.3 million. Further, the upper limit value of Mw is not particularly limited, but is preferably 2.5 million, more preferably 220, from the viewpoint of coatability when the pressure-sensitive adhesive composition is processed into a sheet (for example, coated on a substrate). Million, more preferably 2 million. Mw may be an arbitrary combination of these upper limit value and lower limit value, and may be, for example, 1 to 2.5 million, more preferably 1.1 million to 2.2 million, and still more preferably 1.3 to 2 million. The molecular weight distribution represented by the ratio of the weight average molecular weight Mw to the number average molecular weight Mn (Mw / Mn) is usually 2 to 10, preferably 3 to 8, and more preferably 4 to 6.
　また、（メタ）アクリル系樹脂（Ｂ）は、ＧＰＣにおける排出曲線上のＭｗが１．０×１０３～２．５×１０６の範囲において単一のピークを有することが好ましい。該ピーク数が１である（メタ）アクリル系樹脂（Ｂ）を用いると、粘着剤層の耐久性向上に有利である。 Further, the (meth) acrylic resin (B) preferably has a single peak in the range of 1.0 × 10 3 to 2.5 × 10 6 of Mw on the GPC emission curve. Use of the (meth) acrylic resin (B) having a peak number of 1 is advantageous for improving the durability of the pressure-sensitive adhesive layer.
　得られた排出曲線の上記範囲において「単一のピークを有する」とは、Ｍｗ１．０×１０３～２．５×１０６の範囲において極大値を１つしか持たないことを意味する。本明細書では、ＧＰＣ排出曲線において、Ｓ／Ｎ比が３０以上のものをピークと定義する。なお、ＧＰＣ排出曲線のピーク数及び（メタ）アクリル系樹脂（Ｂ）のＭｗ及びＭｎは、実施例の項に記載のＧＰＣ測定条件により求めることができる。 “Having a single peak” in the above range of the obtained discharge curve means having only one maximum value in the range of Mw 1.0 × 10 3 to 2.5 × 10 6 . In the present specification, a peak having an S / N ratio of 30 or more in the GPC emission curve is defined. The number of peaks in the GPC discharge curve and the Mw and Mn of the (meth) acrylic resin (B) can be determined according to the GPC measurement conditions described in the Examples section.
　（メタ）アクリル系樹脂（Ｂ）は、酢酸エチルに溶解させ、濃度２０質量％の溶液としたとき、２５℃における粘度が、２０Ｐａ・ｓ以下であることが好ましく、０．１～７Ｐａ・ｓであることがより好ましい。該範囲の粘度であると、粘着剤組成物を基材に塗工する際の塗工性の観点から有利である。なお、粘度は、ブルックフィールド粘度計により測定できる。 When the (meth) acrylic resin (B) is dissolved in ethyl acetate to form a solution having a concentration of 20% by mass, the viscosity at 25 ° C. is preferably 20 Pa · s or less, preferably 0.1 to 7 Pa · s. It is more preferable that When the viscosity is within this range, it is advantageous from the viewpoint of coatability when the pressure-sensitive adhesive composition is applied to a substrate. The viscosity can be measured with a Brookfield viscometer.
　（メタ）アクリル系樹脂（Ｂ）のガラス転移温度（Ｔｇ）は、例えば－６０～０℃、好ましくは－５０～－１０℃、より好ましくは－５０～－２０℃、さらに好ましくは－４０～－２０℃、特に－４０～－２５℃であってもよい。Ｔｇが上記範囲であると、粘着剤層の耐久性の向上に有利である。なお、ガラス転移温度は示差走査熱量計（ＤＳＣ）により測定できる。 The glass transition temperature (Tg) of the (meth) acrylic resin (B) is, for example, −60 to 0 ° C., preferably −50 to −10 ° C., more preferably −50 to −20 ° C., and further preferably −40 to It may be −20 ° C., in particular −40 to −25 ° C. When Tg is in the above range, it is advantageous for improving the durability of the pressure-sensitive adhesive layer. The glass transition temperature can be measured with a differential scanning calorimeter (DSC).
　（メタ）アクリル系樹脂（Ｂ）は、例えば、溶液重合法、塊状重合法、懸濁重合法、乳化重合法などの公知の方法によって製造することができ、特に溶液重合法が好ましい。溶液重合法としては、例えば、単量体及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、４０～９０℃、好ましくは５０～８０℃程度の温度条件下、３～１５時間程度攪拌する方法が上げられる。反応制御のため、重合中、連続的又は間歇的に単量体や熱重合開始剤を添加してもよい。該単量体や熱開始剤は有機溶媒に添加した状態であってもよい。 The (meth) acrylic resin (B) can be produced by a known method such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, and the solution polymerization method is particularly preferable. As the solution polymerization method, for example, a monomer and an organic solvent are mixed, a thermal polymerization initiator is added in a nitrogen atmosphere, and the temperature is about 40 to 90 ° C., preferably about 50 to 80 ° C. The method of stirring for about an hour is raised. In order to control the reaction, a monomer or a thermal polymerization initiator may be added continuously or intermittently during the polymerization. The monomer or thermal initiator may be added to an organic solvent.
　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は、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）ケトンなどが挙げられる。熱重合開始剤としては、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）などのアゾ系化合物；ラウリルパーオキサイド、ｔ－ブチルハイドロパーオキサイド、過酸化ベンゾイル、ｔ－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、ｔ－ブチルパーオキシネオデカノエート、ｔ－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）パーオキサイドなどの有機過酸化物；過硫酸カリウム、過硫酸アンモニウム、過酸化水素などの無機過酸化物などが挙げられる。また、過酸化物と還元剤とを併用したレドックス系開始剤なども使用できる。 As the polymerization initiator, a thermal polymerization initiator, a photopolymerization initiator, or the like is used. Examples of the photopolymerization initiator include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone. Examples of the thermal polymerization initiator include 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-methylpro) Azo compounds such as 2,2′-azobis (2-hydroxymethylpropionitrile); lauryl peroxide, t-butyl hydroperoxide, benzoyl peroxide, t-butyl peroxybenzoate, cumene hydroper Oxide, diisopropyl peroxydicarbonate, dipropyl peroxydicarbonate, t-butyl peroxy Organic peroxides such as neodecanoate, t-butyl peroxypivalate, (3,5,5-trimethylhexanoyl) peroxide; inorganic peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide . Moreover, the redox initiator etc. which used the peroxide and the reducing agent together can also be used.
　重合開始剤の割合は、（メタ）アクリル系樹脂を構成する単量体の総量１００質量部に対して、０．００１～５質量部程度である。（メタ）アクリル系樹脂の重合は、活性エネルギー線（例えば紫外線など）による重合法を使用してもよい。 The ratio of the polymerization initiator is about 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of monomers constituting the (meth) acrylic resin. For the polymerization of the (meth) acrylic resin, a polymerization method using active energy rays (for example, ultraviolet rays) may be used.
　有機溶媒としては、例えば、トルエン、キシレンなどの芳香族炭化水素類；酢酸エチル、酢酸ブチルなどのエステル類；プロピルアルコール、イソプロピルアルコールなどの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などのケトン類などが挙げられる。 Examples of the organic solvent 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; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. And the like.
　［１－３］架橋剤（Ｃ）
　粘着剤組成物は、架橋剤（Ｃ）を含むことができる。該架橋剤（Ｃ）は、（メタ）アクリル系樹脂（Ｂ）中の反応性基（例えばヒドロキシル基等）と反応する。架橋剤（Ｃ）は（メタ）アクリル系樹脂等と架橋構造を形成し、耐久性やリワーク性に有利な架橋構造を形成する。 [1-3] Crosslinking agent (C)
The pressure-sensitive adhesive composition can contain a crosslinking agent (C). The crosslinking agent (C) reacts with a reactive group (for example, a hydroxyl group) in the (meth) acrylic resin (B). The crosslinking agent (C) forms a crosslinked structure with a (meth) acrylic resin or the like, and forms a crosslinked structure advantageous for durability and reworkability.
　架橋剤（Ｃ）としては、慣用の架橋剤（例えば、イソシアネート化合物、エポキシ化合物、アジリジン化合物、金属キレート化合物、過酸化物など）が挙げられ、特に粘着剤組成物のポットライフ及び粘着剤層の耐久性、架橋速度などの観点から、イソシアネート系化合物であることが好ましい。 Examples of the crosslinking agent (C) include conventional crosslinking agents (for example, isocyanate compounds, epoxy compounds, aziridine compounds, metal chelate compounds, peroxides, etc.), and particularly the pot life of the pressure-sensitive adhesive composition and the pressure-sensitive adhesive layer. From the viewpoints of durability, crosslinking speed and the like, an isocyanate compound is preferable.
　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など）、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、水添ジフェニルメタンジイソシアネート、水添キシリレ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）などが挙げられる。また架橋剤（Ｃ）は、前記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などによる付加体］、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などの誘導体であってもよい。架橋剤（Ｃ）は単独又は二種以上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）又はこれら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）による付加体、又はイソシアヌレート体が挙げられる。架橋剤（Ｃ）が、芳香族イソシアネート系化合物及び／又はこれらの多価アルコール化合物、又はイソシアヌレート体による付加体であると、最適な架橋密度（又は架橋構造）の形成に有利なためか、粘着剤層の耐久性を向上できる。特に、トリレンジイソシアネート系化合物及び／又はこれらの多価アルコール化合物による付加体であると、例えば粘着剤層を透明電極に適用した場合等であっても耐久性を向上することができる。 The isocyanate compound is preferably a compound having at least two isocyanato groups (—NCO) in the molecule. For example, an aliphatic isocyanate compound (eg, hexamethylene diisocyanate), an alicyclic isocyanate compound (eg, isophorone diisocyanate). , Hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate), aromatic isocyanate compounds (for example, tolylene diisocyanate, xylylene diisocyanate diphenylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, etc.). The crosslinking agent (C) is an adduct (adduct) of the isocyanate compound with a polyhydric alcohol compound [for example, an adduct with glycerol, trimethylolpropane or the like], an isocyanurate, a burette type compound, a polyether polyol, or a polyester. It may be a derivative such as a urethane prepolymer type isocyanate compound obtained by addition reaction with a polyol, an acrylic polyol, a polybutadiene polyol, a polyisoprene polyol or the like. A crosslinking agent (C) can be used individually or in combination of 2 or more types. Of these, typically, aromatic isocyanate compounds (for example, tolylene diisocyanate, xylylene diisocyanate), aliphatic isocyanate compounds (for example, hexamethylene diisocyanate) or their polyhydric alcohol compounds (for example, glycerol, trimethylolpropane). ) Or isocyanurate. If the crosslinking agent (C) is an adduct of an aromatic isocyanate compound and / or a polyhydric alcohol compound thereof, or an isocyanurate, it is advantageous for forming an optimal crosslinking density (or crosslinked structure), The durability of the pressure-sensitive adhesive layer can be improved. In particular, when it is an adduct of a tolylene diisocyanate compound and / or these polyhydric alcohol compounds, durability can be improved even when, for example, the pressure-sensitive adhesive layer is applied to a transparent electrode.
　架橋剤（Ｃ）の割合は、（メタ）アクリル系樹脂（Ｂ）１００質量部に対して、好ましくは０．０１質量部以上、より好ましくは０．０５質量部以上、さらに好ましくは０．１質量部以上、特に好ましくは０．２質量部以上、とりわけ０．３質量部以上であり、好ましくは１０質量部以下、より好ましくは５質量部以下、さらに好ましくは３質量部以下、特に好ましくは２質量部以下、極めて好ましくは１質量部以下、とりわけ０．８質量部以下であり、これらの下限値と上限値の任意の組合せであってよく、例えば０．０１～１０質量部、好ましくは０．０５～５質量部、より好ましくは０．１～３質量部、さらに好ましくは０．１～２質量部、特に好ましくは０．２～１質量部、とりわけ０．３～０．８質量部であってもよい。上限値以下であると、追従性（又は耐剥がれ性）の向上に有利であり、下限値以上であると、耐凝集性（又は耐発泡性）やリワーク性の向上に有利である。 The ratio of the crosslinking agent (C) is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and further preferably 0.1 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin (B). Part by mass or more, particularly preferably 0.2 part by mass or more, especially 0.3 part by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, particularly preferably. 2 parts by weight or less, very preferably 1 part by weight or less, especially 0.8 parts by weight or less, and any combination of these lower limit values and upper limit values, for example, 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, further preferably 0.1 to 2 parts by mass, particularly preferably 0.2 to 1 part by mass, especially 0.3 to 0.8 parts by mass. Part. When it is at most the upper limit value, it is advantageous for improving followability (or peeling resistance), and when it is at least the lower limit value, it is advantageous for improving aggregation resistance (or foam resistance) and reworkability.
　［１－４］シラン化合物（Ｄ）
　粘着剤組成物は、シロキサン化合物（Ａ）以外のシラン化合物（Ｄ）を含むことができる。 [1-4] Silane compound (D)
The pressure-sensitive adhesive composition can contain a silane compound (D) other than the siloxane compound (A).
　シラン化合物（Ｄ）は、（メタ）アクリル系樹脂（Ｂ）の反応性基（例えばヒドロキシル基）と結合可能なシラン化合物、好ましくは分子中に少なくとも１つ以上のアルコキシ基を有するシラン化合物であってよく、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、１，３－ビス（３’－トリメトキシプロピル）ウレアなどが挙げられる。 The silane compound (D) is a silane compound capable of binding to a reactive group (for example, a hydroxyl group) of the (meth) acrylic resin (B), preferably a silane compound having at least one alkoxy group in the molecule. For example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyl Methyldimethoxysilane, 3-glycidoxypropylethoxydimethylsilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyl Trime Kishishiran, 3-mercaptopropyl trimethoxysilane, 1,3-bis (3'-trimethoxy propyl) urea and the like.
　また、シラン化合物（Ｄ）は、シリコーンオリゴマータイプの化合物であってもよく、該シリコーンオリゴマーをモノマー同士の組み合わせで表記すると、例えば、３－メルカプトプロピルジ又は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－メルカプトメチルジ又は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ジ又は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－メルカプトメチルジ又はトリエトキシシラン－テトラエトキシシランオリゴマーなどのメルカプトアルキル基含有オリゴマー；該メルカプトアルキル基含有オリゴマーのメルカプトアルキル基を、他の置換基［３－グリジドキシプロピル基、（メタ）クリロイルオキシプロピル基、ビニル基、アミノ基など］に置き換えたオリゴマーなどが挙げられる。 The silane compound (D) may be a silicone oligomer type compound. When the silicone oligomer is represented by a combination of monomers, for example, 3-mercaptopropyldi or trimethoxysilane-tetramethoxysilane oligomer, 3 -Mercaptoalkyl group-containing oligomers such as mercaptomethyldi or trimethoxysilane-tetraethoxysilane oligomer, 3-mercaptopropyldi or triethoxysilane-tetramethoxysilane oligomer, 3-mercaptomethyldi or triethoxysilane-tetraethoxysilane oligomer The mercaptoalkyl group of the mercaptoalkyl group-containing oligomer is substituted with other substituents [3-glycidoxypropyl group, (meth) acryloyloxypropyl group, vinyl group, amino group, etc. Such as oligomers were replaced with, and the like.
　［１－５］帯電防止剤
　粘着剤組成物は、帯電防止剤をさらに含んでいてもよい。帯電防止剤を含むことで、粘着剤の帯電防止性を向上（例えば離形フィルム、保護フィルムなどを剥離した際に生じる静電気による不具合などを抑制）することができる。帯電防止剤としては、慣用のものが挙げられ、イオン性帯電防止剤が好適である。イオン性帯電防止剤を構成するカチオン成分としては、有機カチオン、無機カチオンなどが挙げられる。有機カチオンとしては、例えばピリジニウムカチオン、イミダゾリウムカチオン、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などが挙げられる。無機カチオンとしては、例えばリチウムカチオン、カリウムカチオン、ナトリウムカチオン、セシウムカチオンなどのアルカリ金属カチオン、マグネシウムカチオン、カルシウムカチオンなどのアルカリ土類金属カチオンなどが挙げられる。イオン性帯電防止剤を構成するアニオン成分としては、無機アニオン及び有機アニオンのいずれでもよいが、帯電防止性能に優れるという点で、フッ素原子を含むアニオン成分が好ましい。フッ素原子を含むアニオン成分としては、例えばヘキサフルオロホスフェートアニオン（ＰＦ６ －）、ビス（トリフルオロメタンスルホニル）イミドアニオン［（ＣＦ３ＳＯ２）２Ｎ－］、ビス（フルオロスルホニル）イミドアニオン［（ＦＳＯ２）２Ｎ－］、テトラ(ペンタフルオロフェニル)ボレートアニオン[（Ｃ６Ｆ５）４Ｂ－]などが挙げられる。これらの帯電防止剤は単独又は二種以上組み合わせて使用できる。特に、ビス（トリフルオロメタンスルホニル）イミドアニオン［（ＣＦ３ＳＯ２）２Ｎ－］、ビス（フルオロスルホニル）イミドアニオン［（ＦＳＯ２）２Ｎ－］、テトラ(ペンタフルオロフェニル)ボレートアニオン[（Ｃ６Ｆ５）４Ｂ－]が好ましい。粘着剤組成物から形成される粘着剤層の帯電防止性能の経時安定性に優れるという点で、室温で固体であるイオン性帯電防止剤が好ましい。 [1-5] Antistatic Agent The pressure-sensitive adhesive composition may further contain an antistatic agent. By including the antistatic agent, the antistatic property of the pressure-sensitive adhesive can be improved (for example, a problem caused by static electricity generated when a release film, a protective film, or the like is peeled off) can be suppressed. Examples of the antistatic agent include conventional ones, and an ionic antistatic agent is preferable. Examples of the cation component constituting the ionic antistatic agent include organic cations and inorganic cations. Examples of the organic cation include a pyridinium cation, an imidazolium cation, an ammonium cation, a sulfonium cation, and a phosphonium cation. Examples of the inorganic cation include alkali metal cations such as lithium cation, potassium cation, sodium cation and cesium cation, and alkaline earth metal cations such as magnesium cation and calcium cation. The anionic component constituting the ionic antistatic agent may be either an inorganic anion or an organic anion, but an anionic component containing a fluorine atom is preferred from the viewpoint of excellent antistatic performance. Examples of the anion component containing a fluorine atom include hexafluorophosphate anion (PF 6 − ), bis (trifluoromethanesulfonyl) imide anion [(CF 3 SO 2 ) 2 N − ], bis (fluorosulfonyl) imide anion [(FSO 2 ) 2 N − ], tetra (pentafluorophenyl) borate anion [(C 6 F 5 ) 4 B − ] and the like. These antistatic agents can be used alone or in combination of two or more. In particular, bis (trifluoromethanesulfonyl) imide anion [(CF 3 SO 2 ) 2 N − ], bis (fluorosulfonyl) imide anion [(FSO 2 ) 2 N − ], tetra (pentafluorophenyl) borate anion [(C 6 F 5 ) 4 B − ] is preferred. An ionic antistatic agent that is solid at room temperature is preferable in that the antistatic performance of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition is excellent over time.
　帯電防止剤の割合は、（メタ）アクリル系樹脂（Ｂ）１００質量部に対して、例えば、０．０１～１０質量部、好ましくは０．１～５質量部、さらに好ましくは１～３質量部である。 The proportion of the antistatic agent is, for example, 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and more preferably 1 to 3 parts by weight with respect to 100 parts by weight of the (meth) acrylic resin (B). Part.
　本発明の粘着剤組成物は、帯電防止剤を含んでいても、高温環境下における良好な耐久性を示す。このため、良好な耐久性と帯電防止性能とを両立することができる。 The pressure-sensitive adhesive composition of the present invention exhibits good durability in a high temperature environment even when it contains an antistatic agent. For this reason, it is possible to achieve both good durability and antistatic performance.
　［１－６］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、光散乱性微粒子等の添加剤を単独又は２種以上含むことができる。また、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。 [1-6] Other components The pressure-sensitive adhesive composition comprises a solvent, a crosslinking catalyst, an ultraviolet absorber, a weathering stabilizer, a tackifier, a plasticizer, a softener, a dye, a pigment, an inorganic filler, light scattering fine particles, and the like. An agent can be contained alone or in combination of two or more. It is also useful to blend an ultraviolet curable compound into the pressure-sensitive adhesive composition and form a pressure-sensitive adhesive layer and then cure it by irradiating with ultraviolet rays to form a harder pressure-sensitive adhesive layer. Examples of the crosslinking catalyst include amine compounds such as hexamethylenediamine, ethylenediamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethylenetetramine, isophoronediamine, trimethylenediamine, polyamino resin, and melamine resin.
　粘着剤組成物は、粘着剤層の耐金属腐食性を高めるという観点から防錆剤を含むことができる。防錆剤としては、例えば、ベンゾトリアゾール系化合物などのトリアゾール系化合物；ベンゾチアゾール系化合物などのチアゾール系化合物；ベンジルイミダゾール系化合物などのイミダゾール系化合物；イミダゾリン系化合物；キノリン系化合物；ピリジン系化合物；ピリミジン系化合物；インドール系化合物；アミン系化合物；ウレア系化合物；ナトリウムベンゾエート；ベンジルメルカプト系化合物；ジ－ｓｅｃ－ブチルスルフィド；及びジフェニルスルホキサイドなどが挙げられる。 The pressure-sensitive adhesive composition can contain a rust preventive agent from the viewpoint of enhancing the metal corrosion resistance of the pressure-sensitive adhesive layer. Examples of the rust inhibitor include triazole compounds such as benzotriazole compounds; thiazole compounds such as benzothiazole compounds; imidazole compounds such as benzylimidazole compounds; imidazoline compounds; quinoline compounds; pyridine compounds; Examples include pyrimidine compounds; indole compounds; amine compounds; urea compounds; sodium benzoates; benzyl mercapto compounds; di-sec-butyl sulfide; and diphenyl sulfoxide.
　好ましい態様において、本発明の粘着剤組成物は、光重合開始剤及びその分解物を実質的に含有しない。これは、粘着剤組成物中の光重合開始剤及びその分解物が、耐久性に優れた粘着剤層の形成を阻害するおそれがあるからである。ここで、実質的に含有しないとは、粘着剤組成物１００質量部に対して、１．０質量部以下であることを意味し、好ましくは０．１質量部以下、より好ましくは０．０１質量部以下、さらに好ましくは０．００１質量部以下、特に０質量部であることが最も好ましい。 In a preferred embodiment, the pressure-sensitive adhesive composition of the present invention does not substantially contain a photopolymerization initiator and a decomposition product thereof. This is because the photopolymerization initiator and its decomposition product in the pressure-sensitive adhesive composition may inhibit formation of a pressure-sensitive adhesive layer having excellent durability. Here, substantially not containing means that it is 1.0 part by mass or less, preferably 0.1 part by mass or less, more preferably 0.01 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive composition. Most preferably, it is at most 0.001 part by mass, more preferably at most 0 part by mass.
　［２］粘着剤層及び粘着剤層付光学フィルムの構成並びに製造方法
　本発明は、前記粘着剤組成物からなる粘着剤層を包含する。該粘着剤層は、例えば、前記粘着剤組成物を、溶剤に溶解又は分散して溶剤含有の粘着剤組成物とし、次いで、これを光学フィルム又は離形フィルムの表面に塗布・乾燥することにより形成できる。 [2] Configuration and production method of pressure-sensitive adhesive layer and optical film with pressure-sensitive adhesive layer The present invention includes a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition. The pressure-sensitive adhesive layer is obtained by, for example, dissolving or dispersing the pressure-sensitive adhesive composition in a solvent to obtain a solvent-containing pressure-sensitive adhesive composition, and then applying and drying this onto the surface of an optical film or a release film. Can be formed.
　また、本発明は、粘着剤層を、光学フィルムの少なくとも一方の面に積層させた粘着剤層付光学フィルムも包含する。 The present invention also includes an optical film with an adhesive layer in which an adhesive layer is laminated on at least one surface of the optical film.
　本発明の粘着剤層及び該粘着剤層付光学フィルムは、前記粘着剤組成物から形成されるため、ＩＴＯ等の透明電極層に適用（又は積層）した場合においても、苛酷な耐久条件で、優れた耐久性を有する。 Since the pressure-sensitive adhesive layer of the present invention and the optical film with the pressure-sensitive adhesive layer are formed from the pressure-sensitive adhesive composition, even when applied (or laminated) to a transparent electrode layer such as ITO, under severe durability conditions, Excellent durability.
　図１は、本発明の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。図１に示される粘着剤層付光学フィルム１は、光学フィルム１０と、該光学フィルムの片面に粘着剤層２０が積層された光学フィルムである。該粘着剤層２０は、通常、光学フィルム１０の表面に直接積層される。なお、粘着剤層２０は、光学フィルム１０の両面に積層されてもよい。 FIG. 1 is a schematic sectional view showing an example of an optical film with an adhesive layer of the present invention. The optical film 1 with an adhesive layer shown in FIG. 1 is an optical film having an optical film 10 and an adhesive layer 20 laminated on one side of the optical film. The pressure-sensitive adhesive layer 20 is usually laminated directly on the surface of the optical film 10. The pressure-sensitive adhesive layer 20 may be laminated on both surfaces of the optical film 10.
　粘着剤層２０を光学フィルム１０の表面に積層する際には、光学フィルム１０の貼合面及び／又は粘着剤層２０の貼合面にプライマー層を形成させること、又は前記表面活性化処理（例えばプラズマ処理、コロナ処理など）を施すことが好ましく、特にコロナ処理を施すことが好ましい。 When laminating the pressure-sensitive adhesive layer 20 on the surface of the optical film 10, a primer layer is formed on the bonding surface of the optical film 10 and / or the bonding surface of the pressure-sensitive adhesive layer 20, or the surface activation treatment ( For example, plasma treatment, corona treatment and the like are preferably performed, and corona treatment is particularly preferable.
　光学フィルム１０が図２に示されるような片面保護偏光板である場合、粘着剤層２０は通常、偏光子面、すなわち、偏光子２における第１樹脂フィルム３とは反対側の面に、積層（好ましくは直接積層）される。光学フィルム１０が図３に示されるような両面保護偏光板である場合、粘着剤層２０を、第１，第２樹脂フィルム３，４のいずれかの外面に積層してもよく、両方の外面に積層してもよい。 When the optical film 10 is a single-sided protective polarizing plate as shown in FIG. 2, the pressure-sensitive adhesive layer 20 is usually laminated on the polarizer surface, that is, the surface of the polarizer 2 opposite to the first resin film 3. (Preferably directly laminated). When the optical film 10 is a double-sided protective polarizing plate as shown in FIG. 3, the pressure-sensitive adhesive layer 20 may be laminated on the outer surface of either the first or second resin film 3 or 4, and both outer surfaces May be laminated.
　光学フィルム１０と粘着剤層２０の間には別途帯電防止層を設けてもよい。帯電防止層として、ポリシロキサンなどのケイ素系材料、スズドープ酸化インジウム、スズドープ酸化アンチモンなどの無機金属系材料、ポリチオフェン、ポリスチレンスルホン酸、ポリアニリンなどの有機高分子系材料を用いることができる。 A separate antistatic layer may be provided between the optical film 10 and the pressure-sensitive adhesive layer 20. As the antistatic layer, silicon materials such as polysiloxane, inorganic metal materials such as tin-doped indium oxide and tin-doped antimony oxide, and organic polymer materials such as polythiophene, polystyrene sulfonic acid, and polyaniline can be used.
　粘着剤層付光学フィルム１は、粘着剤層２０の外面に積層されるセパレートフィルム（剥離フィルム）を含んでいてもよい。このセパレートフィルムは通常、粘着剤層２０の使用時（例えば透明電極やガラス基板への積層時）に剥離除去される。セパレートフィルムは、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、ポリアレートなどの各種樹脂からなるフィルムの粘着剤層２０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ってよい。 The optical film 1 with an adhesive layer may include a separate film (release film) laminated on the outer surface of the adhesive layer 20. This separate film is usually peeled and removed when the pressure-sensitive adhesive layer 20 is used (for example, when laminated on a transparent electrode or a glass substrate). The separate film is obtained by, for example, performing a release treatment such as a silicone treatment on the surface on which the adhesive layer 20 of a film made of various resins such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, and polyarate is formed. Good.
　粘着剤層付光学フィルム１は、上記粘着剤組成物を構成する各成分を溶剤に溶解又は分散して溶剤含有の粘着剤組成物とし、次いで、これを光学フィルム１０の表面に塗布・乾燥して粘着剤層２０を形成することによって得ることができる。また粘着剤層付光学フィルム１は、セパレートフィルムの離型処理面に上記と同様にして粘着剤層２０を形成し、該粘着剤層２０を光学フィルム１０の表面に積層（転写）することによっても得ることができる。 The optical film 1 with the pressure-sensitive adhesive layer is 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 and drying this onto the surface of the optical film 10. And can be obtained by forming the pressure-sensitive adhesive layer 20. Moreover, the optical film 1 with an adhesive layer forms the adhesive layer 20 on the mold release process surface of a separate film similarly to the above, and laminates | transfers this adhesive layer 20 on the surface of the optical film 10 (transfer). Can also be obtained.
　粘着剤層の厚みは、通常２～４０μｍであり、粘着剤層付光学フィルムの耐久性や粘着剤層付光学フィルムのリワーク性などの観点から、好ましくは５～３０μｍであり、さらに好ましくは１０～２５μｍである。粘着剤層の厚みが上記上限値以下であると、リワーク性が良好になり、上記下限値以上であると、光学フィルムの寸法変化に対する粘着剤層の追従性が良好となる。 The thickness of the pressure-sensitive adhesive layer is usually 2 to 40 μm, and preferably 5 to 30 μm, more preferably 10 from the viewpoints of durability of the optical film with the pressure-sensitive adhesive layer and reworkability of the optical film with the pressure-sensitive adhesive layer. ~ 25 μm. When the thickness of the pressure-sensitive adhesive layer is not more than the above upper limit value, the reworkability is good, and when it is more than the above lower limit value, the followability of the pressure-sensitive adhesive layer with respect to the dimensional change of the optical film is good.
　粘着剤層は、２３～１２０℃の温度範囲において０．００１～１０ＭＰａの貯蔵弾性率を示すものであることが好ましい。これにより、粘着剤層付光学フィルムの耐久性をより効果的に高めることができる。「２３～１２０℃の温度範囲において０．００１～１０ＭＰａの貯蔵弾性率を示す」とは、この範囲のいずれの温度においても、貯蔵弾性率が上記範囲内の値であることを意味する。貯蔵弾性率は通常、温度上昇に伴って漸減するので、２３℃及び１２０℃における貯蔵弾性率がいずれも上記範囲内であれば、この範囲の温度において、上記範囲内の貯蔵弾性率を示すと想定できる。粘着剤層の貯蔵弾性率は、市販の粘弾性測定装置、例えば、ＲＥＯＭＥＴＲＩＣ社製の粘弾性測定装置「ＤＹＮＡＭＩＣ　ＡＮＡＬＹＺＥＲ　ＲＤＡ　ＩＩ」を用いて測定することができる。 The pressure-sensitive adhesive layer preferably shows a storage elastic modulus of 0.001 to 10 MPa in a temperature range of 23 to 120 ° C. Thereby, durability of the optical film with an adhesive layer can be improved more effectively. “Showing a storage elastic modulus of 0.001 to 10 MPa in a temperature range of 23 to 120 ° C.” means that the storage elastic modulus is a value within the above range at any temperature within this range. Since the storage elastic modulus usually decreases gradually as the temperature rises, if both the storage elastic modulus at 23 ° C. and 120 ° C. are within the above range, the storage elastic modulus within the above range is exhibited at the temperature within this range. Can be assumed. The storage elastic modulus of the pressure-sensitive adhesive layer can be measured using a commercially available viscoelasticity measuring device, for example, a viscoelasticity measuring device “DYNAMIC ANALYZER RDA II” manufactured by REOMETRIC.
　架橋密度の一指標としてゲル分率を用いることができる。本発明の粘着剤層は、所定の架橋密度を有するため、所定のゲル分率を示す。すなわち、本発明の粘着剤層のゲル分率は、例えば、７０～９０質量％、好ましくは７５～９０質量％、さらに好ましくは７５～８５質量％であってよい。ゲル分率が下限値以上であると、粘着剤層の耐発泡性やリワーク性に有利であり、ゲル分率が上限値以下であると、耐剥がれ性に有利である。なお、ゲル分率は、実施例の項に記載の方法により測定できる。 Gel fraction can be used as an index of crosslinking density. Since the pressure-sensitive adhesive layer of the present invention has a predetermined crosslinking density, it exhibits a predetermined gel fraction. That is, the gel fraction of the pressure-sensitive adhesive layer of the present invention may be, for example, 70 to 90% by mass, preferably 75 to 90% by mass, and more preferably 75 to 85% by mass. When the gel fraction is at least the lower limit value, it is advantageous for foaming resistance and reworkability of the pressure-sensitive adhesive layer, and when the gel fraction is at most the upper limit value, it is advantageous for peeling resistance. The gel fraction can be measured by the method described in the Examples section.
　本発明の粘着剤層付光学フィルムは、所定の粘着力を有し、リワーク性に優れる。すなわち、前記粘着剤層付光学フィルムの、光学フィルムと貼合されていない面の粘着剤層をガラス基板に貼合し、温度２３℃、相対湿度５０％の条件下、２４時間保管した後の粘着力は、剥離速度３００ｍｍ／分において、好ましくは０．５～１０Ｎ／２５ｍｍ、より好ましくは０．７～５Ｎ／２５ｍｍである。粘着力が下限値以上であると、粘着性（又は接着性）が向上し、耐剥がれ性などに有利であり、粘着力が上限値以下であると、リワーク性に有利である。なお、粘着力は、例えば実施例の項に記載の方法により測定できる。 The optical film with a pressure-sensitive adhesive layer of the present invention has a predetermined adhesive strength and is excellent in reworkability. That is, after the pressure-sensitive adhesive layer on the surface not bonded to the optical film of the optical film with the pressure-sensitive adhesive layer is bonded to a glass substrate and stored for 24 hours under conditions of a temperature of 23 ° C. and a relative humidity of 50%. The adhesive strength is preferably 0.5 to 10 N / 25 mm, more preferably 0.7 to 5 N / 25 mm at a peeling speed of 300 mm / min. When the adhesive strength is at least the lower limit, the adhesiveness (or adhesiveness) is improved, which is advantageous for peeling resistance, and when the adhesive strength is at most the upper limit, it is advantageous for reworkability. In addition, adhesive force can be measured by the method as described in the term of an Example, for example.
　［２－１］光学フィルム
　粘着剤層付光学フィルム１を構成する光学フィルム１０は、液晶表示装置等の画像表示装置に組み込まれ得る各種の光学フィルム（光学特性を有するフィルム）であってよい。該光学フィルム１０は、単層構造（例えば偏光子、位相差フィルム、輝度向上フィルム、防眩フィルム、反射防止フィルム、拡散フィルム、集光フィルム等の光学機能性フィルムなど）であってもよく、多層構造（例えば偏光板、位相差板など）であってもよい。光学フィルム１０は、偏光板、偏光子、位相差板又は位相差フィルムであることが好ましく、特に偏光板又は偏光子であることが好ましい。なお、本明細書において、光学フィルムとは、画像表示（表示画面等）のために機能するフィルム（例えば、画像の見やすさの向上のために機能するフィルム）を意味する。また、本明細書において偏光板とは、偏光子の少なくとも一方の面に樹脂フィルム又は樹脂層が積層されたものを意味し、位相差板とは、位相差フィルムの少なくとも一方の面に樹脂フィルム又は樹脂層が積層されたものを意味する。 [2-1] Optical Film The optical film 10 constituting the optical film 1 with a pressure-sensitive adhesive layer may be various optical films (films having optical characteristics) that can be incorporated in an image display device such as a liquid crystal display device. The optical film 10 may have a single layer structure (for example, an optical functional film such as a polarizer, a retardation film, a brightness enhancement film, an antiglare film, an antireflection film, a diffusion film, a light collecting film, etc.) A multilayer structure (for example, a polarizing plate, a phase difference plate, etc.) may be used. The optical film 10 is preferably a polarizing plate, a polarizer, a retardation plate or a retardation film, and particularly preferably a polarizing plate or a polarizer. In the present specification, the optical film means a film that functions for image display (display screen or the like) (for example, a film that functions for improving the visibility of an image). Further, in the present specification, the polarizing plate means that a resin film or a resin layer is laminated on at least one surface of a polarizer, and the retardation plate means a resin film on at least one surface of the retardation film. Or the thing on which the resin layer was laminated | stacked is meant.
［２－２］偏光板
　図２及び図３は、偏光板の層構成の例を示す概略断面図である。図２に示される偏光板１０ａは、偏光子２の一方の面に第１樹脂フィルム３が積層（又は積層貼合）された片面保護偏光板であり、図３に示される偏光板１０ｂは、偏光子２の他方の面にさらに第２樹脂フィルム４が積層（又は積層貼合）された両面保護偏光板である。第１，第２樹脂フィルム３，４は、図示しない接着剤層や粘着剤層を介して偏光子２に貼合することができる。なお、偏光板１０ａ，１０ｂは、第１，第２樹脂フィルム３，４以外の他のフィルムや層を含んでいてよい。 [2-2] Polarizing Plate FIGS. 2 and 3 are schematic cross-sectional views showing examples of the layer structure of the polarizing plate. The polarizing plate 10a shown in FIG. 2 is a single-sided protective polarizing plate in which the first resin film 3 is laminated (or laminated) on one surface of the polarizer 2, and the polarizing plate 10b shown in FIG. This is a double-sided protective polarizing plate in which the second resin film 4 is further laminated (or laminated) on the other surface of the polarizer 2. The first and second resin films 3 and 4 can be bonded to the polarizer 2 via an adhesive layer and an adhesive layer (not shown). The polarizing plates 10a and 10b may include other films and layers other than the first and second resin films 3 and 4.
　偏光子２は、その吸収軸に平行な振動面をもつ直線偏光を吸収し、吸収軸に直交する（透過軸と平行な）振動面をもつ直線偏光を透過する性質を有するフィルムであり、例えば、ポリビニルアルコール系樹脂フィルムに二色性色素を吸着配向させたフィルムを用いることができる。二色性色素としては、例えば、ヨウ素や二色性有機染料などが挙げられる。 The polarizer 2 is a film having a property of absorbing linearly polarized light having a vibration surface parallel to the absorption axis and transmitting linearly polarized light having a vibration surface orthogonal to the absorption axis (parallel to the transmission axis). A film in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol-based resin film can be used. Examples of the dichroic dye include iodine and dichroic organic dyes.
　ポリビニルアルコール系樹脂は、ポリ酢酸ビニル系樹脂をケン化することにより得ることができる。ポリ酢酸ビニル系樹脂としては、例えば、酢酸ビニルの単独重合体であるポリ酢酸ビニル、酢酸ビニルと共重合可能な単量体（例えば不飽和カルボン酸、オレフィン、ビニルエーテル、不飽和スルホン酸、アンモニウム基を有する（メタ）アクリルアミドなど）と酢酸ビニルとの共重合体などが挙げられる。 The polyvinyl alcohol resin can be obtained by saponifying a polyvinyl acetate resin. Examples of the polyvinyl acetate resin include polyvinyl acetate which is a homopolymer of vinyl acetate, and a monomer copolymerizable with vinyl acetate (for example, unsaturated carboxylic acid, olefin, vinyl ether, unsaturated sulfonic acid, ammonium group). (Meth) acrylamide etc.) and vinyl acetate.
　ポリビニルアルコール系樹脂のケン化度は、通常８５～１００モル％、好ましくは９８モル％以上である。ポリビニルアルコール系樹脂は変性されていてもよく、例えば、アルデヒド類で変性されたポリビニルホルマール又はポリビニルアセタールなどであってもよい。ポリビニルアルコール系樹脂の平均重合度は、通常、１０００～１００００、好ましくは１５００～５０００である。なお、ポリビニルアルコール系樹脂の平均重合度は、ＪＩＳ　Ｋ　６７２６に準拠して求めることができる。 The saponification degree of the polyvinyl alcohol resin is usually 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol-based resin may be modified, for example, polyvinyl formal or polyvinyl acetal modified with aldehydes. The average degree of polymerization of the polyvinyl alcohol-based resin is usually 1000 to 10000, preferably 1500 to 5000. The average degree of polymerization of the polyvinyl alcohol resin can be determined according to JIS K 6726.
　通常、ポリビニルアルコール系樹脂を製膜したものを偏光子２の原反フィルムとして用いる。ポリビニルアルコール系樹脂は、公知の方法で製膜することができる。原反フィルムの厚みは、通常１～１５０μｍであり、延伸のしやすさなどを考慮すれば、好ましくは１０μｍ以上である。 Usually, a film made of a polyvinyl alcohol resin is used as the original film of the polarizer 2. A polyvinyl alcohol-type resin can be formed into a film by a well-known method. The thickness of the raw film is usually 1 to 150 μm, and is preferably 10 μm or more in consideration of easiness of stretching.
　偏光子２は、例えば、原反フィルムに対して、一軸延伸する工程、二色性色素でフィルムを染色してその二色性色素を吸着させる工程、ホウ酸水溶液でフィルムを処理する工程、及び、フィルムを水洗する工程が施され、最後に乾燥して製造される。偏光子２の厚みは、通常１～３０μｍであり、粘着剤層付光学フィルム１の薄膜化の観点から、好ましくは２０μｍ以下、さらに好ましくは１５μｍ以下、特に１０μｍ以下である。 The polarizer 2 is, for example, a step of uniaxially stretching the original film, a step of dyeing the film with a dichroic dye and adsorbing the dichroic dye, a step of treating the film with an aqueous boric acid solution, and The film is washed with water and finally dried. The thickness of the polarizer 2 is usually 1 to 30 μm, and preferably 20 μm or less, more preferably 15 μm or less, and particularly 10 μm or less from the viewpoint of thinning the optical film 1 with an adhesive layer.
　ポリビニルアルコール系樹脂フィルムに二色性色素を吸着配向させてなる偏光子２は、原反フィルムとしてポリビニルアルコール系樹脂フィルムの単独フィルムを用い、このフィルムに対して一軸延伸処理及び二色性色素の染色処理を施す方法（方法（１）とする）のほか、基材フィルムにポリビニルアルコール系樹脂を含有する塗工液（水溶液等）を塗工、乾燥させてポリビニルアルコール系樹脂層を有する基材フィルムを得た後、これを基材フィルムごとに一軸延伸し、延伸後のポリビニルアルコール系樹脂層に対して二色性色素の染色処理を施し、次いで基材フィルムを剥離除去する方法（方法（２）とする）によっても得ることができる。基材フィルムとしては、後述する第１，第２樹脂フィルム３，４を構成し得る熱可塑性樹脂と同様の熱可塑性樹脂からなるフィルムを用いることができ、好ましくは、ポリエチレンテレフタレートなどのポリエステル系樹脂、ポリカーボネート系樹脂、トリアセチルセルロースなどのセルロース系樹脂、ノルボルネン系樹脂などの環状ポリオレフィン系樹脂、ポリスチレン系樹脂などからなるフィルムである。上記方法（２）を利用すると、薄膜の偏光子２の作製が容易となり、例えば厚み７μｍ以下の偏光子２の作製であっても容易に行うことができる。 A polarizer 2 formed by adsorbing and orienting a dichroic dye on a polyvinyl alcohol-based resin film uses a single film of a polyvinyl alcohol-based resin film as a raw film, and the uniaxial stretching treatment and dichroic dye of this film are used. A substrate having a polyvinyl alcohol resin layer by applying a coating liquid (such as an aqueous solution) containing a polyvinyl alcohol resin to a substrate film, followed by drying, in addition to a method for performing a dyeing process (method (1)). After the film is obtained, this is uniaxially stretched for each base film, and the stretched polyvinyl alcohol resin layer is dyed with a dichroic dye, and then the base film is peeled and removed (method (method ( 2)). As the base film, a film made of a thermoplastic resin similar to the thermoplastic resin that can constitute the first and second resin films 3 and 4 described later can be used, and preferably a polyester-based resin such as polyethylene terephthalate. , Polycarbonate resins, cellulose resins such as triacetyl cellulose, cyclic polyolefin resins such as norbornene resins, polystyrene resins, and the like. When the method (2) is used, the thin film polarizer 2 can be easily manufactured. For example, the polarizer 2 having a thickness of 7 μm or less can be easily manufactured.
　第１，第２樹脂フィルム３，４はそれぞれ独立して、透光性を有する樹脂フィルムである。第１，第２樹脂フィルム３，４は、好ましくは光学的に透明な熱可塑性樹脂、例えば、鎖状ポリオレフィン系樹脂（例えば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（例えばノルボルネン系樹脂等）などのポリオレフィン系樹脂；セルロース系樹脂（例えばセルロースエステル系樹脂等）；ポリエステル系樹脂（例えば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、ポリブチレンテレフタレート等）；ポリカーボネート系樹脂（例えば、２，２－ビス（４－ヒドロキシフェニル）プロパンなどのビスフェノールから誘導されるポリカーボネートなど）；（メタ）アクリル系樹脂；ポリスチレン系樹脂；ポリエーテルエーテルケトン系樹脂；ポリスルホン系樹脂、又はこれらの混合物、共重合物などからなるフィルムであってもよい。これらのうち、第１，第２樹脂フィルム３，４は、それぞれ、環状ポリオレフィン系樹脂、ポリカーボネート系樹脂、セルロース系樹脂、ポリエステル系樹脂、及び（メタ）アクリル系樹脂などから構成されるフィルムであることが好ましく、特にセルロース系樹脂及び環状ポリオレフィン系樹脂などから構成されるフィルムであることが好ましい。 The first and second resin films 3 and 4 are each independently a translucent resin film. The first and second resin films 3 and 4 are preferably optically transparent thermoplastic resins such as chain polyolefin resins (for example, polyethylene resins and polypropylene resins), cyclic polyolefin resins (for example, norbornene-based resins). Polyolefin resins such as resins); cellulose resins (such as cellulose ester resins); polyester resins (such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate); polycarbonate resins (such as 2,2-bis) (Polycarbonate derived from bisphenol such as (4-hydroxyphenyl) propane); (meth) acrylic resin; polystyrene resin; polyetheretherketone resin; polysulfone resin, or a mixture or copolymer thereof Etc. may be a film made of. Among these, the first and second resin films 3 and 4 are films composed of a cyclic polyolefin resin, a polycarbonate resin, a cellulose resin, a polyester resin, and a (meth) acrylic resin, respectively. It is particularly preferable that the film is composed of a cellulose resin and a cyclic polyolefin resin.
　鎖状ポリオレフィン系樹脂としては、例えばポリエチレン樹脂、ポリプロピレン樹脂等の鎖状オレフィンの単独重合体、２種以上の鎖状オレフィンからなる共重合体などが挙げられる。 Examples of the chain polyolefin resin include a homopolymer of a chain olefin such as a polyethylene resin and a polypropylene resin, and a copolymer composed of two or more chain olefins.
　環状ポリオレフィン系樹脂は、ノルボルネンやテトラシクロドデセン（別名：ジメタノオクタヒドロナフタレン）又はそれらの誘導体を代表例とする環状オレフィンを重合単位として含む樹脂の総称である。環状ポリオレフィン系樹脂としては、環状オレフィンの開環（共）重合体及びその水素添加物、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、プロピレンなどの鎖状オレフィン又はビニル基を有する芳香族化合物との共重合体、並びにこれらを不飽和カルボン酸やその誘導体で変性した変性（共）重合体等が挙げられる。これらのうち、環状オレフィンとしてノルボルネン、多環ノルボルネン系単量体などのノルボルネン系単量体を用いたノルボルネン系樹脂が好ましい。 The cyclic polyolefin-based resin is a general term for resins containing, as polymerization units, cyclic olefins whose representative examples are norbornene, tetracyclododecene (also known as dimethanooctahydronaphthalene) or their derivatives. Cyclic polyolefin resins include ring-opening (co) polymers of cyclic olefins and hydrogenated products thereof, addition polymers of cyclic olefins, cyclic olefins and chain olefins such as ethylene and propylene, and aromatic compounds having a vinyl group And a modified (co) polymer obtained by modifying these with an unsaturated carboxylic acid or a derivative thereof. Among these, norbornene resins using norbornene monomers such as norbornene and polycyclic norbornene monomers as cyclic olefins are preferred.
　セルロース系樹脂は、好ましくはセルロースエステル系樹脂、すなわち、セルロースの部分又は完全エステル化物等であり、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。これらのうち、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い。 The cellulose resin is preferably a cellulose ester resin, that is, a cellulose partial or completely esterified product, and examples thereof include cellulose acetate ester, propionate ester, butyrate ester, and mixed ester thereof. Of these, triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate and the like are preferable.
　ポリエステル系樹脂は、エステル結合を有する、上記セルロースエステル系樹脂以外の樹脂であり、多価カルボン酸又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。ポリエステル系樹脂としては、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などが挙げられる。 The polyester-based resin is a resin other than the cellulose ester-based resin having an ester bond, and is generally made of a polycondensate of a polyvalent carboxylic acid or a derivative thereof and a polyhydric alcohol. Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polycyclohexanedimethyl terephthalate, and polycyclohexanedimethyl naphthalate.
　ポリカーボネート系樹脂は、炭酸とグリコール又はビスフェノールから形成されるポリエステルである。これらのうち、耐熱性、耐候性及び耐酸性の観点から、分子鎖にジフェニルアルカンを有する芳香族ポリカーボネートが好ましい。ポリカーボネートとしては、例えば２，２－ビス（４－ヒドロキシフェニル）プロパン（別名ビスフェノールＡ）、２，２－ビス（４－ヒドロキシフェニル）ブタン、１，１－ビス（４－ヒドロキシフェニル）シクロヘキサン、１，１－ビス（４－ヒドロキシフェニル）イソブタン、１，１－ビス（４－ヒドロキシフェニル）エタンなどのビスフェノールから誘導されるポリカーボネートなどが挙げられる。 Polycarbonate resin is a polyester formed from carbonic acid and glycol or bisphenol. Among these, from the viewpoint of heat resistance, weather resistance, and acid resistance, an aromatic polycarbonate having a diphenylalkane in the molecular chain is preferable. Examples of the polycarbonate include 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, , 1-bis (4-hydroxyphenyl) isobutane, polycarbonates derived from bisphenols such as 1,1-bis (4-hydroxyphenyl) ethane and the like.
　第１，第２樹脂フィルム３，４を構成し得る（メタ）アクリル系樹脂は、メタクリル酸エステル由来の構成単位を主体とする（例えばこれを５０質量％以上含む）重合体であることができ、これに他の共重合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、メタクリル酸エステル由来の構成単位を二種以上含んでいてもよい。メタクリル酸エステルとしては、メチルメタクリレート、エチルメタクリレート、ブチルメタクリレート等のメタクリル酸のＣ１～Ｃ４アルキルエステルが挙げられる。 The (meth) acrylic resin that can constitute the first and second resin films 3 and 4 can be a polymer mainly composed of a structural unit derived from a methacrylic ester (for example, containing 50% by mass or more). The copolymer is preferably a copolymer in which another copolymer component is copolymerized. The (meth) acrylic resin may contain two or more structural units derived from methacrylic acid esters. Examples of methacrylic acid esters include C 1 -C 4 alkyl esters of methacrylic acid such as methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like.
　メタクリル酸エステルと共重合し得る共重合成分としては、アクリル酸エステルが挙げられる。アクリル酸エステルは、好ましくは、メチルアクリレート、エチルアクリレート、ブチルアクリレート、２－エチルへキシルアクリレート等のアクリル酸のＣ１～Ｃ８アルキルエステルである。他の共重合成分の具体例としては、（メタ）アクリル酸等の不飽和酸類；スチレン、ハロゲン化スチレン、α－メチルスチレン、ビニルトルエン等の芳香族ビニル化合物；（メタ）アクリロニトリル等のビニルシアン化合物；無水マレイン酸、無水シトラコン酸等の不飽和酸無水物；フェニルマレイミド、シクロヘキシルマレイミド等の不飽和イミドなどの、分子内に重合性炭素－炭素二重結合を１個有する、アクリル酸エステル以外の化合物が挙げられる。分子内に重合性炭素－炭素二重結合を２個以上有する化合物を共重合成分として用いてもよい。共重合成分は、単独又は二種以上組み合わせて使用できる。 Examples of the copolymer component that can be copolymerized with the methacrylic acid ester include acrylic acid esters. The acrylic ester is preferably a C 1 -C 8 alkyl ester of acrylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like. Specific examples of other copolymerization components include unsaturated acids such as (meth) acrylic acid; aromatic vinyl compounds such as styrene, halogenated styrene, α-methylstyrene, and vinyl toluene; vinylcyan such as (meth) acrylonitrile. Compounds; unsaturated acid anhydrides such as maleic anhydride and citraconic anhydride; unsaturated imides such as phenylmaleimide and cyclohexylmaleimide, etc. other than acrylic acid esters having one polymerizable carbon-carbon double bond in the molecule The compound of this is mentioned. A compound having two or more polymerizable carbon-carbon double bonds in the molecule may be used as a copolymerization component. A copolymerization component can be used individually or in combination of 2 or more types.
　（メタ）アクリル系樹脂は、フィルムの耐久性を高め得る点で、高分子主鎖に環構造を有していてもよい。環構造は、環状酸無水物構造、環状イミド構造、ラクトン環構造等の複素環構造が好ましい。環状酸無水物構造の具体例としては、無水グルタル酸構造、無水コハク酸構造などが挙げられ、環状イミド構造の具体例としては、グルタルイミド構造、コハクイミド構造などが挙げられ、ラクトン環構造の具体例としては、ブチロラクトン環構造、バレロラクトン環構造などが挙げられる。 (Meth) acrylic resin may have a ring structure in the polymer main chain in that the durability of the film can be improved. The ring structure is preferably a heterocyclic structure such as a cyclic acid anhydride structure, a cyclic imide structure, or a lactone ring structure. Specific examples of the cyclic acid anhydride structure include a glutaric anhydride structure and a succinic anhydride structure, and specific examples of the cyclic imide structure include a glutarimide structure and a succinimide structure. Examples include butyrolactone ring structure and valerolactone ring structure.
　（メタ）アクリル系樹脂は、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、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、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。弾性重合体の例としては、アルキルアクリレートを主成分とし、これに共重合可能な他のビニルモノマー及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ルキルアクリレートとしては、例えば、メチルアクリレート、エチルアクリレート、ブチルアクリレート、２－エチルへキシルアクリレート等のアクリル酸のＣ１～Ｃ８アルキルエステルが挙げられる。アルキル基の炭素数は、好ましくは４以上である。 The (meth) acrylic resin may contain acrylic rubber particles from the viewpoints of film-formability on the film and impact resistance of the film. Acrylic rubber particles are particles having an elastic polymer mainly composed of an acrylate ester as an essential component. The acrylic rubber particles have a single-layer structure consisting essentially of this elastic polymer, or an elastic polymer in one layer. And a multilayer structure having Examples of the elastic polymer include a cross-linked elastic copolymer obtained by copolymerizing an alkyl acrylate as a main component with another vinyl monomer and a cross-linkable monomer copolymerizable therewith. Examples of the alkyl acrylate that is a main component of the elastic polymer include C 1 -C 8 alkyl esters of acrylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. The number of carbon atoms of the alkyl group is preferably 4 or more.
　アルキルアクリレート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、（メタ）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）アクリレート等の多価アルコールの（メタ）アクリレート、アリル（メタ）アクリレート等の（メタ）アクリル酸のアルケニルエステル、ジビニルベンゼンなどが挙げられる。 Examples of other vinyl monomers that can be copolymerized with alkyl acrylate include compounds having one polymerizable carbon-carbon double bond in the molecule, and more specifically, methacrylic acid esters such as methyl methacrylate. And aromatic vinyl compounds such as styrene, vinylcyan compounds such as (meth) acrylonitrile, and the like. Examples of the crosslinkable monomer include a crosslinkable compound having at least two polymerizable carbon-carbon double bonds in the molecule, and more specifically, ethylene glycol di (meth) acrylate, butanediol di ( Examples include (meth) acrylates of polyhydric alcohols such as (meth) acrylate, alkenyl esters of (meth) acrylic acid such as allyl (meth) acrylate, and divinylbenzene.
　アクリル系ゴム粒子の含有量は、（メタ）アクリル系樹脂１００質量部に対して、好ましくは５質量部以上、より好ましくは１０質量部以上である。アクリル系ゴム粒子の含有量があまり多いと、フィルムの表面硬度が低下し、また、フィルムに表面処理を施す場合に表面処理剤中の有機溶剤に対する耐溶剤性が低下し得る。従って、アクリル系ゴム粒子の含有量は、（メタ）アクリル系樹脂１００質量部に対して、通常８０質量部以下であり、好ましくは６０質量部以下である。 The content of the acrylic rubber particles is preferably 5 parts by mass or more, more preferably 10 parts by mass or more with respect to 100 parts by mass of the (meth) acrylic resin. When the content of the acrylic rubber particles is too large, the surface hardness of the film is lowered, and when the film is subjected to surface treatment, the solvent resistance against the organic solvent in the surface treatment agent can be lowered. Accordingly, the content of the acrylic rubber particles is usually 80 parts by mass or less, preferably 60 parts by mass or less with respect to 100 parts by mass of the (meth) acrylic resin.
　第１，第２樹脂フィルム３，４は、本発明の技術分野における通常の添加剤を含有することができる。添加剤としては、例えば、紫外線吸収剤、赤外線吸収剤、有機系染料、顔料、無機系色素、酸化防止剤、帯電防止剤、界面活性剤、滑剤、分散剤、熱安定剤等が挙げられる。紫外線吸収剤としては、サリチル酸エステル化合物、ベンゾフェノン化合物、ベンゾトリアゾール化合物、トリアジン化合物、シアノ（メタ）アクリレート化合物、ニッケル錯塩等が挙げられる。 The first and second resin films 3 and 4 can contain usual additives in the technical field of the present invention. Examples of the additive include an ultraviolet absorber, an infrared absorber, an organic dye, a pigment, an inorganic dye, an antioxidant, an antistatic agent, a surfactant, a lubricant, a dispersant, and a heat stabilizer. Examples of the ultraviolet absorber include salicylic acid ester compounds, benzophenone compounds, benzotriazole compounds, triazine compounds, cyano (meth) acrylate compounds, nickel complex salts, and the like.
　第１，第２樹脂フィルム３，４はそれぞれ、延伸されていないフィルム、又は一軸若しくは二軸延伸されたフィルムのいずれであってもよい。第１樹脂フィルム３及び／又は第２樹脂フィルム４は、偏光子２を保護する役割を担う保護フィルムであってもよく、後述する位相差フィルムのような光学機能を併せ持つ保護フィルムであってもよい。なお、第１樹脂フィルム３及び第２樹脂フィルム４は、同一又は異なるフィルムであってもよい。 Each of the first and second resin films 3 and 4 may be an unstretched film or a uniaxially or biaxially stretched film. The first resin film 3 and / or the second resin film 4 may be a protective film that plays a role of protecting the polarizer 2, or may be a protective film having an optical function such as a retardation film described later. Good. The first resin film 3 and the second resin film 4 may be the same or different films.
　また、第１樹脂フィルム３及び／又は第２樹脂フィルム４は、その外面（偏光子２とは反対側の表面）にハードコート層、防眩層、反射防止層、光拡散層、帯電防止層、防汚層、導電層等の表面処理層（コーティング層）を備えていてもよい。該第１樹脂フィルム３及び第２樹脂フィルム４の厚みはそれぞれ、通常１～１５０μｍであり、好ましくは５～１００μｍ、より好ましくは５～６０μｍ、さらに好ましくは５０μｍ以下（例えば１～４０μｍ）、特に３０μｍ以下（例えば５～２５μｍ）である。 The first resin film 3 and / or the second resin film 4 has a hard coat layer, an antiglare layer, an antireflection layer, a light diffusion layer, and an antistatic layer on the outer surface (the surface opposite to the polarizer 2). Further, a surface treatment layer (coating layer) such as an antifouling layer or a conductive layer may be provided. The thickness of each of the first resin film 3 and the second resin film 4 is usually 1 to 150 μm, preferably 5 to 100 μm, more preferably 5 to 60 μm, still more preferably 50 μm or less (eg 1 to 40 μm), particularly 30 μm or less (for example, 5 to 25 μm).
　特にスマートフォンやタブレット型端末といった中小型向けの偏光板では、薄膜化の要求から、第１樹脂フィルム３及び／又は第２樹脂フィルム４として厚み３０μｍ以下の薄いものが用いられることが多いが、このような偏光板は、偏光子２の収縮力を抑える力が弱く、耐久性が不十分となりやすい。このような偏光板を光学フィルム１０として用いる場合であっても、本発明の粘着剤層付光学フィルム１は良好な耐久性を有する。 In particular, a polarizing plate for small and medium-sized devices such as smartphones and tablet terminals is often used as a thin film having a thickness of 30 μm or less as the first resin film 3 and / or the second resin film 4 because of the demand for thinning. Such a polarizing plate has a weak force to suppress the contraction force of the polarizer 2 and tends to have insufficient durability. Even when such a polarizing plate is used as the optical film 10, the optical film 1 with the pressure-sensitive adhesive layer of the present invention has good durability.
　第１，第２樹脂フィルム３，４は、接着剤層や粘着剤層を介して偏光子２に貼合することができる。接着剤層を形成する接着剤として、水系接着剤又は活性エネルギー線硬化性接着剤を用いることができる。 The first and second resin films 3 and 4 can be bonded to the polarizer 2 via an adhesive layer or an adhesive layer. As an adhesive forming the adhesive layer, a water-based adhesive or an active energy ray-curable adhesive can be used.
　水系接着剤としては、慣用の水系接着剤（例えば、ポリビニルアルコール系樹脂水溶液からなる接着剤、水系二液型ウレタン系エマルジョン接着剤、アルデヒド化合物、エポキシ化合物、メラミン系化合物、メチロール化合物、イソシアネート化合物、アミン化合物、多価金属塩等の架橋剤など）が挙げられる。これらのうち、ポリビニルアルコール系樹脂水溶液からなる水系接着剤を好適に用いることができる。なお、水系接着剤を使用する場合は、偏光子２と第１，第２樹脂フィルム３，４とを貼合した後、水系接着剤中に含まれる水を除去するために乾燥させる工程を実施することが好ましい。乾燥工程後、例えば２０～４５℃程度の温度で養生する養生工程を設けてもよい。 As the water-based adhesive, a conventional water-based adhesive (for example, an adhesive comprising a polyvinyl alcohol resin aqueous solution, an aqueous two-component urethane emulsion adhesive, an aldehyde compound, an epoxy compound, a melamine compound, a methylol compound, an isocyanate compound, And crosslinking agents such as amine compounds and polyvalent metal salts). Among these, a water-based adhesive made of a polyvinyl alcohol-based resin aqueous solution can be suitably used. In addition, when using a water-system adhesive, after bonding the polarizer 2 and the 1st, 2nd resin films 3 and 4, it implements the process dried to remove the water contained in a water-system adhesive It is preferable to do. After the drying step, for example, a curing step for curing at a temperature of about 20 to 45 ° C. may be provided.
　上記活性エネルギー線硬化性接着剤とは、紫外線や電子線等の活性エネルギー線を照射することで硬化する接着剤をいい、例えば、重合性化合物及び光重合開始剤を含む硬化性組成物、光反応性樹脂を含む硬化性組成物、バインダー樹脂及び光反応性架橋剤を含む硬化性組成物等が挙げられ、好ましくは紫外線硬化性接着剤である。 The active energy ray-curable adhesive refers to an adhesive that cures when irradiated with active energy rays such as ultraviolet rays and electron beams. For example, a curable composition containing a polymerizable compound and a photopolymerization initiator, light Examples thereof include a curable composition containing a reactive resin, a curable composition containing a binder resin and a photoreactive cross-linking agent, and preferably an ultraviolet curable adhesive.
　活性エネルギー線硬化性接着剤を用いる場合は、偏光子２と第１，第２樹脂フィルム３，４とを貼合した後、必要に応じて乾燥工程を行い、次いで活性エネルギー線を照射することにより活性エネルギー線硬化性接着剤を硬化させる硬化工程を行う。活性エネルギー線の光源は特に限定されないが、波長４００ｎｍ以下に発光分布を有する紫外線が好ましい。 When an active energy ray-curable adhesive is used, after the polarizer 2 and the first and second resin films 3 and 4 are bonded, a drying process is performed as necessary, and then an active energy ray is irradiated. A curing step of curing the active energy ray-curable adhesive is performed. The light source of the active energy ray is not particularly limited, but ultraviolet light having a light emission distribution at a wavelength of 400 nm or less is preferable.
　偏光子２と第１，第２樹脂フィルム３，４とを貼合する方法としては、これらの少なくともいずれか一方の貼合面にケン化処理、コロナ処理、プラズマ処理等の表面活性化処理を施す方法などが挙げられる。偏光子２の両面に樹脂フィルムが貼合される場合、これらの樹脂フィルムを貼合するための接着剤は、同種の接着剤あってもよいし異種の接着剤であってもよい。 As a method of laminating the polarizer 2 and the first and second resin films 3 and 4, surface activation treatment such as saponification treatment, corona treatment, plasma treatment, etc. is applied to at least one of these lamination surfaces. The method of giving is mentioned. When a resin film is bonded to both surfaces of the polarizer 2, the adhesive for bonding these resin films may be the same type of adhesive or a different type of adhesive.
　偏光板１０ａ，１０ｂは、その他のフィルム又は層をさらに含むことができる。その具体例は、後述する位相差フィルムのほか、輝度向上フィルム、防眩フィルム、反射防止フィルム、拡散フィルム、集光フィルム、粘着剤層２０以外の粘着剤層、コーティング層、プロテクトフィルム等である。プロテクトフィルムは、偏光板等の光学フィルム１０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、粘着剤層付光学フィルム１を例えば、金属層や基板上に貼合した後、剥離除去されるのが通例である。 The polarizing plates 10a and 10b can further include other films or layers. Specific examples thereof include a retardation film, a brightness enhancement film, an antiglare film, an antireflection film, a diffusion film, a condensing film, an adhesive layer other than the adhesive layer 20, a coating layer, a protective film, and the like. . The protective film is a film used for the purpose of protecting the surface of the optical film 10 such as a polarizing plate from scratches and dirt. After the optical film 1 with an adhesive layer is bonded onto, for example, a metal layer or a substrate, it is peeled off. It is customary to be removed.
　プロテクトフィルムは通常、基材フィルムと、その上に積層される粘着剤層とで構成される。基材フィルムは、熱可塑性樹脂、例えば、ポリエチレン系樹脂、ポリプロピレン系樹脂等のポリオレフィン系樹脂；ポリエチレンテレフタレートや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）アクリル系樹脂等で構成することができる。 Protect film is usually composed of a base film and an adhesive layer laminated thereon. The base film is composed of a thermoplastic resin, for example, a polyolefin resin such as polyethylene resin or polypropylene resin; a polyester resin such as polyethylene terephthalate or polyethylene naphthalate; a polycarbonate resin; a (meth) acrylic resin, or the like. be able to.
［２－３］位相差板
　位相差板に含まれる位相差フィルムは、上述のとおり、光学異方性を示す光学フィルムであり、第１，第２樹脂フィルム３，４に用いることができるものとして上で例示した熱可塑性樹脂のほか、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。これらのうち、ポリカーボネート系樹脂フィルムや環状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又はセルロース系樹脂フィルムを一軸延伸又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。但し、ゼロレタデーションフィルムを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。 [2-3] Phase difference plate The phase difference film contained in the phase difference plate is an optical film exhibiting optical anisotropy as described above, and can be used for the first and second resin films 3 and 4. In addition to the thermoplastic resins exemplified above, for example, polyvinyl alcohol resins, polyarylate resins, polyimide resins, polyether sulfone resins, polyvinylidene fluoride / polymethyl methacrylate resins, liquid crystal polyester resins, It can be a stretched film obtained by stretching a resin film made of an ethylene-vinyl acetate copolymer saponified product, a polyvinyl chloride resin or the like to about 1.01 to 6 times. Among these, a polycarbonate film, a cyclic olefin resin film, a (meth) acrylic resin film or a cellulose resin film is preferably a uniaxially stretched or biaxially stretched film. In the present specification, a zero retardation film is also included in the retardation film. However, a zero retardation film can also be used as a protective film. In addition, a film called a uniaxial retardation film, a wide viewing angle retardation film, a low photoelastic modulus retardation film, or the like is also applicable as the retardation film.
　ゼロレタデーションフィルムとは、面内位相差値Ｒｅ及び厚み方向位相差値Ｒｔｈがともに－１５～１５ｎｍであるフィルムをいう。この位相差フィルムは、ＩＰＳモードの液晶表示装置に好適に用いられる。面内位相差値Ｒｅ及び厚み方向位相差値Ｒｔｈは、好ましくはともに－１０～１０ｎｍであり、より好ましくはともに－５～５ｎｍである。ここでいう面内位相差値Ｒｅ及び厚み方向位相差値Ｒｔｈは、波長５９０ｎｍにおける値である。 The zero retardation film refers to a film having both an in-plane retardation value Re and a thickness direction retardation value Rth of −15 to 15 nm. This retardation film is suitably used for an IPS mode liquid crystal display device. The in-plane retardation value R e and the thickness direction retardation value R th are both preferably −10 to 10 nm, and more preferably both −5 to 5 nm. The in-plane retardation value R e and the thickness direction retardation value R th here are values at a wavelength of 590 nm.
　面内位相差値Ｒｅ及び厚み方向位相差値Ｒｔｈは、それぞれ下記式：
　Ｒｅ＝（ｎｘ－ｎｙ）×ｄ
　Ｒｔｈ＝〔（ｎｘ＋ｎｙ）／２－ｎｚ〕×ｄ
で定義される。式中、ｎｘはフィルム面内の遅相軸方向（ｘ軸方向）の屈折率であり、ｎｙはフィルム面内の進相軸方向（面内でｘ軸に直交するｙ軸方向）の屈折率であり、ｎｚはフィルム厚み方向（フィルム面に垂直なｚ軸方向）の屈折率であり、ｄはフィルムの厚みである。 The in-plane retardation value R e and the thickness direction retardation value R th are respectively represented by the following formulas:
R e = (n x −n y ) × d
R th = [(n x + n y ) / 2−n z ] × d
Defined by Wherein, n x is a refractive index in a slow axis direction (x-axis direction) in the film plane, n y is the fast axis direction in the film plane of the (y-axis direction orthogonal to the x-axis in a plane) It is a refractive index, nz is the refractive index in the film thickness direction (z-axis direction perpendicular to the film surface), and d is the thickness of the film.
　ゼロレタデーションフィルムには、例えば、セルロース系樹脂、鎖状ポリオレフィン系樹脂及び環状ポリオレフィン系樹脂等のポリオレフィン系樹脂、ポリエチレンテレフタレート系樹脂又は（メタ）アクリル系樹脂からなる樹脂フィルムを用いることができる。特に、位相差値の制御が容易で、入手も容易であることから、セルロース系樹脂、ポリオレフィン系樹脂又は（メタ）アクリル系樹脂が好ましく用いられる。 As the zero retardation film, for example, a resin film made of a polyolefin resin such as a cellulose resin, a chain polyolefin resin, and a cyclic polyolefin resin, a polyethylene terephthalate resin, or a (meth) acrylic resin can be used. In particular, a cellulose resin, a polyolefin resin, or a (meth) acrylic resin is preferably used because the retardation value is easily controlled and easily available.
　また、液晶性化合物の塗布・配向によって光学異方性を発現させたフィルムや、無機層状化合物の塗布によって光学異方性を発現させたフィルムも、位相差フィルムとして用いることができる。このような位相差フィルムには、温度補償型位相差フィルムと称されるもの、また、ＪＸ日鉱日石エネルギー（株）から「ＮＨフィルム」の商品名で販売されている棒状液晶が傾斜配向したフィルム、富士フイルム（株）から「ＷＶフィルム」の商品名で販売されている円盤状液晶が傾斜配向したフィルム、住友化学（株）から「ＶＡＣフィルム」の商品名で販売されている完全二軸配向型のフィルム、同じく住友化学（株）から「ｎｅｗ　ＶＡＣフィルム」の商品名で販売されている二軸配向型のフィルム等がある。なお、位相差フィルムの少なくとも一方の面に積層される樹脂フィルムは、例えば上述の保護フィルムであってよい。 Also, a film that exhibits optical anisotropy by applying and orienting a liquid crystalline compound and a film that exhibits optical anisotropy by applying an inorganic layered compound can be used as the retardation film. In such a retardation film, a so-called temperature compensation type retardation film, and a rod-like liquid crystal sold under the trade name “NH film” from JX Nippon Mining & Energy Co., Ltd. are tilted. Film, a film with a disc-shaped liquid crystal sold under the trade name “WV film” from FUJIFILM Corporation, and a complete biaxial film sold under the trade name “VAC film” from Sumitomo Chemical Co., Ltd. Examples of the orientation type film include a biaxial orientation type film sold by Sumitomo Chemical Co., Ltd. under the trade name “new VAC film”. In addition, the resin film laminated | stacked on the at least one surface of retardation film may be the above-mentioned protective film, for example.
［３］光学積層体
　本発明は、前記粘着剤層付光学フィルムを含む光学積層体を包含する。好ましくは光学積層体は、前記粘着剤層付光学フィルムと、該粘着剤層付光学フィルムの粘着剤層側に積層された基材とを含む。 [3] Optical Laminate The present invention includes an optical laminate including the optical film with the pressure-sensitive adhesive layer. Preferably, an optical laminated body contains the base material laminated | stacked on the adhesive layer side of the said optical film with an adhesive layer, and this optical film with an adhesive layer.
　基材としては、慣用の基材、例えばガラス基板、プラスチックフィルム、有機導電膜、金属層、オーバーコート樹脂層等が挙げられる。本発明の光学積層体は、粘着剤層が前記粘着剤組成物から形成されるため、基材として例えばＩＴＯ等の透明電極層やメタルメッシュ（金属配線層）等の金属層を用いた場合においても、苛酷な耐久条件で、優れた耐久性を有する。 Examples of the substrate include conventional substrates such as glass substrates, plastic films, organic conductive films, metal layers, overcoat resin layers, and the like. In the optical laminate of the present invention, since the pressure-sensitive adhesive layer is formed from the pressure-sensitive adhesive composition, a transparent electrode layer such as ITO or a metal layer such as a metal mesh (metal wiring layer) is used as the base material. Even in harsh durability conditions, it has excellent durability.
　図４～図８は、本発明に係る光学積層体の例を示す概略断面図である。 4 to 8 are schematic cross-sectional views showing examples of the optical layered body according to the present invention.
　図４に示される光学積層体５は、基板４０上に積層された電極層３０を、前記粘着剤層付光学フィルム１ａ（又は粘着剤層付偏光板１ａ）の粘着剤層側の面に積層した光学積層体である。前記粘着剤層付光学フィルム１ａは、前記偏光板１０ａの偏光子２側の面に粘着剤層２０を積層したものである。 The optical layered body 5 shown in FIG. 4 is formed by laminating the electrode layer 30 laminated on the substrate 40 on the surface on the pressure-sensitive adhesive layer side of the optical film 1a with the pressure-sensitive adhesive layer (or the polarizing plate with pressure-sensitive adhesive layer 1a). It is the optical laminated body. The optical film 1a with an adhesive layer is obtained by laminating an adhesive layer 20 on the surface of the polarizing plate 10a on the polarizer 2 side.
　図５に示される光学積層体６は、基板４０上に積層された電極層３０を、粘着剤層付光学フィルム１ｂ（又は粘着剤層付偏光板１ｂ）の粘着剤層側の面に積層した光学積層体である。前記粘着剤層付光学フィルム１ｂは、前記偏光板１０ｂの第２樹脂フィルム４側の面に粘着剤層２０が積層された光学フィルムである。 The optical laminated body 6 shown by FIG. 5 laminated | stacked the electrode layer 30 laminated | stacked on the board | substrate 40 on the surface at the side of the adhesive layer of the optical film 1b with an adhesive layer (or polarizing plate 1b with an adhesive layer). It is an optical laminate. The optical film 1b with an adhesive layer is an optical film in which an adhesive layer 20 is laminated on the surface of the polarizing plate 10b on the second resin film 4 side.
　光学積層体５、６は、基板４０上に積層された電極層３０に、粘着剤層付光学フィルム（１ａ、１ｂ）を、粘着剤層２０を介して貼合することにより得ることができる。 The optical laminates 5 and 6 can be obtained by bonding the optical films with adhesive layer (1a, 1b) to the electrode layer 30 laminated on the substrate 40 via the adhesive layer 20.
　基板４０上に電極層３０を形成する方法としては、例えばスパッタリング法などが挙げられる。基板４０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ってもよく、好ましくはガラス基板である。該ガラス基板の材料として、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を用いることができる。電極層３０は、基板４０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。 Examples of a method for forming the electrode layer 30 on the substrate 40 include a sputtering method. The substrate 40 may be a transparent substrate constituting a liquid crystal cell included in the touch input element, and is preferably a glass substrate. As the material of the glass substrate, soda lime glass, low alkali glass, non-alkali glass, or the like can be used. The electrode layer 30 may be formed on the entire surface of the substrate 40 or a part thereof.
　電極層３０は、例えば、透明電極層又は金属層等が挙げられる。
　透明電極層としては、酸化スズ、酸化インジウム、酸化亜鉛、酸化ガリウム、酸化アルミニウム及びこれらの混合物で構成される層が挙げられる。導電性及び可視光透過率の点で、ＩＴＯであることが好ましい。
　金属層としては、アルミニウム、銅、銀、鉄、スズ、亜鉛、ニッケル、モリブデン、クロム、タングステン、鉛及びこれらの２種以上の金属を含む合金から選択される少なくとも１種の金属元素を含む層等が挙げられる。これらのうち、導電性の観点から、好ましくはアルミニウム、銅、銀及び金から選択される少なくとも１種の金属元素を含む金属層であり、より好ましくはアルミニウム、銅及び銀から選択される少なくとも１種の金属元素を含む層である。 Examples of the electrode layer 30 include a transparent electrode layer and a metal layer.
Examples of the transparent electrode layer include a layer composed of tin oxide, indium oxide, zinc oxide, gallium oxide, aluminum oxide, and a mixture thereof. In view of conductivity and visible light transmittance, ITO is preferable.
As the metal layer, a layer containing at least one metal element selected from aluminum, copper, silver, iron, tin, zinc, nickel, molybdenum, chromium, tungsten, lead, and an alloy containing two or more of these metals Etc. Among these, from the viewpoint of conductivity, it is preferably a metal layer containing at least one metal element selected from aluminum, copper, silver and gold, more preferably at least one selected from aluminum, copper and silver. It is a layer containing a seed metal element.
　なお、金属層は、細線の金属配線層を基板上に配置したメタルメッシュや金属ナノ粒子、金属ナノワイヤーをバインダー中に添加した層であってもよい。 The metal layer may be a layer obtained by adding a metal mesh, metal nanoparticles, or metal nanowires in which a fine metal wiring layer is disposed on a substrate to a binder.
　電極層３０の調製方法は特に限定されず、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あってもよい。
　電極層は、透明電極層及びスパッタリング法、インクジェット印刷法又はグラビア印刷法により形成された金属層であることが好ましく、透明電極層及びスパッタリングにより形成された金属層であることがより好ましい。
　電極層３０の厚みは、特に限定されないが、通常３μｍ以下、好ましくは１μｍ以下、より好ましくは０．８μｍ以下であり、通常０．０１μｍ以上である。さらに、電極層３０が金属配線層（例えばメタルメッシュ）の場合、該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以下であり、通常０．５μｍ以上である。 The method for preparing the electrode layer 30 is not particularly limited, and the electrode layer 30 may be formed by a vacuum deposition method, a sputtering method, an ion plating method, an ink jet printing method, or a gravure printing method.
The electrode layer is preferably a transparent electrode layer and a metal layer formed by a sputtering method, an inkjet printing method or a gravure printing method, and more preferably a transparent electrode layer and a metal layer formed by sputtering.
The thickness of the electrode layer 30 is not particularly limited, but is usually 3 μm or less, preferably 1 μm or less, more preferably 0.8 μm or less, and usually 0.01 μm or more. Further, when the electrode layer 30 is a metal wiring layer (for example, a metal mesh), the line width of the metal wiring is usually 10 μm or less, preferably 5 μm or less, more preferably 3 μm or less, and usually 0.5 μm or more. It is.
　図６に示される光学積層体７は、基板４０上に、前記粘着剤層付光学フィルム１の粘着剤層２０を積層した光学積層体である。 The optical laminate 7 shown in FIG. 6 is an optical laminate in which the adhesive layer 20 of the optical film 1 with an adhesive layer is laminated on a substrate 40.
　図７に示される光学積層体８は、基板４０上に積層された電極層３０の面上（基板４０と反対側の面上）に、さらに積層された樹脂層５０を、前記粘着剤層付光学フィルム１の粘着剤層２０側の面に積層した光学積層体である。樹脂層５０を形成する樹脂としては、例えば、前記例示の第１又は第２樹脂フィルムを構成する樹脂などが挙げられる。 The optical layered body 8 shown in FIG. 7 has a resin layer 50 further laminated on the surface of the electrode layer 30 laminated on the substrate 40 (on the surface opposite to the substrate 40). It is an optical laminate laminated on the surface of the optical film 1 on the pressure-sensitive adhesive layer 20 side. As resin which forms the resin layer 50, resin etc. which comprise the 1st or 2nd resin film of the said illustration are mentioned, for example.
　図８に示される光学積層体９は、基板４０上に、複数の電極層３０が縦横方向に所定間隔おいて積層され、該複数の電極層３０の間（又は隙間）かつ該電極層３０の面上（基板４０と反対側の面上）に樹脂層５０が形成（又は積層）されたこと以外は光学積層体７と同様である。該光学積層体９の形態（電極層３０が所定形状にパターニングされた形態）である場合、金属層３０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）であってもよい。 In the optical laminate 9 shown in FIG. 8, a plurality of electrode layers 30 are laminated on a substrate 40 at predetermined intervals in the vertical and horizontal directions, and between the electrode layers 30 (or gaps) and between the electrode layers 30. It is the same as the optical laminate 7 except that the resin layer 50 is formed (or laminated) on the surface (on the surface opposite to the substrate 40). When the optical layered body 9 is in the form (the electrode layer 30 is patterned into a predetermined shape), the metal layer 30 is, for example, a metal wiring layer (that is, an electrode layer) of a touch input element included in the touch input type liquid crystal display device. ).
　光学積層体９において、複数の電極層３０は、全体的又は部分的に粘着剤層２０に接触していてもよく、接触していなくてもよい。また、電極層３０は、上記金属又は合金を含む連続膜であってもよい。なお、樹脂層５０は省略されてもよい。 In the optical laminate 9, the plurality of electrode layers 30 may or may not be in contact with the pressure-sensitive adhesive layer 20 in whole or in part. The electrode layer 30 may be a continuous film containing the metal or alloy. The resin layer 50 may be omitted.
　粘着剤層付光学フィルム（１、１ａ、１ｂ）と、基板４０（ガラス基板、透明基板など）又は電極層３０とを貼着して光学積層体を作製した後、何らかの不具合があった場合には、粘着剤層付光学フィルムを基板４０又は電極層３０から剥離し、別の粘着剤層付光学フィルム１を基板４０又は電極層３０に貼り直す、いわゆるリワーク作業が必要となることがある。本発明に係る粘着剤層付光学フィルム１は、剥離した後のガラス基板又は電極層（例えばＩＴＯ等の透明導電層）の表面に曇りや糊残りなどが発生しにくく、リワーク性に優れている。 When there is some trouble after the optical film (1, 1a, 1b) with the adhesive layer and the substrate 40 (glass substrate, transparent substrate, etc.) or the electrode layer 30 are bonded to produce an optical laminate. May require a so-called rework operation in which the optical film with an adhesive layer is peeled off from the substrate 40 or the electrode layer 30 and another optical film 1 with an adhesive layer is reattached to the substrate 40 or the electrode layer 30. The optical film 1 with a pressure-sensitive adhesive layer according to the present invention is less likely to cause fogging or adhesive residue on the surface of a glass substrate or electrode layer (for example, a transparent conductive layer such as ITO) after peeling, and is excellent in reworkability. .
［４］液晶表示装置
　本発明の粘着剤層、粘着剤層付光学フィルム及び光学積層体は、液晶表示装置に用いることができ、該液晶表示装置は良好な耐久性を有する。 [4] Liquid Crystal Display Device The pressure-sensitive adhesive layer, the optical film with the pressure-sensitive adhesive layer, and the optical laminate of the present invention can be used in a liquid crystal display device, and the liquid crystal display device has good durability.
　液晶表示装置は、タッチパネル機能を有するタッチ入力式液晶表示装置であってもよい。タッチ入力式液晶表示装置は、液晶セルを含むタッチ入力素子と、バックライトとを備える。タッチパネルの構成は、公知の方式（例えばアウトセル型、オンセル型、インセル型など）であってもよく、またタッチパネルの動作方式は、公知の方式、例えば抵抗膜方式、静電容量方式（表面型静電容量方式、投影型静電容量方式）などであってもよい。本発明に係る粘着剤層付光学フィルムは、タッチ入力素子（液晶セル）の視認側に配置されてもよく、バックライト側に配置されてもよく、両方に配置されてもよい。液晶セルの駆動方式は、ＴＮ方式、ＶＡ方式、ＩＰＳ方式、マルチドメイン方式、ＯＣＢ方式等、従来公知のいかなる方式であってもよい。なお、前記液晶表示装置において、光学積層体が有する基板４０は、上記液晶セルに含まれる基板（典型的にはガラス基板）であってもよい。 The liquid crystal display device may be a touch input type liquid crystal display device having a touch panel function. The touch input type liquid crystal display device includes a touch input element including a liquid crystal cell and a backlight. The configuration of the touch panel may be a known method (for example, an out-cell type, an on-cell type, an in-cell type, etc.), and the operation method of the touch panel may be a known method, for example, a resistive film type, a capacitance type (surface type static type). (Capacitance method, projection type capacitance method) or the like. The optical film with an adhesive layer according to the present invention may be disposed on the viewing side of the touch input element (liquid crystal cell), may be disposed on the backlight side, or may be disposed on both. The driving method of the liquid crystal cell may be any conventionally known method such as a TN method, a VA method, an IPS method, a multi-domain method, and an OCB method. In the liquid crystal display device, the substrate 40 included in the optical laminate may be a substrate (typically a glass substrate) included in the liquid crystal cell.
［５］粘着剤用シロキサン化合物（Ａ）
　本発明は、粘着剤用シロキサン化合物（Ａ）を包含する。前記粘着剤用シロキサン化合物（Ａ）は、上述のシロキサン化合物（Ａ）と同じものであり、加水分解縮合物（ａ）のアルコキシ基の割合、加水分解縮合物（ａ）の重量平均分子量、及びその好ましい範囲等も同じである。なお、粘着剤用シロキサン化合物（Ａ）を適用する粘着剤層としては、特に限定されないが、好ましくは上記［１］に記載の粘着剤組成物からなる粘着剤層が挙げられる。 [5] Siloxane compound (A) for pressure-sensitive adhesive
This invention includes the siloxane compound (A) for adhesives. The pressure-sensitive adhesive siloxane compound (A) is the same as the above-described siloxane compound (A), the proportion of the alkoxy group of the hydrolysis condensate (a), the weight average molecular weight of the hydrolysis condensate (a), and The preferable range is the same. The pressure-sensitive adhesive layer to which the siloxane compound for pressure-sensitive adhesive (A) is applied is not particularly limited, but preferably includes a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition described in [1] above.
　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、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。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. Hereinafter, the part and% showing usage-amount and content are a mass reference | standard unless there is particular notice.
　＜製造例１：粘着剤用（メタ）アクリル系樹脂（Ｂ－１）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、表１に示す組成（表１の数値は質量部である。）の単量体を酢酸エチル８１．８部と混合して得られた溶液を仕込んだ。反応容器内の空気を窒素ガスで置換した後、内温を６０℃にした。その後、アゾビスイソブチロニトリル０．１２部を酢酸エチル１０部に溶解させた溶液を添加した。１時間同温で保持した後、内温を５４～５６℃に保ちながら、添加速度１７．３部／Ｈｒで酢酸エチルを、重合体の濃度がほぼ３５％となるように反応容器内へ連続的に加えた。酢酸エチルの添加開始から１２時間経過するまで内温を５４～５６℃に保持した後、酢酸エチルをさらに加えて重合体の濃度が２０％となるように調整し、（メタ）アクリル系樹脂（Ｂ－１）の酢酸エチル溶液を得た。得られた（メタ）アクリル系樹脂（Ｂ－１）の重量平均分子量Ｍｗは１３８万、重量平均分子量Ｍｗと数平均分子量Ｍｎとの比（Ｍｗ／Ｍｎ）は４．８であった。 <Production Example 1: Production of (meth) acrylic resin (B-1) for pressure-sensitive adhesive>
In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer, a monomer having the composition shown in Table 1 (the numerical values in Table 1 are parts by mass) is mixed with 81.8 parts of ethyl acetate. The resulting solution was charged. After the air in the reaction vessel was replaced with nitrogen gas, the internal temperature was set to 60 ° C. Thereafter, a solution in which 0.12 part of azobisisobutyronitrile was dissolved in 10 parts of ethyl acetate was added. After maintaining at the same temperature for 1 hour, while maintaining the internal temperature at 54 to 56 ° C., ethyl acetate was continuously fed into the reaction vessel at an addition rate of 17.3 parts / hr so that the polymer concentration was approximately 35%. Added. After maintaining the internal temperature at 54 to 56 ° C. until 12 hours have passed since the start of the addition of ethyl acetate, ethyl acetate was further added to adjust the polymer concentration to 20%, and a (meth) acrylic resin ( An ethyl acetate solution of B-1) was obtained. The obtained (meth) acrylic resin (B-1) had a weight average molecular weight Mw of 1.38 million and a ratio (Mw / Mn) of the weight average molecular weight Mw to the number average molecular weight Mn was 4.8.
　＜製造例２：粘着剤用（メタ）アクリル系樹脂（Ｂ－２）の製造＞
　単量体の組成を、表１に示す組成にしたこと以外は、製造例１と同様にして、（メタ）アクリル系樹脂（Ｂ－２）の酢酸エチル溶液を得た（樹脂濃度：２０％）。得られた（メタ）アクリル系樹脂（Ｂ－２）の重量平均分子量Ｍｗは１４２万であり、Ｍｗ／Ｍｎは５．２であった。 <Production Example 2: Production of (meth) acrylic resin (B-2) for pressure-sensitive adhesive>
An ethyl acetate solution of (meth) acrylic resin (B-2) was obtained in the same manner as in Production Example 1 except that the monomer composition was changed to the composition shown in Table 1 (resin concentration: 20% ). The resulting (meth) acrylic resin (B-2) had a weight average molecular weight Mw of 1,420,000 and Mw / Mn of 5.2.
　上の製造例において、重量平均分子量Ｍｗ及び数平均分子量Ｍｎは、ＧＰＣ装置にカラムとして、東ソー（株）製の「ＴＳＫｇｅｌ　ＸＬ」を４本、及び昭和電工（株）製の「Ｓｈｏｄｅｘ　ＧＰＣ　ＫＦ－８０２」を１本の計５本を直列につないで配置し、溶離液としてテトラヒドロフランを用い、試料濃度５ｍｇ／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。ＧＰＣの排出曲線を得る際の条件もこれと同様にした。 In the above production example, the weight average molecular weight Mw and the number average molecular weight Mn are 4 columns of “TSKgel XL” manufactured by Tosoh Corp. and “Shodex GPC KF-” manufactured by Showa Denko K.K. "802" is connected in series, a total of 5 are connected in series, tetrahydrofuran is used as the eluent, sample concentration is 5mg / mL, sample introduction amount is 100μL, temperature is 40 ° C, flow rate is 1mL / min. It was measured by. The conditions for obtaining the GPC discharge curve were also the same.
　ガラス転移温度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 was measured using a differential scanning calorimeter (DSC) “EXSTAR DSC6000” manufactured by SII NanoTechnology Co., Ltd. under a nitrogen atmosphere, a measurement temperature range of −80 to 50 ° C., and a temperature increase rate of 10 ° C./min. It measured on condition of this.
　各製造例における単量体の組成（表１の数値は質量部である）を表１に示した。 Table 1 shows the composition of the monomers in each production example (the numerical values in Table 1 are parts by mass).
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
　表１の「単量体組成」の欄にある略称は、次のモノマーを意味する。
　ＢＡ：ノルマルブチルアクリレート（ホモポリマーのガラス転移温度：－５４℃）
　ＭＡ：メチルアクリレート（ホモポリマーのガラス転移温度：１０℃）
　ＨＥＡ：２－ヒドロキシエチルアクリレート
　５ＨＰＡ：５－ヒドロキシペンチルアクリレート
　ＰＥＡ：フェノキシエチルアクリレート
　ＡＡ：アクリル酸。 Abbreviations in the column of “monomer composition” in Table 1 mean the following monomers.
BA: normal butyl acrylate (glass transition temperature of homopolymer: −54 ° C.)
MA: methyl acrylate (glass transition temperature of homopolymer: 10 ° C.)
HEA: 2-hydroxyethyl acrylate 5HPA: 5-hydroxypentyl acrylate PEA: phenoxyethyl acrylate AA: acrylic acid.
＜製造例３：シロキサン化合物Ａ－１の製造方法＞
　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、１，６－ビストリメトキシシリルヘキサン３２６部、メタノール９７．２部を仕込んだ。反応容器内の空気を窒素ガスで置換した後、内温を２５℃にした。その後、１規定塩酸水溶液０．６部、水１０．２部及びメタノール１０．２部を混合した混合溶液を反応容器に加えた。得られた混合物を１時間攪拌した後、還流を２時間行った。冷却後、得られた混合物に１０％酢酸ナトリウムメタノール溶液１．０部を加え、さらに２時間還流を行った。得られた混合物から溶媒留去を行い、シロキサン化合物（Ａ－１）を得た。
　得られたシロキサン化合物（Ａ－１）の重量平均分子量は１３００であった。また、１Ｈ－ＮＭＲより、添加した水の量に矛盾することなく、２０％のアルコキシ基が加水分解されていることを確認した。つまり、シロキサン化合物（Ａ－１）に含まれるアルコキシ基の含有量は、１，６－ビストリメトキシシリルヘキサンに含まれるアルコキシ基の総量１００モル％に対して、８０モル％である。 <Production Example 3: Production Method of Siloxane Compound A-1>
Into a reaction vessel equipped with a cooling tube, a nitrogen introducing tube, a thermometer and a stirrer, 326 parts of 1,6-bistrimethoxysilylhexane and 97.2 parts of methanol were charged. After the air in the reaction vessel was replaced with nitrogen gas, the internal temperature was adjusted to 25 ° C. Thereafter, a mixed solution obtained by mixing 0.6 part of 1N hydrochloric acid aqueous solution, 10.2 parts of water and 10.2 parts of methanol was added to the reaction vessel. The resulting mixture was stirred for 1 hour and then refluxed for 2 hours. After cooling, 1.0 part of a 10% sodium acetate methanol solution was added to the resulting mixture, and the mixture was further refluxed for 2 hours. The solvent was distilled off from the obtained mixture to obtain a siloxane compound (A-1).
The weight average molecular weight of the obtained siloxane compound (A-1) was 1300. From 1 H-NMR, it was confirmed that 20% of the alkoxy groups were hydrolyzed without contradiction to the amount of added water. That is, the content of alkoxy groups contained in the siloxane compound (A-1) is 80 mol% with respect to 100 mol% of the total amount of alkoxy groups contained in 1,6-bistrimethoxysilylhexane.
＜製造例４：シロキサン化合物Ａ－２の製造方法＞
　冷却管、温度計及び攪拌機を備えた反応容器に、１，６－ビストリメトキシシリルヘキサン３２６部、メタノール９７．２部を仕込んだ。反応容器内の空気を窒素ガスで置換した後、内温を２５℃にした。その後、１規定塩酸水溶液０．６部、水７．５部及びメタノール１０．２部を混合した混合溶液を反応容器に加えた。得られた混合物を１時間攪拌した後、還流を２時間行った。冷却後、得られた混合物に１０％酢酸ナトリウムメタノール溶液１．０部を加え、さらに２時間還流を行った。得られた混合物から溶媒留去を行い、シロキサン化合物（Ａ－２）を得た。
　得られたシロキサン化合物（Ａ－２）の重量平均分子量は９２０であった。また、１Ｈ－ＮＭＲより、添加した水の量に矛盾することなく、１５％のアルコキシ基が加水分解されていることを確認した。つまり、シロキサン化合物（Ａ－２）に含まれるアルコキシ基の含有量は、１，６－ビストリメトキシシリルヘキサンに含まれるアルコキシ基の総量１００モル％に対して、８５モル％である。 <Production Example 4: Production Method of Siloxane Compound A-2>
A reaction vessel equipped with a condenser, a thermometer and a stirrer was charged with 326 parts of 1,6-bistrimethoxysilylhexane and 97.2 parts of methanol. After the air in the reaction vessel was replaced with nitrogen gas, the internal temperature was adjusted to 25 ° C. Thereafter, a mixed solution obtained by mixing 0.6 part of 1N hydrochloric acid aqueous solution, 7.5 parts of water and 10.2 parts of methanol was added to the reaction vessel. The resulting mixture was stirred for 1 hour and then refluxed for 2 hours. After cooling, 1.0 part of a 10% sodium acetate methanol solution was added to the resulting mixture, and the mixture was further refluxed for 2 hours. The solvent was distilled off from the obtained mixture to obtain a siloxane compound (A-2).
The resulting siloxane compound (A-2) had a weight average molecular weight of 920. From 1 H-NMR, it was confirmed that 15% of the alkoxy groups were hydrolyzed without contradicting the amount of added water. That is, the content of alkoxy groups contained in the siloxane compound (A-2) is 85 mol% with respect to 100 mol% of the total amount of alkoxy groups contained in 1,6-bistrimethoxysilylhexane.
　＜実施例１～９及び比較例１～３＞
　（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部に対して、表２に示す量（質量部）のシロキサン化合物（Ａ）、架橋剤（Ｃ）、実施例４、７及び８ではさらに帯電防止剤（Ｅ）を混合し、次いで固形分濃度が１４％となるように酢酸エチルを添加して粘着剤組成物を得た。表２に示す各配合成分の配合量は、使用した商品が溶剤等を含む場合は、そこに含まれる有効成分としての質量部数である。 <Examples 1 to 9 and Comparative Examples 1 to 3>
(1) Preparation of pressure-sensitive adhesive composition The ethyl acetate solution (resin concentration: 20%) of the (meth) acrylic resin obtained in the above production example is shown in Table 2 with respect to 100 parts of the solid content of the solution. In the amount (parts by mass) of the siloxane compound (A), the crosslinking agent (C), and Examples 4, 7 and 8, the antistatic agent (E) was further mixed, and then ethyl acetate was added so that the solid content concentration was 14%. Was added to obtain a pressure-sensitive adhesive composition. The compounding quantity of each compounding component shown in Table 2 is the number of parts by mass as an active ingredient contained therein when the product used contains a solvent or the like.
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
　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。 The details of each compounding component indicated by an abbreviation in Table 2 are as follows.
　（シロキサン化合物（Ａ））
　Ａ－１：製造例３で得られたシロキサン化合物（Ａ）（１，６－ビス（トリメトキシシリル）ヘキサンの加水分解縮合物、加水分解率が２０％）
　Ａ－２：製造例４で得られたシロキサン化合物（Ａ）（１，６－ビス（トリメトキシシリル）ヘキサンの加水分解縮合物、加水分解率が１５％）
　Ａ－３：信越化学工業（株）製、商品名「Ｘ－１２－９６７Ｃ」（トリメトキシシリルプロピルコハク酸無水物）
　Ａ－４：１，３－ビス［３－（トリメトキシシリル）プロピル］尿素
　Ａ－５：ＫＢＭ４０３（３－グリシドキシプロピルトリメトキシシラン）
　（架橋剤（Ｃ））
　Ｃ－１：東ソー（株）製、商品名「コロネートＬ」（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％））
　（帯電防止剤（Ｅ））
　Ｅ－１：Ｎ－デシルピリジニウム　ビス（フルオロスルホニル）イミド。 (Siloxane compound (A))
A-1: Siloxane compound (A) obtained in Production Example 3 (hydrolysis condensate of 1,6-bis (trimethoxysilyl) hexane, hydrolysis rate 20%)
A-2: Siloxane compound (A) obtained in Production Example 4 (hydrolysis condensate of 1,6-bis (trimethoxysilyl) hexane, hydrolysis rate is 15%)
A-3: Shin-Etsu Chemical Co., Ltd., trade name “X-12-967C” (trimethoxysilylpropyl succinic anhydride)
A-4: 1,3-bis [3- (trimethoxysilyl) propyl] urea A-5: KBM403 (3-glycidoxypropyltrimethoxysilane)
(Crosslinking agent (C))
C-1: Product name “Coronate L” manufactured by Tosoh Corporation (ethyl acetate solution of trimethylolpropane adduct of tolylene diisocyanate (solid content concentration 75%))
(Antistatic agent (E))
E-1: N-decylpyridinium bis (fluorosulfonyl) imide.
　（２）粘着剤層の作製
　上記（１）で調製した各粘着剤組成物を、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〔リンテック（株）から入手した商品名「ＰＬＲ－３８２０５１」〕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２０μｍ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) Production of pressure-sensitive adhesive layer Each pressure-sensitive adhesive composition prepared in (1) above was separated from a polyethylene terephthalate film subjected to a release treatment [trade name “PLR-382051 obtained from Lintec Corporation]. ]] Was applied using an applicator so that the thickness after drying was 20 μm, and dried at 100 ° C. for 1 minute to prepare an adhesive layer (adhesive sheet).
　（３）粘着剤層付光学フィルム（Ｐ－１）の作製
　平均重合度約２４００、ケン化度９９．９モル％、厚み６０μｍのポリビニルアルコールフィルム〔（株）クラレ製の商品名「クラレビニロン　ＶＦ－ＰＥ♯６０００」〕を、３７℃の純水に浸漬した後、ヨウ素とヨウ化カリウムとを含む水溶液（ヨウ素／ヨウ化カリウム／水（質量比）＝０．０４／１．５／１００）に３０℃で浸漬した。その後、ヨウ化カリウムとホウ酸とを含む水溶液（ヨウ化カリウム／ホウ酸／水（質量比）＝１２／３．６／１００）に５６．５℃で浸漬した。フィルムを１０℃の純水で洗浄した後、８５℃で乾燥して、ポリビニルアルコールにヨウ素が吸着配向された厚み約２３μｍの偏光子を得た。延伸は、主に、ヨウ素染色及びホウ酸処理の工程で行い、トータルの延伸倍率は５．３倍であった。 (3) Production of optical film (P-1) with pressure-sensitive adhesive layer Polyvinyl alcohol film having an average degree of polymerization of about 2400, a saponification degree of 99.9 mol% and a thickness of 60 μm [trade name “Kuraray Vinylon VF manufactured by Kuraray Co., Ltd.” -PE # 6000 "] is immersed in pure water at 37 ° C, and then an aqueous solution containing iodine and potassium iodide (iodine / potassium iodide / water (mass ratio) = 0.04 / 1.5 / 100). Soaked at 30 ° C. Then, it was immersed at 56.5 ° C. in an aqueous solution containing potassium iodide and boric acid (potassium iodide / boric acid / water (mass ratio) = 12 / 3.6 / 100). The film was washed with pure water at 10 ° C. and then dried at 85 ° C. to obtain a polarizer having a thickness of about 23 μm in which iodine was adsorbed and oriented on polyvinyl alcohol. Stretching was mainly performed in the iodine staining and boric acid treatment steps, and the total stretching ratio was 5.3 times.
　得られた偏光子の片面に、厚み２５μｍのトリアセチルセルロースフィルムからなる透明保護フィルム〔コニカミノルタオプト（株）製の商品名「ＫＣ２ＵＡ」〕を、ポリビニルアルコール系樹脂の水溶液からなる接着剤を介して貼合した。次に上記偏光子におけるトリアセチルセルロースフィルムとは反対側の面に、厚み２３μｍの環状ポリオレフィン系樹脂からなるゼロ位相差フィルム〔日本ゼオン（株）製の商品名「ＺＥＯＮＯＲ」〕を、ポリビニルアルコール系樹脂の水溶液からなる接着剤を介して貼り合わせ偏光板を作製した。次いで、ゼロ位相差フィルムにおける偏光子が接する面とは反対側の面に、密着性向上のためのコロナ放電処理を施した後、上記（２）で作製した粘着剤層の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６５％の条件で７日間養生し、粘着剤層付光学フィルム（Ｐ－１）を得た。 A transparent protective film [trade name “KC2UA” manufactured by Konica Minolta Opto Co., Ltd.] made of a 25 μm-thick triacetyl cellulose film is placed on one side of the obtained polarizer with an adhesive made of an aqueous solution of a polyvinyl alcohol resin. And pasted. Next, a zero retardation film [trade name “ZEONOR” manufactured by Nippon Zeon Co., Ltd.] made of a cyclic polyolefin resin having a thickness of 23 μm is formed on the surface opposite to the triacetyl cellulose film in the polarizer. A bonded polarizing plate was produced through an adhesive made of an aqueous resin solution. Next, after the corona discharge treatment for improving adhesion is performed on the surface of the zero retardation film opposite to the surface in contact with the polarizer, it is opposite to the separate film of the pressure-sensitive adhesive layer prepared in (2) above. The side surface (pressure-sensitive adhesive layer surface) was bonded with a laminator and then cured for 7 days under the conditions of a temperature of 23 ° C. and a relative humidity of 65% to obtain an optical film (P-1) with a pressure-sensitive adhesive layer.
　（４）粘着剤層付光学フィルムの耐久性評価
　上記（３）で作製した粘着剤層付光学フィルム（Ｐ－１）を、偏光板の延伸軸方向が長辺となるように３００ｍｍ×２２０ｍｍの大きさに裁断してセパレートフィルムを剥離し、露出した粘着剤層面をガラス基板又はＩＴＯ（錫ドープ酸化インジウム）付きガラス基板に貼合した。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光学フィルム）を、オートクレーブ中、温度５０℃、圧力５ｋｇ／ｃｍ2（４９０．３ｋＰａ）で、２０分間加圧した。ガラス基板には、コーニング社製の無アルカリガラス　商品名「Ｅａｇｌｅ　ＸＧ」を使用した。また、ＩＴＯ付きガラス基板として、コーニング社製の無アルカリガラス［商品名「Eagle XG」］に、ＩＴＯ蒸着によって３０ｎｍのＩＴＯ層を形成したものを使用した。
　得られた光学積層体について、次の耐久性試験を実施した。 (4) Durability evaluation of optical film with pressure-sensitive adhesive layer The optical film with pressure-sensitive adhesive layer (P-1) produced in the above (3) is 300 mm × 220 mm so that the stretching axis direction of the polarizing plate is the long side. It cut | judged to a magnitude | size, the separate film was peeled, and the exposed adhesive layer surface was bonded to the glass substrate or the glass substrate with ITO (tin dope indium oxide). The test piece (the optical film with the pressure-sensitive adhesive layer to which the glass substrate was attached) obtained by attaching the obtained glass substrate was placed in an autoclave at a temperature of 50 ° C. and a pressure of 5 kg / cm 2 (490.3 kPa) for 20 minutes. Pressurized. A non-alkali glass product name “Eagle XG” manufactured by Corning was used for the glass substrate. In addition, as a glass substrate with ITO, a non-alkali glass manufactured by Corning [trade name “Eagle XG”] having a 30 nm ITO layer formed by ITO deposition was used.
The following durability test was implemented about the obtained optical laminated body.
　〔耐久性試験〕
　・温度９５℃の乾燥条件下で１０００時間保持する耐熱試験、（ガラス基板）
　・温度９５℃の乾燥条件下で１０００時間保持する耐熱試験、（ＩＴＯ付きガラス）
　・温度６０℃、相対湿度９０％の環境下で１０００時間保持する耐湿熱試験（ガラス基板）、
　・温度８５℃の乾燥条件下で３０分保持し、次いで温度－４０℃の乾燥条件下で３０分保持する操作を１サイクルとし、これを１０００サイクル繰り返す耐ヒートショック（ＨＳ）試験（ガラス基板）。 [Durability test]
・ Heat resistance test held at a temperature of 95 ℃ for 1000 hours (glass substrate)
・ Heat resistance test held at a temperature of 95 ℃ for 1000 hours (Glass with ITO)
-Moisture and heat resistance test (glass substrate) held for 1000 hours in an environment of temperature 60 ° C and relative humidity 90%,
・ Heat shock (HS) test (glass substrate) that is held for 30 minutes under a drying condition at a temperature of 85 ° C. and then held for 30 minutes under a drying condition at a temperature of −40 ° C. for one cycle. .
　各試験後の光学積層体を目視観察し、粘着剤層の浮き、剥れ、発泡等の外観変化の有無を目視で観察し、下記の評価基準に従って耐久性を評価した。結果を表３に示す。 The optical laminate after each test was visually observed, and the presence or absence of appearance changes such as lifting, peeling, and foaming of the pressure-sensitive adhesive layer was visually observed, and durability was evaluated according to the following evaluation criteria. The results are shown in Table 3.
　５：浮き、剥れ、発泡等の外観変化が全くみられない、
　４：浮き、剥れ、発泡等の外観変化がほとんどみられない、
　３：浮き、剥れ、発泡等の外観変化が少しばかり認められる、
　２：浮き、剥れ、発泡等の外観変化が目立つ、
　１：浮き、剥れ、発泡等の外観変化が顕著に認められる。
　なお、３以上である場合には、耐久性は良好である。 5: No change in appearance such as floating, peeling, foaming, etc.
4: Almost no change in appearance such as floating, peeling, foaming, etc.
3: Appearance changes such as floating, peeling and foaming are slightly observed.
2: Appearance changes such as floating, peeling, foaming are conspicuous,
1: Appearance changes such as floating, peeling, foaming, etc. are noticeable.
In addition, when it is 3 or more, durability is favorable.
　（５）粘着剤層付光学フィルムの粘着力評価
　上記（３）で作製した粘着剤層付光学フィルム（Ｐ－１）を、２５ｍｍ×１５０ｍｍの大きさの試験片に裁断した。試験片からセパレーターを剥がし、その粘着剤面をガラス基板に貼り付けた。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光学フィルム）を、オートクレーブ中、温度５０℃、圧力５ｋｇ／ｃｍ2（４９０．３ｋＰａ）で、２０分間加圧した。温度２３℃、相対湿度５０％の雰囲気中で２４時間保管したのちに、試験片から光学フィルムを粘着剤層とともに３００ｍｍ／分の速度で１８０°方向に剥離した。剥離時の平均剥離力を粘着力として表３に示す。
　粘着力が６Ｎ以下である場合にはリワーク性に優れ、また０．５Ｎ以上である場合には、偏光板端部から衝撃を受けた際にも剥がれが生じにくい。 (5) Evaluation of adhesive strength of optical film with pressure-sensitive adhesive layer The optical film with pressure-sensitive adhesive layer (P-1) produced in the above (3) was cut into a test piece having a size of 25 mm × 150 mm. The separator was peeled off from the test piece, and the pressure-sensitive adhesive surface was attached to a glass substrate. The test piece (the optical film with the pressure-sensitive adhesive layer to which the glass substrate was attached) obtained by attaching the obtained glass substrate was placed in an autoclave at a temperature of 50 ° C. and a pressure of 5 kg / cm 2 (490.3 kPa) for 20 minutes. Pressurized. After storing for 24 hours in an atmosphere having a temperature of 23 ° C. and a relative humidity of 50%, the optical film was peeled from the test piece together with the pressure-sensitive adhesive layer in the direction of 180 ° at a speed of 300 mm / min. Table 3 shows the average peeling force at the time of peeling as the adhesive strength.
When the adhesive strength is 6N or less, the rework property is excellent, and when it is 0.5N or more, peeling hardly occurs even when an impact is applied from the end of the polarizing plate.
　（６）粘着剤層付光学フィルムの帯電防止性評価
　得られた粘着剤層付き偏光フィルムのセパレーターを剥離したのちに、粘着剤の表面抵抗値を表面固有抵抗測定装置〔三菱化学（株）製の「ハイレスタ-up MCP-HT450」（商品名）〕により測定した。印加電圧２５０Ｖ、印加時間１０秒の測定条件で実施した。表面抵抗値が１．０×１０12Ω／□以下であれば、良好な帯電防止性が得られる。 (6) Evaluation of antistatic property of optical film with pressure-sensitive adhesive layer After peeling off the separator of the obtained polarizing film with pressure-sensitive adhesive layer, the surface resistance value of the pressure-sensitive adhesive is measured by a surface resistivity measuring device [manufactured by Mitsubishi Chemical Corporation]. "Hiresta-up MCP-HT450" (trade name)]. The measurement was performed under the measurement conditions of an applied voltage of 250 V and an applied time of 10 seconds. If the surface resistance value is 1.0 × 10 12 Ω / □ or less, good antistatic properties can be obtained.
〔粘着剤シートのゲル分率〕
　本発明の粘着剤シートのゲル分率評価方法を示す。ゲル分率が大きいほど粘着剤中で多くの架橋反応が進行していることになり、架橋密度の目安とすることができる。ゲル分率は、以下の（ａ）～（ｄ）に従って測定される値である。 [Gel fraction of adhesive sheet]
The gel fraction evaluation method of the adhesive sheet of this invention is shown. The larger the gel fraction, the more cross-linking reactions are progressing in the pressure-sensitive adhesive, and this can be used as a measure of the cross-linking density. The gel fraction is a value measured according to the following (a) to (d).
　（ａ）約８ｃｍ×約８ｃｍの面積の粘着剤シートと、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（I）で得られた貼合物を秤量して、その質量をＷs とし、次に粘着剤シートを包み込むように４回折りたたんでホッチキス（ステープラー）で留めた後秤量し、その質量をＷbとする。
　（ｃ）上記（II）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２４時間乾燥した後秤量し、その質量をＷaとし、次式に基づいてゲル分率を計算する。
　　ゲル分率（質量％）＝〔{Ｗa－(Ｗb－Ｗs)－Ｗm}／(Ｗs－Ｗm)〕×１００ (A) A pressure-sensitive adhesive sheet having an area of about 8 cm × about 8 cm and a metal mesh made of SUS304 (about 10 cm × about 10 cm) (with a mass of Wm) are bonded.
(B) Weighing the bonded product obtained in (I) above, setting its mass to Ws, then folding it 4 times so as to wrap the adhesive sheet, and then weighing with a stapler (stapler). Let the mass be Wb.
(C) The mesh stapled in (II) above is placed in a glass container, and 60 mL of ethyl acetate is added and immersed, and then the glass container is stored at room temperature for 3 days.
(D) The mesh is taken out from the glass container, dried at 120 ° C. for 24 hours, and weighed. The mass is defined as Wa, and the gel fraction is calculated based on the following formula.
Gel fraction (mass%) = [{Wa− (Wb−Ws) −Wm} / (Ws−Wm)] × 100
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
　実施例１～９で得られた粘着剤層付光学フィルムは、苛酷な耐久条件下であっても良好な耐久性を示した。ＩＴＯ基板に適用した場合においても良好な耐久性を示した。また、良好なリワーク性も有し、耐久性とリワーク性とを両立できることが確認された。 The optical films with pressure-sensitive adhesive layers obtained in Examples 1 to 9 showed good durability even under severe durability conditions. Even when applied to an ITO substrate, good durability was exhibited. Moreover, it has also confirmed that it has favorable reworkability and can make durability and reworkability compatible.
　１，１ａ，１ｂ…粘着剤層付光学フィルム、２…偏光子、３…第１樹脂フィルム、４…第２樹脂フィルム、５，６，７，８，９…光学積層体、１０…光学フィルム、１０ａ，１０ｂ…偏光板、２０…粘着剤層、３０…電極層、４０…基板、５０…樹脂層。 DESCRIPTION OF SYMBOLS 1,1a, 1b ... Optical film with an adhesive layer, 2 ... Polarizer, 3 ... 1st resin film, 4 ... 2nd resin film, 5, 6, 7, 8, 9 ... Optical laminated body, 10 ... Optical film DESCRIPTION OF SYMBOLS 10a, 10b ... Polarizing plate, 20 ... Adhesive layer, 30 ... Electrode layer, 40 ... Substrate, 50 ... Resin layer.

Claims (15)

  1. 　シロキサン化合物（Ａ）を含む粘着剤組成物であって、
    シロキサン化合物（Ａ）は、下記式（ａ１）
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｂは、炭素数１～２０のアルカンジイル基又は炭素数３～２０の二価の脂環式炭化水素基を示し、前記アルカンジイル基及び前記脂環式炭化水素基を構成する－ＣＨ２－は、－Ｏ－又は－ＣＯ－に置換されてもよく、Ｒ１及びＲ２はそれぞれ独立して炭素数１～５のアルキル基を示し、Ｒ３、Ｒ４、Ｒ５及びＲ６はそれぞれ独立して、炭素数１～５のアルキル基又は炭素数１～５のアルコキシ基を示す）
    で表される加水分解縮合性シラン化合物の加水分解縮合物（ａ）である、粘着剤組成物。     A pressure-sensitive adhesive composition containing a siloxane compound (A),
    The siloxane compound (A) is represented by the following formula (a1)
    Figure JPOXMLDOC01-appb-C000001
     (In the formula, B represents an alkanediyl group having 1 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and constitutes the alkanediyl group and the alicyclic hydrocarbon group. —CH 2 — may be substituted with —O— or —CO—, R 1 and R 2 each independently represents an alkyl group having 1 to 5 carbon atoms, and R 3 , R 4 , R 5 and R 6 each independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms)
    A pressure-sensitive adhesive composition, which is a hydrolysis-condensation product (a) of a hydrolysis-condensable silane compound represented by:
  2. 　シロキサン化合物（Ａ）に含まれるアルコキシ基の含有量は、加水分解縮合性シラン化合物（ａ１）に含まれるアルコキシ基の総量１００モル％に対して、６０～９５モル％である、請求項１に記載の粘着剤組成物。 The content of alkoxy groups contained in the siloxane compound (A) is 60 to 95 mol% with respect to 100 mol% of the total amount of alkoxy groups contained in the hydrolytic condensable silane compound (a1). The pressure-sensitive adhesive composition described.
  3. 　シロキサン化合物（Ａ）の重量平均分子量は、ポリスチレン換算で、６００～４０００である、請求項１又は２に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1 or 2, wherein the siloxane compound (A) has a weight average molecular weight of 600 to 4000 in terms of polystyrene.
  4. 　さらに（メタ）アクリル系樹脂（Ｂ）及び架橋剤（Ｃ）を含む、請求項１～３のいずれかに記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 1 to 3, further comprising a (meth) acrylic resin (B) and a crosslinking agent (C).
  5. 　シロキサン化合物（Ａ）の割合は、（メタ）アクリル系樹脂（Ｂ）１００質量部に対して、０．０１～１０質量部である、請求項４に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 4, wherein the proportion of the siloxane compound (A) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin (B).
  6. 　（メタ）アクリル系樹脂（Ｂ）は、ホモポリマーのガラス転移温度が０℃未満のアルキルアクリレート（ｂ１）由来の構成単位と、ホモポリマーのガラス転移温度が０℃以上のアルキルアクリレート（ｂ２）由来の構成単位とを含む、請求項４又は５に記載の粘着剤組成物。 The (meth) acrylic resin (B) is derived from a structural unit derived from an alkyl acrylate (b1) having a homopolymer glass transition temperature of less than 0 ° C. and an alkyl acrylate (b2) derived from a homopolymer having a glass transition temperature of 0 ° C. or higher. The pressure-sensitive adhesive composition according to claim 4, comprising:
  7. 　（メタ）アクリル系樹脂（Ｂ）に含まれるカルボキシル基含有（メタ）アクリレート由来の構成単位の割合は、（メタ）アクリル系樹脂（Ｂ）を構成する全構成単位１００質量部に対して１．０質量部以下である、請求項４～６のいずれかに記載の粘着剤組成物。 The ratio of the structural unit derived from the carboxyl group-containing (meth) acrylate contained in the (meth) acrylic resin (B) is 1. with respect to 100 parts by mass of all the structural units constituting the (meth) acrylic resin (B). The pressure-sensitive adhesive composition according to any one of claims 4 to 6, which is 0 part by mass or less.
  8. 　（メタ）アクリル系樹脂（Ｂ）の重量平均分子量は、ポリスチレン換算で、１００～２５０万である、請求項４～７のいずれかに記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 4 to 7, wherein the weight average molecular weight of the (meth) acrylic resin (B) is 1 to 2.5 million in terms of polystyrene.
  9. 　架橋剤（Ｃ）はイソシアネート系化合物である、請求項４～８のいずれかに記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 4 to 8, wherein the crosslinking agent (C) is an isocyanate compound.
  10. 　架橋剤（Ｃ）の割合は、（メタ）アクリル系樹脂（Ｂ）１００質量部に対して、０．０１～１０質量部である、請求項４～９のいずれかに記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to any one of claims 4 to 9, wherein the ratio of the crosslinking agent (C) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the (meth) acrylic resin (B). .
  11. 　請求項１～１０のいずれかに記載の粘着剤組成物からなる粘着剤層。 A pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition according to any one of claims 1 to 10.
  12. 　請求項１１に記載の粘着剤層を、光学フィルムの少なくとも一方の面に積層させた粘着剤層付光学フィルム。 An optical film with an adhesive layer in which the adhesive layer according to claim 11 is laminated on at least one surface of the optical film.
  13. 　前記粘着剤層付光学フィルムの、光学フィルムと貼合されていない面の粘着剤層をガラス基板に貼合し、温度２３℃、相対湿度５０％の条件下、２４時間保管した後の粘着力は、剥離速度３００ｍｍ／分において、０．５～１０Ｎ／２５ｍｍである、請求項１２に記載の粘着剤層付光学フィルム。 The pressure-sensitive adhesive strength after the pressure-sensitive adhesive layer on the surface of the optical film with the pressure-sensitive adhesive layer not bonded to the optical film is bonded to a glass substrate and stored for 24 hours under conditions of a temperature of 23 ° C. and a relative humidity of 50%. The optical film with an adhesive layer according to claim 12, which has a thickness of 0.5 to 10 N / 25 mm at a peeling speed of 300 mm / min.
  14. 　請求項１２又は１３に記載の粘着剤層付光学フィルムを含む、光学積層体。 An optical laminate comprising the optical film with an adhesive layer according to claim 12 or 13.
  15. 　下記式（ａ１）
    Figure JPOXMLDOC01-appb-C000002
     （式中、Ｂは、炭素数１～２０のアルカンジイル基又は炭素数３～２０の二価の脂環式炭化水素基を示し、前記アルカンジイル基及び前記脂環式炭化水素基を構成する－ＣＨ２－は、－Ｏ－又は－ＣＯ－に置換されてもよく、Ｒ１及びＲ２はそれぞれ独立して炭素数１～５のアルキル基を示し、Ｒ３、Ｒ４、Ｒ５及びＲ６はそれぞれ独立して、炭素数１～５のアルキル基又は炭素数１～５のアルコキシ基を示す）
    で表される加水分解縮合性シラン化合物の加水分解縮合物（ａ）である、粘着剤用シロキサン化合物（Ａ）。     The following formula (a1)
    Figure JPOXMLDOC01-appb-C000002
     (In the formula, B represents an alkanediyl group having 1 to 20 carbon atoms or a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and constitutes the alkanediyl group and the alicyclic hydrocarbon group. —CH 2 — may be substituted with —O— or —CO—, R 1 and R 2 each independently represents an alkyl group having 1 to 5 carbon atoms, and R 3 , R 4 , R 5 and R 6 each independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms)
    The siloxane compound (A) for adhesives which is a hydrolysis-condensation product (a) of the hydrolytic condensable silane compound represented by these.
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