WO2020122146A1 - Polarizing film provided with adhesive layer - Google Patents

Polarizing film provided with adhesive layer Download PDF

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Publication number
WO2020122146A1
WO2020122146A1 PCT/JP2019/048563 JP2019048563W WO2020122146A1 WO 2020122146 A1 WO2020122146 A1 WO 2020122146A1 JP 2019048563 W JP2019048563 W JP 2019048563W WO 2020122146 A1 WO2020122146 A1 WO 2020122146A1
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WIPO (PCT)
Prior art keywords
meth
monomer
acrylate
weight
adhesive layer
Prior art date
Application number
PCT/JP2019/048563
Other languages
French (fr)
Japanese (ja)
Inventor
有 森本
雄祐 外山
武史 仲野
立也 鈴木
博基 家田
Original Assignee
日東電工株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2018234330A external-priority patent/JP7208782B2/en
Priority claimed from JP2019007970A external-priority patent/JP2020118768A/en
Priority claimed from JP2019007971A external-priority patent/JP2020118769A/en
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to CN202311280377.2A priority Critical patent/CN117518328A/en
Priority to KR1020217009560A priority patent/KR20210102185A/en
Priority to CN201980081837.4A priority patent/CN113167964B/en
Publication of WO2020122146A1 publication Critical patent/WO2020122146A1/en

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    • 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]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/023—Optical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/064—Copolymers with monomers not covered by C09J133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • 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
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • 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
    • G02F1/133528—Polarisers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays

Definitions

  • the present invention relates to a polarizing film with an adhesive layer.
  • the image forming method it is essential for liquid crystal display devices to place polarizing films on both sides of the glass substrate that forms the surface of the liquid crystal panel.
  • polarizing film generally, a polyvinyl alcohol-based film and a polarizer made of a dichroic material such as iodine having a protective film bonded to one or both surfaces thereof with a polyvinyl alcohol-based adhesive or the like are used. ..
  • an adhesive When attaching the polarizing film to a liquid crystal cell etc., an adhesive is usually used.
  • the pressure-sensitive adhesive is preliminarily provided as a pressure-sensitive adhesive layer on one surface of the polarizing film, since it has advantages such as being able to instantly fix the polarizing film and not requiring a drying step to fix the polarizing film. .. That is, a polarizing film with an adhesive layer is generally used for sticking a polarizing film (Patent Documents 1 and 2).
  • a polarizing film or a polarizing film with a pressure-sensitive adhesive layer is attached to a glass substrate of a liquid crystal panel, durability is required, and for example, in a durability test such as heating and humidification that is usually performed as an environmental promotion test, adhesion It is required that problems such as peeling and floating due to the agent layer do not occur.
  • the present inventors have found that the polarizing film with an adhesive layer of the present invention can solve the above problems, and have completed the present invention.
  • the present invention includes the following embodiments.
  • a polarizing film with an adhesive layer which comprises a polarizing film and an adhesive layer
  • the pressure-sensitive adhesive layer includes a base polymer and a silicone oligomer Ps
  • the base polymer is a (meth)acrylic polymer
  • the silicone oligomer Ps is included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the (meth)acrylic polymer.
  • the silicone oligomer Ps has a Tg of ⁇ 50° C. or higher and 100° C. or lower, a side chain silicone functional group equivalent of 1000 to 20000 g/mol, and a weight average molecular weight Mw of 10,000 or more and 300,000 or less.
  • Polarizing film is a Tg of ⁇ 50° C. or higher and 100° C. or lower, a side chain silicone functional group equivalent of 1000 to 20000 g/mol, and a weight average molecular weight Mw of 10,000 or more and 300,000 or less.
  • silicone oligomer Ps contains a monomer S1 having a polyorganosiloxane skeleton and a monomer having a homopolymer glass transition temperature of ⁇ 70° C. or higher and 180° C. or lower as monomer units.
  • Polarizing film with agent layer contains a monomer S1 having a polyorganosiloxane skeleton and a monomer having a homopolymer glass transition temperature of ⁇ 70° C. or higher and 180° C. or lower as monomer units.
  • At least one polar monomer (B) selected from the group consisting of a carboxyl group-containing monomer (b1) and a nitrogen-containing monomer (b2) is further contained in an amount of 0 to 20% by weight.
  • a polarizing film with a pressure-sensitive adhesive layer which can give reworkability immediately after bonding and can increase durability after heating and have increased durability.
  • FIG. 1 is an example of a schematic cross-sectional view of a polarizing film with an adhesive layer of the present invention.
  • the polarizing film with a pressure-sensitive adhesive layer of the present invention includes a polarizing film and a pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive layer may be present on one side or both sides of the polarizing film.
  • the structure of a polarizing film with an adhesive layer is schematically shown in FIG.
  • the polarizing film with an adhesive layer 10 is configured as a polarizing film with an adhesive layer, which includes the polarizing film 3 and the adhesive layer 4 provided on one surface thereof.
  • the polarizing film 3 is composed of a polarizer 1 and protective films 2 and 2′ provided on both sides of the polarizer 1, but the protective film may be provided only on one side of the polarizer. ..
  • the adhesive layer 4 is fixedly provided on one side of the polarizing film 3, that is, without the intention of separating the adhesive layer 4 from the polarizing film 3.
  • the polarizing film 10 with an adhesive layer is used by attaching the adhesive layer 4 to an adherend.
  • a sheet-shaped base material (liner base material) which has a release layer provided with a release treatment agent on one surface so that the one surface serves as a release surface can be preferably used.
  • the structure of the polarizing film with an adhesive layer is not limited to the embodiment schematically shown in FIG.
  • the polarizer is not particularly limited, and various kinds can be used.
  • the polarizer include hydrophilic polymer films such as polyvinyl alcohol film, partially formalized polyvinyl alcohol film, and ethylene/vinyl acetate copolymer partially saponified film, and dichroism of iodine or dichroic dye.
  • examples include polyene-oriented films such as those obtained by adsorbing a substance and uniaxially stretched, polyvinyl alcohol dehydrated products, polyvinyl chloride dehydrochlorinated products, and the like.
  • a polarizer made of a polyvinyl alcohol film and a dichroic substance such as iodine is preferable.
  • the thickness of these polarizers is not particularly limited, but is generally 2 to 25 ⁇ m.
  • a uniaxially stretched polarizer obtained by dyeing a polyvinyl alcohol film with iodine can be produced, for example, by dyeing a polyvinyl alcohol film by immersing it in an aqueous solution of iodine and stretching it to 3 to 7 times its original length. it can. If necessary, it can be immersed in an aqueous solution of potassium iodide or the like which may contain boric acid, zinc sulfate, zinc chloride or the like. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed with water before dyeing.
  • Stretching may be performed after dyeing with iodine, stretching while dyeing, or stretching and then dyeing with iodine. Stretching can be performed in an aqueous solution of boric acid or potassium iodide or in a water bath.
  • the pressure-sensitive adhesive layer used in the present invention contains a base polymer and a silicone oligomer Ps.
  • the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer used in the present invention is not particularly limited, and it is a rubber-based pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a vinyl alkyl ether-based pressure-sensitive adhesive, a polyvinyl alcohol-based pressure-sensitive adhesive.
  • Adhesives, polyvinylpyrrolidone-based adhesives, polyacrylamide-based adhesives, cellulose-based adhesives and the like can be used.
  • Various base polymers can be used depending on the adhesive used.
  • a (meth)acrylic polymer is used as the base polymer of the acrylic pressure-sensitive adhesive.
  • the (meth)acrylate contains acrylate and/or methacrylate.
  • a (meth)acrylic polymer is usually used as the base polymer.
  • Alkyl (meth)acrylate (A) The (meth)acrylic polymer usually contains, as a monomer unit, an alkyl (meth)acrylate as a main component.
  • an alkyl (meth)acrylate (A) constituting the main skeleton of the (meth)acrylic polymer a linear or branched C1 to C20 (meth)acrylic acid alkyl ester can be used.
  • the C1 to C20 (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and isopropyl (meth)acrylate.
  • N-butyl (meth)acrylate N-butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, ( Hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, Decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (me
  • the (meth)acrylic polymer may preferably contain one or both of n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA) as a monomer unit.
  • BA n-butyl acrylate
  • 2EHA 2-ethylhexyl acrylate
  • examples of other (meth)acrylic acid alkyl esters that can be preferably used as the monomer unit of the (meth)acrylic polymer include methyl acrylate, methyl methacrylate (MMA), n-butyl methacrylate (BMA), and methacrylic acid.
  • 2-ethylhexyl (2EHMA) and the like can be mentioned.
  • the alkyl (meth)acrylate (A) used as a monomer unit of the base polymer has a homopolymer glass transition temperature of ⁇ 80° C. or higher and 0° C. or lower.
  • the glass transition temperature of the homopolymer of alkyl (meth)acrylate (A) is preferably ⁇ 70° C. to ⁇ 5° C., more preferably ⁇ 60° C. to ⁇ 10° C.
  • the alkyl (meth)acrylate (A) used as a monomer unit of the base polymer can be contained in an amount of 80% by weight or more based on the weight of the base polymer.
  • the alkyl (meth)acrylate (A) is preferably 85% by weight or more, more preferably 90% by weight or more, based on the weight of the base polymer.
  • 80% by weight or more of an alkyl (meth)acrylate (A) whose homopolymer has a glass transition temperature of ⁇ 60° C. or higher and 0° C. or lower can be contained as a base polymer monomer unit. ..
  • the (meth)acrylic polymer is, in addition to the alkyl (meth)acrylate (A) as a main component, other monomer that is copolymerizable with the alkyl (meth)acrylate, if necessary. It may further contain (copolymerizable monomer).
  • a monomer having a polar group for example, a carboxy group, a hydroxyl group, a nitrogen atom-containing ring, etc.
  • the monomer having a polar group can be useful for introducing a cross-linking point in the acrylic polymer and for enhancing the cohesive force of the (meth)acrylic polymer.
  • the copolymerizable monomer may be used alone or in combination of two or more.
  • Non-limiting specific examples of the copolymerizable monomer include a carboxy group-containing monomer, an acid anhydride group-containing monomer, a hydroxyl group-containing monomer, a sulfonic acid group- or phosphoric acid group-containing monomer, an epoxy group-containing monomer, and a cyano group-containing monomer.
  • Examples of the carboxy group-containing monomer include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid and the like;
  • Examples of the acid anhydride group-containing monomer include maleic anhydride and itaconic anhydride;
  • Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and (meth)acrylate.
  • Examples of the monomer having a sulfonic acid group or a phosphoric acid group include styrenesulfonic acid, allylsulfonic acid, sodium vinylsulfonate, 2-(meth)acrylamido-2-methylpropanesulfonic acid, (meth)acrylamidopropanesulfonic acid.
  • epoxy group-containing monomer examples include epoxy group-containing acrylates such as (meth)acrylic acid glycidyl and (meth)acrylic acid-2-ethylglycidyl ether, allyl glycidyl ether, and (meth)acrylic acid glycidyl ether;
  • the cyano group-containing monomer examples include acrylonitrile and methacrylonitrile.
  • Examples of the isocyanate group-containing monomer include 2-isocyanatoethyl (meth)acrylate and the like;
  • Examples of the amide group-containing monomer include (meth)acrylamide; N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dipropyl(meth)acrylamide, N,N-diisopropyl( N,N-dialkyl(meth)acrylamides such as (meth)acrylamide, N,N-di(n-butyl)(meth)acrylamide, N,N-di(t-butyl)(meth)acrylamide; N-ethyl (meth ) N-alkyl(meth)acrylamides such as acrylamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, Nn-butyl(meth)acrylamide; N-vinylcarboxylic amides such
  • Examples of the maleimides include N-cyclohexyl maleimide, N-isopropyl maleimide, N-lauryl maleimide, N-phenyl maleimide and the like;
  • Examples of itaconimides include N-methyl itaconimide, N-ethyl itaconimide, N-butyl itaconimide, N-octyl itaconimide, N-2-ethylhexyl itaconimide, N-cyclohexyl itaconimide, N -Lauryl itaconimide and the like;
  • Examples of aminoalkyl (meth)acrylates include aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, and (meth)acrylic.
  • alkoxyalkyl (meth)acrylates examples include methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, propoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, and (meth)acrylic acid.
  • Ethoxypropyl and the like can be mentioned;
  • vinyl esters include vinyl acetate, vinyl propionate and the like;
  • vinyl ethers include vinyl alkyl ethers such as methyl vinyl ether and ethyl vinyl ether;
  • aromatic vinyl compound include styrene, ⁇ -methylstyrene, vinyltoluene and the like;
  • olefins include ethylene, butadiene, isoprene, and isobutylene;
  • Examples of the (meth)acrylic acid ester having an alicyclic hydrocarbon group include cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate and the like;
  • Examples of the (meth)acrylic acid ester having an aromatic hydrocarbon group include phenyl(meth)acrylate, phenoxyethyl(meth)acrylate, and benz
  • the amount thereof is not particularly limited, but it is usually suitable to be 0.01% by weight or more of the total amount of the monomer components. From the viewpoint of better exerting the effect of using the copolymerizable monomer, the amount of the copolymerizable monomer used may be 0.1% by weight or more, or 1% by weight or more based on the total amount of the monomer components.
  • the amount of the copolymerizable monomer used can be 50% by weight or less, and preferably 40% by weight or less, based on the total amount of the monomer components. This can prevent the cohesive force of the pressure-sensitive adhesive from becoming too high, and improve the tackiness at room temperature (25° C.).
  • the (meth)acrylic polymer is, in addition to the alkyl (meth)acrylate as a main component, optionally a hydroxyl group-containing monomer (typically, as described above) as a monomer unit.
  • a (meth)acrylic monomer containing a hydroxyl group examples include, as described above, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 3-hydroxy (meth)acrylate.
  • hydroxyalkyl (meth)acrylate such as hydroxylauryl, (4-hydroxymethylcyclohexyl)methyl (meth)acrylate, and the like, 2-hydroxyethyl (meth)acrylate, 4-hydroxy (meth)acrylate.
  • Butyl, 6-hydroxyhexyl (meth)acrylate and the like can be preferably used.
  • preferable examples include 2-hydroxyethyl acrylate (HEA) and 4-hydroxybutyl acrylate (4HBA).
  • HSA 2-hydroxyethyl acrylate
  • 4HBA 4-hydroxybutyl acrylate
  • the hydroxyl group-containing monomer can also serve to suppress the decrease in transparency due to moisture by increasing the hydrophilicity of the pressure-sensitive adhesive layer.
  • the amount of the hydroxyl group-containing monomer to be used is not particularly limited, but usually 0.01% by weight or more, 0.1% by weight or more, based on the total amount of the monomer unit for preparing the (meth)acrylic polymer. It can be 1% by weight or more, 0.5% by weight or more.
  • the (meth)acrylic polymer is, in addition to the alkyl (meth)acrylate as the main component, a polyfunctional polymer for the purpose of adjusting the cohesive force of the pressure-sensitive adhesive layer, if necessary. It may contain a polymerizable monomer.
  • polyfunctional monomer examples include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, Pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,12-dodecane Diol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, allyl(meth)acrylate, vinyl(meth)acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate,
  • trimethylolpropane tri(meth)acrylate, 1,6-hexanediol di(meth)acrylate and dipentaerythritol hexa(meth)acrylate can be preferably used.
  • the polyfunctional monomers may be used alone or in combination of two or more.
  • the amount of the polyfunctional monomer used varies depending on the molecular weight, the number of functional groups, etc., but is usually 0.01% by weight to 3.0% by weight based on the total amount of the monomer components for preparing the alkyl (meth)acrylate (A). It is suitable to set it in the range of wt%, and it may be 0.02 wt% to 2.0 wt% or 0.03 wt% to 1.0 wt%.
  • the base polymer contains, as a copolymerizable monomer unit, at least one polar monomer (B) selected from the group consisting of a carboxyl group-containing monomer (b1) and a nitrogen-containing monomer (b2). It can also be included.
  • the polar monomer (B) may be included in an amount of 0 to 20% by weight based on the weight of the base polymer.
  • the polar monomer (B) is preferably 0.1 to 17.5% by weight, more preferably 1 to 15% by weight, based on the weight of the base polymer.
  • the base polymer may contain a carboxyl group-containing monomer (b1) as a copolymerizable monomer unit.
  • the carboxy group-containing monomer (b1) include, but are not limited to, acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid and the like. ..
  • the carboxyl group-containing monomer (b1) may be acrylic acid or methacrylic acid.
  • the carboxyl group-containing monomer (b1) may be acrylic acid (AA).
  • the base polymer may include a nitrogen-containing monomer (b2) as a copolymerizable monomer unit.
  • the nitrogen-containing monomer (b2) include vinyl monomers having a lactam ring (for example, vinylpyrrolidone monomers such as N-vinylpyrrolidone and methylvinylpyrrolidone, ⁇ -lactam ring, ⁇ -lactam ring, and ⁇ -).
  • Maleimide-based monomers such as maleimide, N-cyclohexylmaleimide, N-phenylmaleimide;
  • the nitrogen-containing monomer (b2) may be N-vinylpyrrolidone, methylvinylpyrrolidone, N,N-dimethyl(meth)acrylamide. In a more preferred embodiment of the present invention, the nitrogen-containing monomer (b2) may be N-vinylpyrrolidone.
  • the method for obtaining the (meth)acrylic polymer is not particularly limited, and various known methods for synthesizing acrylic polymers, such as solution polymerization method, emulsion polymerization method, bulk polymerization method, suspension polymerization method, and photopolymerization method.
  • the above-mentioned polymerization method can be appropriately adopted.
  • the solution polymerization method may be preferably adopted.
  • the polymerization temperature at the time of performing solution polymerization can be appropriately selected according to the type of monomer and solvent used, the type of polymerization initiator, etc., and is, for example, about 20°C to 170°C (typically 40°C to 140°C). C.).
  • the initiator used for the polymerization can be appropriately selected from conventionally known thermal polymerization initiators, photopolymerization initiators, etc. according to the polymerization method.
  • the polymerization initiators may be used alone or in combination of two or more.
  • thermal polymerization initiator examples include azo polymerization initiators (eg, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobis( 2-methylpropionic acid)dimethyl, 4,4′-azobis-4-cyanovaleric acid, azobisisovaleronitrile, 2,2′-azobis(2-amidinopropane)dihydrochloride, 2,2′-azobis[2 -(5-Methyl-2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis(2-methylpropionamidine)disulfate, 2,2'-azobis(N,N'-dimethylene Isobutylamidine) dihydrochloride, etc.); Persulfate such as potassium persulfate; Peroxide type polymerization initiator (eg, dibenzoyl peroxide, t-butyl permaleate, lau
  • the amount of the thermal polymerization initiator used is not particularly limited, but is, for example, 0.01 parts by weight to 5 parts by weight, preferably 0.05 parts by weight to 100 parts by weight of the monomer component used for preparing the acrylic polymer.
  • the amount can be within the range of 3 parts by weight.
  • the photopolymerization initiator is not particularly limited, and examples thereof include benzoin ether photopolymerization initiators, acetophenone photopolymerization initiators, ⁇ -ketol photopolymerization initiators, aromatic sulfonyl chloride photopolymerization initiators, and photoactivators.
  • Oxime photopolymerization initiator, benzoin photopolymerization initiator, benzyl photopolymerization initiator, benzophenone photopolymerization initiator, ketal photopolymerization initiator, thioxanthone photopolymerization initiator, acylphosphine oxide photopolymerization initiator Agents and the like can be used.
  • the amount of the photopolymerization initiator used is not particularly limited, but for example, 0.01 part by weight to 5 parts by weight, preferably 0.05 part by weight to 100 parts by weight of the monomer component used for the preparation of the acrylic polymer.
  • the amount can be within the range of 3 parts by weight.
  • the (meth)acrylic polymer is obtained by solution polymerization using a mixture of a monomer component as described above and a polymerization initiator, for example, ethyl acetate or toluene as a polymerization solvent.
  • a (meth)acrylic polymer can be obtained.
  • the reaction is usually carried out under a stream of an inert gas such as nitrogen with a polymerization initiator at about 50 to 70° C. for about 5 to 30 hours.
  • the pressure-sensitive adhesive layer disclosed in the present specification can be formed using, for example, a pressure-sensitive adhesive composition containing the (meth)acrylic polymer, the silicone oligomer Ps described below, and other additives.
  • the weight average molecular weight Mw of the above-mentioned base polymer may be 500,000 to 2,500,000. In one embodiment of the present invention, the weight average molecular weight Mw of the base polymer may be preferably 700,000 to 2.7 million, more preferably 800,000 to 2.5 million.
  • the pressure-sensitive adhesive layer contains silicone oligomer Ps.
  • Silicone oligomer Ps can function as a tackiness increase retarder that contributes to suppression of initial tackiness and improvement of tackiness increase ratio due to the low polarity and mobility of the siloxane structure.
  • a polymer having a siloxane structure in its side chain can be preferably used.
  • the silicone oligomer Ps used in the present invention has a glass transition temperature (Tg) in the range of -50°C to 100°C.
  • Tg glass transition temperature
  • the Tg of the silicone oligomer Ps may preferably be -30°C or higher and 70°C or lower, and more preferably -20°C or higher and 60°C or lower.
  • the silicone oligomer Ps used in the present invention has a weight average molecular weight Mw of 10,000 or more and 300,000 or less.
  • the weight average molecular weight Mw of the silicone oligomer Ps may be preferably 12,500 or more and 2500000 or less, more preferably 15000 or more and 2000000 or less.
  • the weight average molecular weight Mw of the silicone oligomer Ps is within the above range, it is easy to adjust the compatibility and mobility in the pressure-sensitive adhesive layer to an appropriate range, and the initial low tackiness and strong tackiness during use are high. It becomes easier to realize a pressure-sensitive adhesive sheet that is compatible at both levels.
  • the silicone oligomer Ps has a Tg of ⁇ 70° C. or higher and 30° C. or lower, a side chain silicone functional group equivalent of 1000 to 20000 g/mol, and a weight average molecular weight Mw of 10,000 to 300,000. May be
  • the silicone oligomer Ps may include a monomer S1 having a polyorganosiloxane skeleton and a monomer having a homopolymer glass transition temperature of ⁇ 70° C. or higher and 180° C. or lower as monomer units.
  • Monomer S1 having a polyorganosiloxane skeleton The monomer S1 having a polyorganosiloxane skeleton that can be used in the silicone oligomer Ps of the present invention is not particularly limited, and any monomer having a polyorganosiloxane skeleton can be used.
  • the polyorganosiloxane skeleton include, but are not limited to, trimethylsiloxane (TM), dimethylsiloxane (DM), polyoxyethylmethylsiloxane (EOM), and the like.
  • the monomer S1 having a polyorganosiloxane skeleton for example, a compound represented by the following general formula (1) or (2) can be used. More specifically, as one-end reactive silicone oil manufactured by Shin-Etsu Chemical Co., Ltd., X-22-174ASX, X-22-2426, X-22-2475, KF-2012, X-22-174BX, X -22-2404 and the like.
  • the monomer S1 having a polyorganosiloxane skeleton may be used alone or in combination of two or more.
  • R 3 in the general formulas (1) and (2) is hydrogen or methyl
  • R 4 is a methyl group or a monovalent organic group
  • m and n are integers of 0 or more.
  • the silicone oligomer Ps used in the present invention has a silicone functional group equivalent of its side chain of 1000 to 20000 g/mol.
  • the silicone functional group equivalent of the side chain of the silicone oligomer Ps may be preferably 1200 to 18000 g/mol, more preferably 1500 to 15000 g/mol.
  • the silicone functional group equivalent of the side chain of the silicone oligomer Ps is within the above range, it is easy to adjust the compatibility (for example, the compatibility with the base polymer) and the mobility in the pressure-sensitive adhesive layer to an appropriate range and It becomes easy to realize a pressure-sensitive adhesive sheet that achieves both low tackiness and strong tackiness during use at a high level.
  • the “functional group equivalent” means the weight of the main skeleton (for example, polydimethylsiloxane) bonded to each functional group.
  • the unit of g/mol is converted to 1 mol of the functional group.
  • the functional group equivalent of the monomer S1 having a polyorganosiloxane skeleton can be calculated from the spectrum intensity of 1 H-NMR (proton NMR) based on nuclear magnetic resonance (NMR), for example. Calculation of the functional group equivalent (g/mol) of the monomer S1 having a polyorganosiloxane skeleton based on the 1 H-NMR spectrum intensity is required based on a general structural analysis method related to 1 H-NMR spectrum analysis. In that case, it can be performed by referring to the description of Japanese Patent No. 5915153.
  • an arithmetic average value can be used as the functional group equivalent of the monomer S1. That is, the functional group equivalent of the monomer S1 composed of n kinds of monomers (monomer S1 1 , monomer S1 2 ... Monomer S1 n ) having different functional group equivalents can be calculated by the following formula.
  • Functional group equivalent of the monomer S1 (g / mol) (monomer S1 1 functional group equivalent ⁇ monomer S1 1 of the amount + monomer S1 2 functional group equivalent ⁇ monomer S1 2 of the amount + ... + monomer S1 n
  • the content of the monomer S1 having a polyorganosiloxane skeleton may be, for example, 5% by weight or more based on the total monomer components for preparing the silicone oligomer Ps, and the effect as a tackiness increase retarder can be better exhibited. From the viewpoint of the above, the amount is preferably 10% by weight or more, and may be 15% by weight or more. In some embodiments, the content of the monomer S1 may be, for example, 20% by weight or more. From the viewpoint of polymerization reactivity and compatibility, the content of the monomer S1 having a polyorganosiloxane skeleton is appropriately 60% by weight or less based on the total monomer components for preparing the silicone oligomer Ps.
  • the content of the monomer S1 having a polyorganosiloxane skeleton is within the above range, it is easy to realize a pressure-sensitive adhesive sheet that achieves a high level of both low initial tackiness and increase in tackiness (strong tackiness) during use. Become.
  • the silicone oligomer Ps of the present invention is a (meth)acryl-based monomer or another monomer copolymerizable with the monomer S1 having the polyorganosiloxane skeleton. It contains a copolymerizable monomer.
  • a homopolymer having a glass transition temperature of ⁇ 70° C. to 180° C. is used as the copolymerizable (meth)acrylic monomer or other copolymerizable monomer that can be used in the silicone oligomer Ps of the present invention.
  • Examples thereof include, but are not limited to, (meth)acrylic acid alkyl ester and (meth)acrylic acid ester having an alicyclic hydrocarbon group.
  • the (meth)acrylic acid alkyl ester include methyl methacrylate (MMA), butyl methacrylate (BMA), 2-ethylhexyl methacrylate (2-EHMA), butyl acrylate (BA), and 2-ethylhexyl acrylate (2-EHA).
  • Examples of the (meth)acrylic acid ester having an alicyclic hydrocarbon group include 2-((3-hydroxymethyl)-adamantan-1-yl)methoxy-2-oxoethyl methacrylate (2EHAMA), cyclopentyl (meth)acrylate, Examples thereof include, but are not limited to, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, 1-adamantyl (meth)acrylate, and the like.
  • At least one selected from 2-((3-hydroxymethyl)-adamantan-1-yl)methoxy-2-oxoethyl methacrylate (2EHAMA) and isobornyl methacrylate (IBXMA) is a monomer unit.
  • it may contain at least one selected from dicyclopentanyl methacrylate, isobornyl methacrylate and cyclohexyl methacrylate as a monomer unit. These monomers may be used alone or in combination of two or more.
  • the amount of the above-mentioned (meth)acrylic acid alkyl ester and the above-mentioned (meth)acrylic acid ester having an alicyclic hydrocarbon group used is, for example, 10% by weight or more and 95% by weight or more based on all the monomer components for preparing the silicone oligomer Ps. May be 20% by weight or more, 95% by weight or less, 30% by weight or more and 90% by weight or less, or 40% by weight or more and 90% by weight or less, It may be 50% by weight or more and 85% by weight or less.
  • a carboxyl group-containing monomer and an acid anhydride group-containing monomer exemplified above as the monomer that can be used in the alkyl (meth)acrylate (A) are included.
  • the total amount of the monomer S1 and the (meth)acrylic monomer in the entire monomer component is, for example, 50% by weight.
  • the amount may be 70% by weight or more, 85% by weight or more, 90% by weight or more, 95% by weight or more, or substantially 100% by weight.
  • the composition of the (meth)acrylic monomer contained in the monomer component can be set such that the glass transition temperature T m1 based on the composition of the (meth)acrylic monomer is higher than 0° C., for example.
  • the glass transition temperature T m1 based on the composition of the (meth)acrylic monomer is based on the composition of only the (meth)acrylic monomer among the monomer components used for the preparation of the silicone oligomer Ps, and according to the Fox equation. Refers to the required Tg.
  • T m1 is the glass transition temperature of the homopolymer of each (meth)acrylic monomer, which is obtained by applying the above-described Fox equation to only the (meth)acrylic monomer among the monomer components used for the preparation of the silicone oligomer Ps. And the weight fraction of each (meth)acrylic monomer in the total amount of the (meth)acrylic monomer.
  • the silicone oligomer Ps having a glass transition temperature T m1 higher than 0° C. the initial adhesive force is easily suppressed. Further, by using the silicone oligomer Ps having a glass transition temperature T m1 higher than 0° C., it is easy to obtain a pressure-sensitive adhesive sheet having a large adhesive force increase ratio.
  • T m1 may be ⁇ 20° C. or higher, ⁇ 10° C. or higher, 0° C. or higher, or 10° C. or higher. At higher T m1, the adhesive strength in the early stage of application generally tends to be better suppressed. Further, T m1 may be, for example, 90° C. or lower, 80° C. or lower, 70° C. or lower, or lower than 70° C. When T m1 is low, increase in adhesive strength due to heating tends to be facilitated.
  • the technique disclosed herein can be preferably carried out using a silicone oligomer Ps having T m1 in the range of, for example, ⁇ 20° C. to 90° C., or ⁇ 10° C. to 80° C., and 0° C. to 70° C.
  • the silicone oligomer Ps can be produced, for example, by polymerizing the above-mentioned monomer by a known method such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, or a photopolymerization method.
  • a chain transfer agent can be used to adjust the molecular weight of the silicone oligomer Ps.
  • the chain transfer agent to be used include compounds having a mercapto group such as octyl mercaptan, lauryl mercaptan, t-nonyl mercaptan, t-dodecyl mercaptan, mercaptoethanol and ⁇ -thioglycerol; thioglycolic acid, methyl thioglycolate, Ethyl thioglycolate, propyl thioglycolate, butyl thioglycolate, t-butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate, isooctyl thioglycolate, decyl thioglycolate, dodecyl thioglycolate, ethylene Examples thereof include
  • the amount of the chain transfer agent used is not particularly limited, but is usually 0.05 to 20 parts by weight, preferably 0.1 to 15 parts by weight with respect to 100 parts by weight of the monomer. And more preferably 0.2 to 10 parts by weight.
  • the chain transfer agents may be used alone or in combination of two or more.
  • the silicone oligomer Ps may be included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the (meth)acrylic polymer.
  • the silicone oligomer Ps is preferably contained in an amount of 0.25 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the above-mentioned (meth)acrylic polymer. May be included in the section.
  • the content of the silicone oligomer Ps contained in the adhesive layer is within the above range, the initial adhesive force can be suppressed and a higher adhesive force after heating can be obtained.
  • the silicone oligomer Ps as described above can function favorably as an agent for increasing the adhesive strength by being mixed in the adhesive layer.
  • the pressure-sensitive adhesive sheet disclosed herein can be preferably implemented in a mode in which the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer contains a base polymer and a pressure-sensitive adhesive force increase retarder, and the pressure-sensitive adhesive force increase retarder contains a silicone oligomer Ps.
  • the silicone oligomer Ps functions as an adhesive force increase retarder because the initial adhesive force is suppressed by the silicone oligomer Ps existing on the surface of the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet from before attachment to the adherend and in the initial stage of attachment.
  • the amount of the silicone oligomer Ps present on the surface of the pressure-sensitive adhesive layer decreases due to the pressure-sensitive adhesive flowing due to the passage of time after application, heating, etc., and the silicone oligomer Ps is compatible with the pressure-sensitive adhesive, increasing the adhesive strength. Conceivable. Therefore, as the above-mentioned adhesive force increase retarder in the technology disclosed herein, other materials capable of exhibiting the same kind of function may be used instead of the silicone oligomer Ps or in combination with the silicone oligomer Ps.
  • a non-limiting example of such a material is a polymer having a polyoxyalkylene structure in the molecule (hereinafter, also referred to as “polymer Po”).
  • the polymer Po can be, for example, a polymer including a monomer unit derived from a monomer having a polyoxyalkylene skeleton. Specific examples thereof include homopolymers or copolymers of any one of the above-mentioned monomers having a polyoxyalkylene skeleton, and one or more of monomers having a polyoxyalkylene skeleton and others.
  • a copolymer with the monomer (eg, a (meth)acrylic monomer) or the like can be used as the polymer Po.
  • the amount of the monomer having a polyoxyalkylene skeleton is not particularly limited, but for example, the amount of the monomer S1 used in the silicone oligomer Ps described above may be applied to the amount of the monomer having a polyoxyalkylene skeleton in the polymer Po. You can The amount of the polymer Po used in the pressure-sensitive adhesive layer is not particularly limited. For example, the amount of the silicone oligomer Ps used for the base polymer described above can be applied to the amount of the polymer Po used for the base polymer.
  • a part of the amount of the silicone oligomer Ps used with respect to the above-mentioned base polymer may be replaced with the polymer Po.
  • the melting temperature of the silicone oligomer Ps may be -20 to 120°C. In another embodiment of the present invention, the melting temperature of the silicone oligomer Ps may be ⁇ 10 to 90° C., 0 to 80° C.
  • a crosslinking agent may be used in the pressure-sensitive adhesive layer disclosed in the present specification for the purpose of adjusting cohesive force and the like.
  • a commonly used cross-linking agent can be used, and examples thereof include epoxy cross-linking agents, isocyanate cross-linking agents, silicone cross-linking agents, oxazoline cross-linking agents, aziridine cross-linking agents, silane cross-linking agents, alkyl etherifications. Examples thereof include a melamine-based crosslinking agent and a metal chelate-based crosslinking agent.
  • an isocyanate cross-linking agent, an epoxy cross-linking agent, and a metal chelate cross-linking agent can be preferably used.
  • the cross-linking agents can be used alone or in combination of two or more.
  • examples of the isocyanate cross-linking agent include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene.
  • examples thereof include diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, and adducts of these with polyols such as trimethylolpropane.
  • a compound having at least one or more isocyanate group and one or more unsaturated bond in one molecule should also be used as an isocyanate cross-linking agent. You can These may be used alone or in combination of two or more.
  • Epoxy crosslinking agents include bisphenol A, epichlorohydrin type epoxy resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol glycidyl ether, trimethylolpropane tri Glycidyl ether, diglycidyl aniline, diamine glycidyl amine, N,N,N',N'-tetraglycidyl-m-xylylenediamine and 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane You can These may be used alone or in combination of two or more.
  • metal chelate compound examples include aluminum, iron, tin, titanium and nickel as metal components, and acetylene, methyl acetoacetate and ethyl lactate as chelate components. These may be used alone or in combination of two or more.
  • the amount of the crosslinking agent used can be, for example, 0.01 part by weight or more, and preferably 0.05 part by weight or more, based on 100 parts by weight of the base polymer. A higher cohesive force tends to be obtained by increasing the amount of the crosslinking agent used.
  • the amount of the cross-linking agent used may be 0.1 part by weight or more, 100 parts by weight or more, 0.5 parts by weight or more, and 1 part by weight or more. Good.
  • the amount of the cross-linking agent to be used is usually 15 parts by weight or less, preferably 10 parts by weight or less, based on 100 parts by weight of the base polymer. It may be 5 parts by weight or less.
  • the use amount of the crosslinking agent is not too large. It may be advantageous from the viewpoint of good expression.
  • the technique disclosed in the present specification can be preferably carried out in a mode in which at least an isocyanate cross-linking agent is used as the cross-linking agent.
  • the amount of the isocyanate-based cross-linking agent based on 100 parts by weight of the base polymer is, for example, 5 parts by weight or less. It may be 3 parts by weight or less, 1 part by weight or less, 0.7 parts by weight or less, and 0.5 parts by weight or less.
  • a cross-linking catalyst may be used in order to more effectively promote any of the above-mentioned cross-linking reactions.
  • a crosslinking catalyst for example, a tin-based catalyst (particularly dioctyltin dilaurate) can be preferably used.
  • the amount of the crosslinking catalyst used is not particularly limited, but can be, for example, approximately 0.0001 parts by weight to 1 part by weight with respect to 100 parts by weight of the base polymer.
  • the pressure-sensitive adhesive layer disclosed in the present specification may further contain a silane coupling agent.
  • the durability can be improved by using the silane coupling agent.
  • the silane coupling agent one having any appropriate functional group can be used. Specific examples of the functional group include a vinyl group, an epoxy group, an amino group, a mercapto group, a (meth)acryloxy group, an acetoacetyl group, an isocyanate group, a styryl group, and a polysulfide group.
  • vinyl group-containing silane coupling agents such as vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, and vinyltributoxysilane; ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycine Epoxy group-containing silane coupling agents such as cidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; ⁇ -aminopropyltrimethoxysilane, N- ⁇ -(aminoethyl)- ⁇ -aminopropylmethyldimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane, ⁇ -triethoxysilyl-N-(1,3-dimethylbutylidene) Amino group-
  • silane coupling agent for example, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane and ⁇ -mercaptopropylmethyldimethoxysilane are preferably used. You can
  • the silane coupling agent may be used alone or in combination of two or more kinds, but the total content is 100 parts by weight of the base polymer and the silane coupling agent.
  • the amount is preferably 0.001 to 5 parts by weight, more preferably 0.01 to 1 part by weight, further preferably 0.02 to 1 part by weight, further preferably 0.05 to 0.6 part by weight.
  • the pressure-sensitive adhesive layer in the technique disclosed herein is a tackifier, a leveling agent, a plasticizer, a softening agent, a colorant (a dye, a pigment, etc.), a filler, etc. within a range that does not significantly impair the effects of the present invention.
  • known additives such as antistatic agents, antiaging agents, ultraviolet absorbers, antioxidants, light stabilizers and preservatives that can be used for pressure-sensitive adhesives may be included.
  • a method for forming a pressure-sensitive adhesive layer for example, a method in which the pressure-sensitive adhesive composition is applied to a release-treated separator or the like, and a polymerization solvent or the like is dried and removed to form a pressure-sensitive adhesive layer, and then transferred to a polarizing film, or It is prepared by a method of applying the above-mentioned pressure-sensitive adhesive composition to a polarizing film, drying and removing a polymerization solvent and the like to form an adhesive layer on the polarizing film.
  • one or more solvents other than the polymerization solvent may be newly added as appropriate.
  • a silicone release liner is preferably used as the release-treated separator.
  • the step of forming the pressure-sensitive adhesive layer by applying the adhesive composition of the present invention on such a liner, and drying the pressure-sensitive adhesive layer as a method for drying the pressure-sensitive adhesive, an appropriate method is appropriately adopted depending on the purpose. obtain.
  • a method of heating and drying the above coating film is used.
  • the heat drying temperature is preferably 40°C to 200°C, more preferably 50°C to 180°C, and particularly preferably 70°C to 170°C.
  • the drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and particularly preferably 10 seconds to 5 minutes.
  • an anchor layer can be formed on the surface of the polarizing film, or an adhesive layer can be formed after various types of easy adhesion treatment such as corona treatment and plasma treatment. Further, the surface of the pressure-sensitive adhesive layer may be subjected to easy adhesion treatment.
  • Various methods are used to form the adhesive layer. Specifically, for example, roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, die coater, etc. Examples of the method include an extrusion coating method.
  • the thickness of the adhesive layer is not particularly limited and is, for example, about 1 to 100 ⁇ m.
  • the thickness is preferably 2 to 50 ⁇ m, more preferably 2 to 40 ⁇ m, and further preferably 5 to 35 ⁇ m.
  • the pressure-sensitive adhesive layer When the pressure-sensitive adhesive layer is exposed, the pressure-sensitive adhesive layer may be protected with a release-treated sheet (separator) until practical use.
  • a constituent material of the separator for example, polyethylene, polypropylene, polyethylene terephthalate, a plastic film such as a polyester film, a porous material such as paper, cloth, non-woven fabric, a net, a foamed sheet, a metal foil, and a laminated body thereof are appropriately used.
  • a plastic film such as a polyester film
  • a porous material such as paper, cloth, non-woven fabric, a net, a foamed sheet, a metal foil, and a laminated body thereof
  • plastic thin films and plastic films are preferably used because they have excellent surface smoothness.
  • the plastic film is not particularly limited as long as it is a film capable of protecting the pressure-sensitive adhesive layer, and examples thereof include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film and vinyl chloride. Examples thereof include polymer films, polyethylene terephthalate films, polybutylene terephthalate films, polyurethane films, ethylene-vinyl acetate copolymer films and the like.
  • the thickness of the separator is usually 5 to 200 ⁇ m, preferably about 5 to 100 ⁇ m.
  • a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, release and antifouling treatment with silica powder or the like, coating type, kneading type, vapor deposition type It is also possible to perform antistatic treatment such as. Particularly, by appropriately performing a peeling treatment such as a silicone treatment, a long-chain alkyl treatment, or a fluorine treatment on the surface of the separator, the peelability from the pressure-sensitive adhesive layer can be further enhanced.
  • the release-treated sheet used in the production of the pressure-sensitive adhesive layer-attached polarizing film can be used as it is as a separator for the pressure-sensitive adhesive layer-attached polarizing film, which simplifies the process.
  • the present invention will be described below with reference to examples, but the present invention is not limited to the examples shown below. In addition, all parts and% in each example are based on weight. Unless otherwise specified below, the room temperature standing condition is 23° C. and 65% RH.
  • the weight average molecular weight Mw of each of the following polymers was determined by using a GPC device (manufactured by Tosoh Corporation, HLC-8220GPC) under the following conditions, and calculated in terms of polystyrene.
  • THF tetrahydrofuran
  • Eluent THF
  • Flow rate 0.6 ml/min
  • Measuring temperature 40°C
  • SP value 32.8 thickness 23 ⁇ m
  • ⁇ Active energy ray> As active energy rays, ⁇ Ultraviolet irradiation device (gallium-encapsulated metal halide lamp): Fusion UV Systems, Inc. Light HAMMER10 ⁇ Valve: V valve ⁇ Peak illuminance: 1600 mW/cm 2 , An integrated dose of 1000/mJ/cm 2 (wavelength 380 to 440 nm) was used. The illuminance of ultraviolet rays was measured using a Sola-Check system manufactured by Solatell.
  • the active energy ray-curable adhesive was applied to the easy-adhesive layer by an MCD coater (manufactured by Fuji Machine Co., Ltd.). (Cell shape: honeycomb, gravure roll number of lines: 1000/inch, rotation speed 140%/vs line speed) was used to coat the adhesive layer to a thickness of 0.5 ⁇ m. Then, the acrylic resin film was bonded to both sides of the above-mentioned polarizer with a roll machine as a transparent protective film on the viewing side and/or the panel side via the adhesive.
  • the both sides of the bonded acrylic resin film were heated to 50° C. using an IR heater, and both sides were irradiated with the above-mentioned ultraviolet rays to cure the active energy ray-curable adhesive. Further, it was dried with hot air at 70° C. for 3 minutes to obtain a polarizing film having transparent protective films on both sides of the polarizer (Table 1).
  • the bonding line speed was 25 m/min.
  • cross-linking agent based on 100 parts of the solid content of the acrylic polymer solution A, a cross-linking agent containing 0.6 part of a compound having an isocyanate group as a main component (manufactured by Nippon Polyurethane Co., Ltd., trade name “Coronate L”) ) And 0.075 part of ⁇ -glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-403”) as a silane coupling agent in this order, and the adhesive agent Polymer solution A was prepared.
  • cross-linking agent a cross-linking agent containing 0.6 part of a compound having an isocyanate group as a main component based on 100 parts of the solid content of the acrylic polymer solution (B) (manufactured by Nippon Polyurethane Co., Ltd., trade name “Coronate”) L”) and 0.075 part of ⁇ -glycidoxypropyltrimethoxysilane (trade name “KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent in this order, An adhesive polymer solution B was prepared.
  • compositions of the acrylic polymer solution (A) (polymer A) and the acrylic polymer solution (B) (polymer B) are shown in Table 2 below.
  • Silicone Oligomer B to F were produced in the same manner as Silicone Oligomer A except that the monomer composition and parts by weight were changed to the constituent components shown in Table 3.
  • Comparative Example 1 A polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1 except that the silicone oligomer A was removed in Comparative Example 1.
  • the measurement was performed 200 times at intervals of 1 time/0.5 s, and the average value was used as the measured value.
  • the number of samples was three.
  • the average value thereof is shown in the column of "2 kg roller" in Table 4 as the initial adhesive strength.
  • the reworkability was judged based on the level of adhesive strength according to the following criteria.
  • C More than 5N/25mm and 6N/25mm or less, and rework succeeds 70% or more.
  • D More than 6 N/25 mm and 7 N/25 mm or less, and rework succeeds 60% or more.
  • E Over 7 N/25 mm, rework fails more than 40%.
  • the produced polarizing film with an adhesive layer was cut into a length of 120 mm and a width of 25 mm to obtain a sample.
  • the sample was attached to a 0.7 mm-thick non-alkali glass plate (EG-XG, manufactured by Corning Incorporated) using a laminator, and then autoclaved at 50° C. and 5 atm for 15 minutes for complete adhesion.
  • the adhesive strength of the sample was measured.
  • the adhesive force is measured by a tensile tester (Autograph SHIMAZU AG-1 1OKN) at a peeling angle of 90° and a peeling speed of 300 mm/min. (N/25 mm, measuring length 80 mm) was obtained by doing.

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Abstract

Provided is a polarizing film with an adhesive layer, provided with high durability and reworkability. Provided is a polarizing film with an adhesive layer, comprising a polarizing film and an adhesive layer, wherein the adhesive layer includes a base polymer and a silicone oligomer, the base polymer being a (meth)acrylic polymer, the silicone oligomer being included in the amount of 0.1-20 parts by weight with respect to 100 parts by weight of the (meth)acrylic polymer, and the silicone oligomer having a Tg of -50°C to 100°C, a side chain silicone functional group equivalent weight of 1,000-20,000 g/mol, and a weight-average molecular weight of 10,000 to 300,000.

Description

粘着剤層付き偏光フィルムPolarizing film with adhesive layer
　本発明は、粘着剤層付偏光フィルムに関する。 The present invention relates to a polarizing film with an adhesive layer.
　液晶表示装置には、その画像形成方式から液晶パネル表面を形成するガラス基板の両側に偏光フィルムを配置することが必要不可欠である。偏光フィルムは、一般的には、ポリビニルアルコール系フィルムとヨウ素等の二色性材料からなる偏光子の片面または両面に、保護フィルムをポリビニルアルコール系接着剤等により貼り合わせたものが用いられている。 According to the image forming method, it is essential for liquid crystal display devices to place polarizing films on both sides of the glass substrate that forms the surface of the liquid crystal panel. As the polarizing film, generally, a polyvinyl alcohol-based film and a polarizer made of a dichroic material such as iodine having a protective film bonded to one or both surfaces thereof with a polyvinyl alcohol-based adhesive or the like are used. ..
　前記偏光フィルムを液晶セル等に貼着する際には、通常、粘着剤が使用される。また、偏光フィルムを瞬時に固定できること、偏光フィルムを固着させるのに乾燥工程を必要としないこと等のメリットを有することから、粘着剤は、偏光フィルムの片面に予め粘着剤層として設けられている。即ち、偏光フィルムの貼着には粘着剤層付偏光フィルムが一般的に用いられる（特許文献１および２）。 When attaching the polarizing film to a liquid crystal cell etc., an adhesive is usually used. In addition, the pressure-sensitive adhesive is preliminarily provided as a pressure-sensitive adhesive layer on one surface of the polarizing film, since it has advantages such as being able to instantly fix the polarizing film and not requiring a drying step to fix the polarizing film. .. That is, a polarizing film with an adhesive layer is generally used for sticking a polarizing film (Patent Documents 1 and 2).
　また、偏光フィルムや粘着剤層付き偏光フィルムを液晶パネルのガラス基板に貼り合わせた場合、耐久性が求められており、例えば、環境促進試験として通常行われる加熱および加湿等による耐久試験において、粘着剤層に起因する剥がれや浮き等の不具合が発生しないことが求められる。 Further, when a polarizing film or a polarizing film with a pressure-sensitive adhesive layer is attached to a glass substrate of a liquid crystal panel, durability is required, and for example, in a durability test such as heating and humidification that is usually performed as an environmental promotion test, adhesion It is required that problems such as peeling and floating due to the agent layer do not occur.
　このように偏光フィルムに使用する粘着剤は、高耐久性が求められる反面、偏光板を貼り合わせる際の工程不良で発生した欠点や貼りミスをリカバリーするために、リワーク性の要望も高まっている。近年パネルの薄型化や大型化のトレンドにより、パネルの再活要望が高くなっているため、リワーク性は重要な項目である。しかしながら、高耐久性とリワーク性はトレードオフの関係にあり、両立が非常に難しい特性である。 As described above, while the pressure-sensitive adhesive used for the polarizing film is required to have high durability, there is an increasing demand for reworkability in order to recover a defect or a bonding error caused by a process defect in bonding the polarizing plate. .. Due to the trend of thinner and larger panels in recent years, the demand for re-activating panels is increasing, and reworkability is an important item. However, there is a trade-off relationship between high durability and reworkability, and it is very difficult to achieve both at the same time.
特開２０１１－２１９７６５号Japanese Patent Laid-Open No. 2011-219765 特開２０１８－１６９６１２号JP-A-2018-169612
　上記の背景技術に鑑み、トレードオフの関係にある高耐久性とリワーク性とを両立して備えることができる、粘着剤層付き偏光フィルムが強く望まれている。 In view of the above background art, there is a strong demand for a polarizing film with a pressure-sensitive adhesive layer that can provide both high durability and reworkability that are in a trade-off relationship.
　本発明者らは、鋭意検討の結果、本発明の粘着剤層付き偏光フィルムにより上記の課題を解決し得ることを見出し、本発明を完成するに至った。 As a result of intensive studies, the present inventors have found that the polarizing film with an adhesive layer of the present invention can solve the above problems, and have completed the present invention.
　すなわち、本発明は、下記の実施形態を含む。 That is, the present invention includes the following embodiments.
　（１）偏光フィルムと、粘着剤層とを備える、粘着剤層付き偏光フィルムであって、
　前記粘着剤層は、ベースポリマーと、シリコーンオリゴマーＰｓとを含み、
　前記ベースポリマーは、（メタ）アクリル系ポリマーであり、
　前記シリコーンオリゴマーＰｓは、前記（メタ）アクリル系ポリマー１００重量部に対し、０．１～２０重量部で含まれ、
　前記シリコーンオリゴマーＰｓは、Ｔｇが－５０℃以上１００℃以下であり、側鎖のシリコーン官能基当量が１０００～２００００ｇ／ｍｏｌであり、重量平均分子量Ｍｗが１００００以上３０００００以下である、粘着剤層付き偏光フィルム。 (1) A polarizing film with an adhesive layer, which comprises a polarizing film and an adhesive layer,
The pressure-sensitive adhesive layer includes a base polymer and a silicone oligomer Ps,
The base polymer is a (meth)acrylic polymer,
The silicone oligomer Ps is included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the (meth)acrylic polymer.
The silicone oligomer Ps has a Tg of −50° C. or higher and 100° C. or lower, a side chain silicone functional group equivalent of 1000 to 20000 g/mol, and a weight average molecular weight Mw of 10,000 or more and 300,000 or less. Polarizing film.
　（２）前記シリコーンオリゴマーＰｓが、ポリオルガノシロキサン骨格を有するモノマーＳ１と、ホモポリマーのガラス転移温度が－７０℃以上１８０℃以下のモノマーとをモノマー単位として含む、上記（１）に記載の粘着剤層付き偏光フィルム。 (2) The adhesive according to (1) above, wherein the silicone oligomer Ps contains a monomer S1 having a polyorganosiloxane skeleton and a monomer having a homopolymer glass transition temperature of −70° C. or higher and 180° C. or lower as monomer units. Polarizing film with agent layer.
　（３）前記ベースポリマーのモノマー単位として、ホモポリマーのガラス転移温度が－６０℃以上０℃以下であるアルキル（メタ）アクリレート（Ａ）を８０重量％以上で含有する、上記（１）または（２）に記載の粘着剤層付き偏光フィルム。 (3) As the monomer unit of the base polymer, 80% by weight or more of an alkyl (meth)acrylate (A) having a homopolymer glass transition temperature of −60° C. or higher and 0° C. or lower is contained, or the above (1) or ( The polarizing film with an adhesive layer according to 2).
　（４）前記ベースポリマーのモノマー単位として、カルボキシル基含有モノマー（ｂ１）および窒素含有モノマー（ｂ２）からなる群より選択される少なくとも１種の極性モノマー（Ｂ）を０～２０重量％で更に含有する、上記（３）に記載の粘着剤層付き偏光フィルム。 (4) As the monomer unit of the base polymer, at least one polar monomer (B) selected from the group consisting of a carboxyl group-containing monomer (b1) and a nitrogen-containing monomer (b2) is further contained in an amount of 0 to 20% by weight. The polarizing film with an adhesive layer according to (3) above.
　（５）前記ベースポリマーの重量平均分子量Ｍｗが５０～２５０万である、上記（１）～（４）のいずれかに記載の粘着剤層付き偏光フィルム。 (5) The pressure-sensitive adhesive layer-attached polarizing film as described in any of (1) to (4) above, wherein the base polymer has a weight average molecular weight Mw of 500 to 2,500,000.
　（６）前記シリコーンオリゴマーＰｓの溶融温度が０～１００℃である、上記（１）～（５）のいずれかに記載の粘着剤層付き偏光フィルム。 (6) The polarizing film with a pressure-sensitive adhesive layer according to any one of (1) to (5) above, wherein the silicone oligomer Ps has a melting temperature of 0 to 100° C.
　本発明によれば、貼り合わせ直後のリワーク性を付与しながら、加熱後に粘着力が上昇して耐久性を付与することができる、粘着剤層付き偏光フィルムを提供することができる。 According to the present invention, it is possible to provide a polarizing film with a pressure-sensitive adhesive layer, which can give reworkability immediately after bonding and can increase durability after heating and have increased durability.
図１は、本発明の粘着剤層付き偏光フィルムの概略断面図の一例である。FIG. 1 is an example of a schematic cross-sectional view of a polarizing film with an adhesive layer of the present invention.
　以下、本発明の好適な実施形態について説明する。本明細書において特に言及している事項以外の事柄であって本発明の実施に必要な事柄は、本明細書に記載された発明の実施についての教示と出願時の技術常識とに基づいて当業者に理解され得る。本発明は、本明細書に開示されている内容と当該分野における技術常識とに基づいて実施することができる。 A preferred embodiment of the present invention will be described below. Matters other than the matters particularly referred to in the present specification and necessary for the implementation of the present invention should be determined based on the teaching about the implementation of the invention described in the present specification and the common general knowledge as of the filing. It can be understood by those skilled in the art. The present invention can be carried out based on the contents disclosed in this specification and the common general technical knowledge in the field.
　＜粘着剤層付き偏光フィルム＞
　本発明の粘着剤層付き偏光フィルムは、偏光フィルムと、粘着剤層とを備える。本発明において、粘着剤層は、偏光フィルムの片面に存在してもよいし、両面に存在してもよい。 <Polarizing film with adhesive layer>
The polarizing film with a pressure-sensitive adhesive layer of the present invention includes a polarizing film and a pressure-sensitive adhesive layer. In the present invention, the pressure-sensitive adhesive layer may be present on one side or both sides of the polarizing film.
　一実施形態に係る粘着剤層付き偏光フィルムの構造を図１に模式的に示す。この粘着剤層付き偏光フィルム１０は、偏光フィルム３と、その片面に設けられた粘着剤層４とを備える粘着剤層付き偏光フィルムとして構成されている。図１において、偏光フィルム３は、偏光子１と偏光子１の両面に設けられた保護フィルム２、２’とから構成されているが、保護フィルムは偏光子の片面にのみ設けられてもよい。粘着剤層４は、偏光フィルム３の片側に固定的に、すなわち当該偏光フィルム３から粘着剤層４を分離する意図なく、設けられている。粘着剤層付き偏光フィルム１０は、粘着剤層４を被着体に貼り付けて用いられる。セパレータ５としては、例えば、シート状の基材（ライナー基材）の片面に剥離処理剤による剥離層を設けることで当該片面が剥離面となるように構成されたものを好ましく使用し得る。粘着剤層付き偏光フィルムの構造は、図１に模式的に示された実施形態には限定されない。 The structure of a polarizing film with an adhesive layer according to one embodiment is schematically shown in FIG. The polarizing film with an adhesive layer 10 is configured as a polarizing film with an adhesive layer, which includes the polarizing film 3 and the adhesive layer 4 provided on one surface thereof. In FIG. 1, the polarizing film 3 is composed of a polarizer 1 and protective films 2 and 2′ provided on both sides of the polarizer 1, but the protective film may be provided only on one side of the polarizer. .. The adhesive layer 4 is fixedly provided on one side of the polarizing film 3, that is, without the intention of separating the adhesive layer 4 from the polarizing film 3. The polarizing film 10 with an adhesive layer is used by attaching the adhesive layer 4 to an adherend. As the separator 5, for example, a sheet-shaped base material (liner base material) which has a release layer provided with a release treatment agent on one surface so that the one surface serves as a release surface can be preferably used. The structure of the polarizing film with an adhesive layer is not limited to the embodiment schematically shown in FIG.
　＜偏光子＞
　偏光子は、特に限定されず、各種のものを使用できる。偏光子としては、例えば、ポリビニルアルコール系フィルム、部分ホルマール化ポリビニルアルコール系フィルム、エチレン・酢酸ビニル共重合体系部分ケン化フィルム等の親水性高分子フィルムに、ヨウ素や二色性染料の二色性物質を吸着させて一軸延伸したもの、ポリビニルアルコールの脱水処理物やポリ塩化ビニルの脱塩酸処理物等ポリエン系配向フィルム等が挙げられる。これらの中でも、ポリビニルアルコール系フィルムとヨウ素などの二色性物質からなる偏光子が好適である。これらの偏光子の厚さは特に制限されないが、一般的には２～２５μｍである。 <Polarizer>
The polarizer is not particularly limited, and various kinds can be used. Examples of the polarizer include hydrophilic polymer films such as polyvinyl alcohol film, partially formalized polyvinyl alcohol film, and ethylene/vinyl acetate copolymer partially saponified film, and dichroism of iodine or dichroic dye. Examples include polyene-oriented films such as those obtained by adsorbing a substance and uniaxially stretched, polyvinyl alcohol dehydrated products, polyvinyl chloride dehydrochlorinated products, and the like. Among these, a polarizer made of a polyvinyl alcohol film and a dichroic substance such as iodine is preferable. The thickness of these polarizers is not particularly limited, but is generally 2 to 25 μm.
　ポリビニルアルコール系フィルムをヨウ素で染色し一軸延伸した偏光子は、例えば、ポリビニルアルコール系フィルムをヨウ素の水溶液に浸漬することによって染色し、元長の３～７倍に延伸することで作製することができる。必要に応じてホウ酸や硫酸亜鉛、塩化亜鉛等を含んでいても良いヨウ化カリウムなどの水溶液に浸漬することもできる。さらに必要に応じて染色前にポリビニルアルコール系フィルムを水に浸漬して水洗してもよい。ポリビニルアルコール系フィルムを水洗することでポリビニルアルコール系フィルム表面の汚れやブロッキング防止剤を洗浄することができるほかに、ポリビニルアルコール系フィルムを膨潤させることで染色のムラなどの不均一を防止する効果もある。延伸はヨウ素で染色した後に行っても良いし、染色しながら延伸しても良いし、また延伸してからヨウ素で染色しても良い。ホウ酸やヨウ化カリウムなどの水溶液や水浴中でも延伸することができる。 A uniaxially stretched polarizer obtained by dyeing a polyvinyl alcohol film with iodine can be produced, for example, by dyeing a polyvinyl alcohol film by immersing it in an aqueous solution of iodine and stretching it to 3 to 7 times its original length. it can. If necessary, it can be immersed in an aqueous solution of potassium iodide or the like which may contain boric acid, zinc sulfate, zinc chloride or the like. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed with water before dyeing. By washing the polyvinyl alcohol-based film with water, it is possible to wash the stains and anti-blocking agent on the surface of the polyvinyl alcohol-based film, and by swelling the polyvinyl alcohol-based film, the effect of preventing unevenness such as uneven dyeing is also obtained. is there. Stretching may be performed after dyeing with iodine, stretching while dyeing, or stretching and then dyeing with iodine. Stretching can be performed in an aqueous solution of boric acid or potassium iodide or in a water bath.
　＜粘着剤層＞
　本発明において用いられる粘着剤層は、ベースポリマーと、シリコーンオリゴマーＰｓとを含む。 <Adhesive layer>
The pressure-sensitive adhesive layer used in the present invention contains a base polymer and a silicone oligomer Ps.
　本発明において用いられる粘着剤層を構成する粘着剤は、特に限定されず、ゴム系粘着剤、アクリル系粘着剤、シリコーン系粘着剤、ウレタン系粘着剤、ビニルアルキルエーテル系粘着剤、ポリビニルアルコール系粘着剤、ポリビニルピロリドン系粘着剤、ポリアクリルアミド系粘着剤、セルロース系粘着剤などを用いることができる。使用される粘着剤に応じて各種のベースポリマーを用いることができる。 The pressure-sensitive adhesive forming the pressure-sensitive adhesive layer used in the present invention is not particularly limited, and it is a rubber-based pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a vinyl alkyl ether-based pressure-sensitive adhesive, a polyvinyl alcohol-based pressure-sensitive adhesive. Adhesives, polyvinylpyrrolidone-based adhesives, polyacrylamide-based adhesives, cellulose-based adhesives and the like can be used. Various base polymers can be used depending on the adhesive used.
　上記の粘着剤の中でも、光学的透明性に優れ、適宜な濡れ性と凝集性と接着性の粘着特性を示して、耐候性や耐熱性などに優れるものが好ましく使用される。このような特徴を示すものとしてアクリル系粘着剤が好ましく使用される。アクリル系粘着剤のベースポリマーとしては（メタ）アクリル系ポリマーが用いられる。なお、（メタ）アクリレートはアクリレートおよび／またはメタクリレートを含む。 Among the above-mentioned pressure-sensitive adhesives, those having excellent optical transparency, exhibiting appropriate wettability, cohesiveness and adhesiveness, and excellent weather resistance and heat resistance are preferably used. Acrylic pressure-sensitive adhesives are preferably used as those exhibiting such characteristics. A (meth)acrylic polymer is used as the base polymer of the acrylic pressure-sensitive adhesive. The (meth)acrylate contains acrylate and/or methacrylate.
　＜ベースポリマー＞
　本発明において、ベースポリマーとしては通常、（メタ）アクリル系ポリマーが用いられる。 <Base polymer>
In the present invention, a (meth)acrylic polymer is usually used as the base polymer.
　（１）アルキル（メタ）アクリレート（Ａ）
　（メタ）アクリル系ポリマーは、通常、モノマー単位として、アルキル（メタ）アクリレートを主成分として含有する。（メタ)アクリル系ポリマーの主骨格を構成する、アルキル（メタ）アクリレート（Ａ）としては、直鎖状または分岐鎖状のＣ１～Ｃ２０の（メタ）アクリル酸アルキルエステルを用いることができる。Ｃ１～Ｃ２０の（メタ）アクリル酸アルキルエステルとしては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｓ－ブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸ペンチル、（メタ）アクリル酸イソペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸ヘプチル、（メタ）アクリル酸オクチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸イソオクチル、（メタ）アクリル酸ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸デシル、（メタ）アクリル酸イソデシル、（メタ）アクリル酸ウンデシル、（メタ）アクリル酸ドデシル、（メタ）アクリル酸トリデシル、（メタ）アクリル酸テトラデシル、（メタ）アクリル酸ペンタデシル、（メタ）アクリル酸ヘキサデシル、（メタ）アクリル酸ヘプタデシル、（メタ）アクリル酸オクタデシル、（メタ）アクリル酸イソオクタデシル、（メタ）アクリル酸ノナデシル、（メタ）アクリル酸エイコシル等が挙げられるが、これらに限定されない。これらの（メタ）アクリル酸アルキルエステルは単独であるいは組み合わせて使用することができる。 (1) Alkyl (meth)acrylate (A)
The (meth)acrylic polymer usually contains, as a monomer unit, an alkyl (meth)acrylate as a main component. As the alkyl (meth)acrylate (A) constituting the main skeleton of the (meth)acrylic polymer, a linear or branched C1 to C20 (meth)acrylic acid alkyl ester can be used. Examples of the C1 to C20 (meth)acrylic acid alkyl ester include methyl (meth)acrylate, ethyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and isopropyl (meth)acrylate. , N-butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, isopentyl (meth)acrylate, ( Hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, Decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, ( Examples include, but are not limited to, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, isooctadecyl (meth)acrylate, nonadecyl (meth)acrylate, and eicosyl (meth)acrylate. Not done. These (meth)acrylic acid alkyl esters can be used alone or in combination.
　本発明の一実施形態において、（メタ）アクリル系ポリマーは、好ましくは、アクリル酸ｎ－ブチル（ＢＡ）およびアクリル酸２－エチルヘキシル（２ＥＨＡ）の一方または両方をモノマー単位として含み得る。（メタ）アクリル系ポリマーのモノマー単位として好ましく用いられ得る他の（メタ）アクリル酸アルキルエステルの例としては、アクリル酸メチル、メタクリル酸メチル（ＭＭＡ）、メタクリル酸ｎ－ブチル（ＢＭＡ）、メタクリル酸２－エチルヘキシル（２ＥＨＭＡ）等が挙げられる。 In one embodiment of the present invention, the (meth)acrylic polymer may preferably contain one or both of n-butyl acrylate (BA) and 2-ethylhexyl acrylate (2EHA) as a monomer unit. Examples of other (meth)acrylic acid alkyl esters that can be preferably used as the monomer unit of the (meth)acrylic polymer include methyl acrylate, methyl methacrylate (MMA), n-butyl methacrylate (BMA), and methacrylic acid. 2-ethylhexyl (2EHMA) and the like can be mentioned.
　本発明の一実施形態において、ベースポリマーのモノマー単位として用いられるアルキル（メタ）アクリレート（Ａ）は、そのホモポリマーのガラス転移温度が－８０℃以上０℃以下である。アルキル（メタ）アクリレート（Ａ）のホモポリマーのガラス転移温度は、好ましくは、－７０℃～－５℃であり、より好ましくは、－６０℃～－１０℃である。 In one embodiment of the present invention, the alkyl (meth)acrylate (A) used as a monomer unit of the base polymer has a homopolymer glass transition temperature of −80° C. or higher and 0° C. or lower. The glass transition temperature of the homopolymer of alkyl (meth)acrylate (A) is preferably −70° C. to −5° C., more preferably −60° C. to −10° C.
　本発明の一実施形態において、ベースポリマーのモノマー単位として用いられるアルキル（メタ）アクリレート（Ａ）は、ベースポリマーの重量を基準として８０重量％以上で含有することができる。アルキル（メタ）アクリレート（Ａ）は、ベースポリマーの重量を基準として、好ましくは８５重量％以上であり、より好ましくは９０重量％以上である。 In one embodiment of the present invention, the alkyl (meth)acrylate (A) used as a monomer unit of the base polymer can be contained in an amount of 80% by weight or more based on the weight of the base polymer. The alkyl (meth)acrylate (A) is preferably 85% by weight or more, more preferably 90% by weight or more, based on the weight of the base polymer.
　本発明の好ましい実施形態において、ベースポリマーのモノマー単位として、ホモポリマーのガラス転移温度が－６０℃以上０℃以下であるアルキル（メタ）アクリレート（Ａ）を８０重量％以上で含有することができる。 In a preferred embodiment of the present invention, 80% by weight or more of an alkyl (meth)acrylate (A) whose homopolymer has a glass transition temperature of −60° C. or higher and 0° C. or lower can be contained as a base polymer monomer unit. ..
　本発明の一実施形態において、（メタ）アクリル系ポリマーは、主成分としてのアルキル（メタ）アクリレート（Ａ）に加えて、必要に応じて、アルキル（メタ）アクリレートと共重合可能な他のモノマー（共重合性モノマー）を更に含んでいてもよい。共重合性モノマーとしては、極性基（例えば、カルボキシ基、水酸基、窒素原子含有環等）を有するモノマーを好適に使用することができる。極性基を有するモノマーは、アクリル系ポリマーに架橋点を導入したり、（メタ）アクリル系ポリマーの凝集力を高めたりするために役立ち得る。共重合性モノマーは、１種を単独でまたは２種以上を組み合わせて用いることができる。 In one embodiment of the present invention, the (meth)acrylic polymer is, in addition to the alkyl (meth)acrylate (A) as a main component, other monomer that is copolymerizable with the alkyl (meth)acrylate, if necessary. It may further contain (copolymerizable monomer). As the copolymerizable monomer, a monomer having a polar group (for example, a carboxy group, a hydroxyl group, a nitrogen atom-containing ring, etc.) can be preferably used. The monomer having a polar group can be useful for introducing a cross-linking point in the acrylic polymer and for enhancing the cohesive force of the (meth)acrylic polymer. The copolymerizable monomer may be used alone or in combination of two or more.
　共重合性モノマーの非限定的な具体例としては、カルボキシ基含有モノマー、酸無水物基含有モノマー、水酸基含有モノマー、スルホン酸基またはリン酸基を含有するモノマー、エポキシ基含有モノマー、シアノ基含有モノマー、イソシアネート基含有モノマー、アミド基含有モノマー、窒素原子含有環を有するモノマー、スクシンイミド骨格を有するモノマー、マレイミド類、イタコンイミド類、（メタ）アクリル酸アミノアルキル類、（メタ）アクリル酸アルコキシアルキル類、ビニルエステル類、ビニルエーテル類、芳香族ビニル化合物、オレフィン類、脂環式炭化水素基を有する（メタ）アクリル酸エステル、芳香族炭化水素基を有する（メタ）アクリル酸エステル、その他、（メタ）アクリル酸テトラヒドロフルフリル等の複素環含有（メタ）アクリレート、塩化ビニルやフッ素原子含有（メタ）アクリレート等のハロゲン原子含有（メタ）アクリレート、シリコーン（メタ）アクリレート等のケイ素原子含有（メタ）アクリレート、テルペン化合物誘導体アルコールから得られる（メタ）アクリル酸エステル等が挙げられる。 Non-limiting specific examples of the copolymerizable monomer include a carboxy group-containing monomer, an acid anhydride group-containing monomer, a hydroxyl group-containing monomer, a sulfonic acid group- or phosphoric acid group-containing monomer, an epoxy group-containing monomer, and a cyano group-containing monomer. Monomers, isocyanate group-containing monomers, amide group-containing monomers, nitrogen atom-containing ring-containing monomers, succinimide skeleton-containing monomers, maleimides, itaconic imides, (meth)acrylic acid aminoalkyls, (meth)acrylic acid alkoxyalkyls, Vinyl esters, vinyl ethers, aromatic vinyl compounds, olefins, (meth)acrylic acid esters having an alicyclic hydrocarbon group, (meth)acrylic acid esters having an aromatic hydrocarbon group, other, (meth)acrylic Heterocycle-containing (meth)acrylates such as acid tetrahydrofurfuryl, halogen atom-containing (meth)acrylates such as vinyl chloride and fluorine atom-containing (meth)acrylate, silicon atom-containing (meth)acrylates such as silicone (meth)acrylate, terpenes Examples thereof include (meth)acrylic acid ester obtained from a compound derivative alcohol.
　カルボキシ基含有モノマーとしては、例えば、アクリル酸、メタクリル酸、カルボキシエチルアクリレート、カルボキシペンチルアクリレート、イタコン酸、マレイン酸、フマル酸、クロトン酸、イソクロトン酸等が挙げられ；
　酸無水物基含有モノマーとしては、例えば、無水マレイン酸、無水イタコン酸が挙げられ；
　水酸基含有モノマーとしては、例えば、（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３－ヒドロキシプロピル、（メタ）アクリル酸４－ヒドロキシブチル、（メタ）アクリル酸６－ヒドロキシヘキシル、（メタ）アクリル酸８－ヒドロキシオクチル、（メタ）アクリル酸１０－ヒドロキシデシル、（メタ）アクリル酸１２－ヒドロキシラウリル、（４－ヒドロキシメチルシクロへキシル）メチル（メタ）アクリレート等の（メタ）アクリル酸ヒドロキシアルキル等が挙げられ；
　スルホン酸基またはリン酸基を含有するモノマーとしては、例えば、スチレンスルホン酸、アリルスルホン酸、ビニルスルホン酸ナトリウム、２－（メタ）アクリルアミド－２－メチルプロパンスルホン酸、（メタ）アクリルアミドプロパンスルホン酸、スルホプロピル（メタ）アクリレート、（メタ）アクリロイルオキシナフタレンスルホン酸、２－ヒドロキシエチルアクリロイルホスフェート等が挙げられ；
　エポキシ基含有モノマーとしては、例えば、（メタ）アクリル酸グリシジルや（メタ）アクリル酸－２－エチルグリシジルエーテル等のエポキシ基含有アクリレート、アリルグリシジルエーテル、（メタ）アクリル酸グリシジルエーテル等が挙げられ；
　シアノ基含有モノマーとしては、例えば、アクリロニトリル、メタクリロニトリル等が挙げられ；
　イソシアネート基含有モノマーとしては、例えば、２－イソシアナートエチル（メタ）アクリレート等が挙げられ；
　アミド基含有モノマーとしては、例えば、（メタ）アクリルアミド；Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド、Ｎ，Ｎ－ジプロピル（メタ）アクリルアミド、Ｎ，Ｎ－ジイソプロピル（メタ）アクリルアミド、Ｎ，Ｎ－ジ（ｎ－ブチル）（メタ）アクリルアミド、Ｎ，Ｎ－ジ（ｔ－ブチル）（メタ）アクリルアミド等のＮ，Ｎ－ジアルキル（メタ）アクリルアミド；Ｎ－エチル（メタ）アクリルアミド、Ｎ－イソプロピル（メタ）アクリルアミド、Ｎ－ブチル（メタ）アクリルアミド、Ｎ－ｎ－ブチル（メタ）アクリルアミド等のＮ－アルキル（メタ）アクリルアミド；Ｎ－ビニルアセトアミド等のＮ－ビニルカルボン酸アミド類；その他、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリルアミド、ヒドロキシエチルアクリルアミド、Ｎ－メチロール（メタ）アクリルアミド、Ｎ－エチロール（メタ）アクリルアミド、Ｎ－メチロールプロパン（メタ）アクリルアミド、Ｎ－メトキシメチル（メタ）アクリルアミド、Ｎ－メトキシエチル（メタ）アクリルアミド、Ｎ－ブトキシメチル（メタ）アクリルアミド、Ｎ－（メタ）アクリロイルモルホリン等が挙げられ；
　窒素原子含有環を有するモノマーとしては、例えば、Ｎ－ビニル－２－ピロリドン、Ｎ－メチルビニルピロリドン、Ｎ－ビニルピリジン、Ｎ－ビニルピペリドン、Ｎ－ビニルピリミジン、Ｎ－ビニルピペラジン、Ｎ－ビニルピラジン、Ｎ－ビニルピロール、Ｎ－ビニルイミダゾール、Ｎ－ビニルオキサゾール、Ｎ－（メタ）アクリロイル－２－ピロリドン、Ｎ－（メタ）アクリロイルピペリジン、Ｎ－（メタ）アクリロイルピロリジン、Ｎ－ビニルモルホリン、Ｎ－ビニル－３－モルホリノン、Ｎ－ビニル－２－カプロラクタム、Ｎ－ビニル－１，３－オキサジン－２－オン、Ｎ－ビニル－３，５－モルホリンジオン、Ｎ－ビニルピラゾール、Ｎ－ビニルイソオキサゾール、Ｎ－ビニルチアゾール、Ｎ－ビニルイソチアゾール、Ｎ－ビニルピリダジン等（例えば、Ｎ－ビニル－２－カプロラクタム等のラクタム類）が挙げられ；
　スクシンイミド骨格を有するモノマーとしては、例えば、Ｎ－（メタ）アクリロイルオキシメチレンスクシンイミド、Ｎ－（メタ）アクリロイル－６－オキシヘキサメチレンスクシンイミド、Ｎ－（メタ）アクリロイル－８－オキシヘキサメチレンスクシンイミド等が挙げられ；
　マレイミド類としては、例えば、Ｎ－シクロヘキシルマレイミド、Ｎ－イソプロピルマレイミド、Ｎ－ラウリルマレイミド、Ｎ－フェニルマレイミド等が挙げられ；
　イタコンイミド類としては、例えば、Ｎ－メチルイタコンイミド、Ｎ－エチルイタコンイミド、Ｎ－ブチルイタコンイミド、Ｎ－オクチルイタコンイミド、Ｎ－２－エチルへキシルイタコンイミド、Ｎ－シクロへキシルイタコンイミド、Ｎ－ラウリルイタコンイミド等が挙げられ；
　（メタ）アクリル酸アミノアルキル類としては、例えば、（メタ）アクリル酸アミノエチル、（メタ）アクリル酸Ｎ，Ｎ－ジメチルアミノエチル、（メタ）アクリル酸Ｎ，Ｎ－ジエチルアミノエチル、（メタ）アクリル酸ｔ－ブチルアミノエチルが挙げられ；
　（メタ）アクリル酸アルコキシアルキル類としては、例えば、（メタ）アクリル酸メトキシエチル、（メタ）アクリル酸エトキシエチル、（メタ）アクリル酸プロポキシエチル、（メタ）アクリル酸ブトキシエチル、（メタ）アクリル酸エトキシプロピル等が挙げられ；
　ビニルエステル類としては、例えば、酢酸ビニル、プロピオン酸ビニル等が挙げられ；
　ビニルエーテル類としては、例えば、例えば、メチルビニルエーテルやエチルビニルエーテル等のビニルアルキルエーテルが挙げられ；
　芳香族ビニル化合物としては、例えば、スチレン、α－メチルスチレン、ビニルトルエン等が挙げられ；
　オレフィン類としては、例えば、エチレン、ブタジエン、イソプレン、イソブチレン等が挙げられ；
　脂環式炭化水素基を有する（メタ）アクリル酸エステルとしては、例えば、シクロペンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート等が挙げられ；
　芳香族炭化水素基を有する（メタ）アクリル酸エステルとしては、例えば、フェニル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、ベンジル（メタ）アクリレート等が挙げられる。 Examples of the carboxy group-containing monomer include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid and the like;
Examples of the acid anhydride group-containing monomer include maleic anhydride and itaconic anhydride;
Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and (meth)acrylate. ) 4-hydroxybutyl acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4 -Hydroxymethylcyclohexyl)methyl (meth)acrylate and the like hydroxyalkyl (meth)acrylate and the like;
Examples of the monomer having a sulfonic acid group or a phosphoric acid group include styrenesulfonic acid, allylsulfonic acid, sodium vinylsulfonate, 2-(meth)acrylamido-2-methylpropanesulfonic acid, (meth)acrylamidopropanesulfonic acid. , Sulfopropyl (meth)acrylate, (meth)acryloyloxynaphthalene sulfonic acid, 2-hydroxyethyl acryloyl phosphate and the like;
Examples of the epoxy group-containing monomer include epoxy group-containing acrylates such as (meth)acrylic acid glycidyl and (meth)acrylic acid-2-ethylglycidyl ether, allyl glycidyl ether, and (meth)acrylic acid glycidyl ether;
Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.
Examples of the isocyanate group-containing monomer include 2-isocyanatoethyl (meth)acrylate and the like;
Examples of the amide group-containing monomer include (meth)acrylamide; N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dipropyl(meth)acrylamide, N,N-diisopropyl( N,N-dialkyl(meth)acrylamides such as (meth)acrylamide, N,N-di(n-butyl)(meth)acrylamide, N,N-di(t-butyl)(meth)acrylamide; N-ethyl (meth ) N-alkyl(meth)acrylamides such as acrylamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, Nn-butyl(meth)acrylamide; N-vinylcarboxylic amides such as N-vinylacetamide Others: N,N-dimethylaminopropyl(meth)acrylamide, hydroxyethylacrylamide, N-methylol(meth)acrylamide, N-ethylol(meth)acrylamide, N-methylolpropane(meth)acrylamide, N-methoxymethyl( (Meth)acrylamide, N-methoxyethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-(meth)acryloylmorpholine and the like;
Examples of the monomer having a nitrogen atom-containing ring include N-vinyl-2-pyrrolidone, N-methylvinylpyrrolidone, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrazine, N-vinylpyrrole, N-vinylimidazole, N-vinyloxazole, N-(meth)acryloyl-2-pyrrolidone, N-(meth)acryloylpiperidine, N-(meth)acryloylpyrrolidine, N-vinylmorpholine, N-vinyl -3-morpholinone, N-vinyl-2-caprolactam, N-vinyl-1,3-oxazin-2-one, N-vinyl-3,5-morpholinedione, N-vinylpyrazole, N-vinylisoxazole, N -Vinylthiazole, N-vinylisothiazole, N-vinylpyridazine and the like (for example, lactams such as N-vinyl-2-caprolactam);
Examples of the monomer having a succinimide skeleton include N-(meth)acryloyloxymethylenesuccinimide, N-(meth)acryloyl-6-oxyhexamethylenesuccinimide, N-(meth)acryloyl-8-oxyhexamethylenesuccinimide and the like. Given;
Examples of the maleimides include N-cyclohexyl maleimide, N-isopropyl maleimide, N-lauryl maleimide, N-phenyl maleimide and the like;
Examples of itaconimides include N-methyl itaconimide, N-ethyl itaconimide, N-butyl itaconimide, N-octyl itaconimide, N-2-ethylhexyl itaconimide, N-cyclohexyl itaconimide, N -Lauryl itaconimide and the like;
Examples of aminoalkyl (meth)acrylates include aminoethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, and (meth)acrylic. T-butylaminoethyl acid acid;
Examples of the alkoxyalkyl (meth)acrylates include methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, propoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, and (meth)acrylic acid. Ethoxypropyl and the like can be mentioned;
Examples of vinyl esters include vinyl acetate, vinyl propionate and the like;
Examples of vinyl ethers include vinyl alkyl ethers such as methyl vinyl ether and ethyl vinyl ether;
Examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyltoluene and the like;
Examples of olefins include ethylene, butadiene, isoprene, and isobutylene;
Examples of the (meth)acrylic acid ester having an alicyclic hydrocarbon group include cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate and the like;
Examples of the (meth)acrylic acid ester having an aromatic hydrocarbon group include phenyl(meth)acrylate, phenoxyethyl(meth)acrylate, and benzyl(meth)acrylate.
　このような共重合性モノマーを使用する場合、その使用量は特に限定されないが、通常はモノマー成分全量の０．０１重量％以上とすることが適当である。共重合性モノマーの使用による効果をよりよく発揮する観点から、共重合性モノマーの使用量をモノマー成分全量の０．１重量％以上としてもよく、１重量％以上としてもよい。また、共重合性モノマーの使用量は、モノマー成分全量の５０重量％以下とすることができ、４０重量％以下とすることが好ましい。これにより、粘着剤の凝集力が高くなり過ぎることを防ぎ、常温（２５℃）でのタック感を向上させ得る。 When such a copolymerizable monomer is used, the amount thereof is not particularly limited, but it is usually suitable to be 0.01% by weight or more of the total amount of the monomer components. From the viewpoint of better exerting the effect of using the copolymerizable monomer, the amount of the copolymerizable monomer used may be 0.1% by weight or more, or 1% by weight or more based on the total amount of the monomer components. The amount of the copolymerizable monomer used can be 50% by weight or less, and preferably 40% by weight or less, based on the total amount of the monomer components. This can prevent the cohesive force of the pressure-sensitive adhesive from becoming too high, and improve the tackiness at room temperature (25° C.).
　本発明の一実施形態において、（メタ）アクリル系ポリマーは、主成分としてのアルキル（メタ）アクリレートに加えて、必要に応じて、モノマー単位として、上述のような水酸基含有モノマー（典型的には、水酸基を含有する（メタ）アクリル系モノマー）を含み得る。水酸基含有モノマーとしては、上述のように、例えば、（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３－ヒドロキシプロピル、（メタ）アクリル酸４－ヒドロキシブチル、（メタ）アクリル酸６－ヒドロキシヘキシル、（メタ）アクリル酸８－ヒドロキシオクチル、（メタ）アクリル酸１０－ヒドロキシデシル、（メタ）アクリル酸１２－ヒドロキシラウリル、（４－ヒドロキシメチルシクロへキシル）メチル（メタ）アクリレート等の（メタ）アクリル酸ヒドロキシアルキル等が挙げられるが、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸４－ヒドロキシブチル、（メタ）アクリル酸６－ヒドロキシヘキシル等を好適に使用することができる。なかでも好ましい例として、アクリル酸２－ヒドロキシエチル（ＨＥＡ）、アクリル酸４－ヒドロキシブチル（４ＨＢＡ）が挙げられる。水酸基含有モノマーの使用により、粘着剤の凝集力や極性を調整し、加熱後粘着力を向上させることができる。また、水酸基含有モノマーは、粘着剤層の親水性を高めることで、湿気による透明性低下を抑制するためにも役立ち得る。水酸基含有モノマーを含める場合、水酸基含有モノマーの使用量は、特に制限されないが、通常、（メタ）アクリル系ポリマーを調製するためのモノマー単位全量を基準として、例えば０．０１重量％以上、０．１重量％以上、０．５重量％以上などとすることができる。 In one embodiment of the present invention, the (meth)acrylic polymer is, in addition to the alkyl (meth)acrylate as a main component, optionally a hydroxyl group-containing monomer (typically, as described above) as a monomer unit. , A (meth)acrylic monomer containing a hydroxyl group). Examples of the hydroxyl group-containing monomer include, as described above, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 3-hydroxy (meth)acrylate. Hydroxypropyl, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-(meth)acrylic acid Examples thereof include hydroxyalkyl (meth)acrylate such as hydroxylauryl, (4-hydroxymethylcyclohexyl)methyl (meth)acrylate, and the like, 2-hydroxyethyl (meth)acrylate, 4-hydroxy (meth)acrylate. Butyl, 6-hydroxyhexyl (meth)acrylate and the like can be preferably used. Among these, preferable examples include 2-hydroxyethyl acrylate (HEA) and 4-hydroxybutyl acrylate (4HBA). By using the hydroxyl group-containing monomer, the cohesive force and polarity of the pressure-sensitive adhesive can be adjusted and the pressure-sensitive adhesive force after heating can be improved. Further, the hydroxyl group-containing monomer can also serve to suppress the decrease in transparency due to moisture by increasing the hydrophilicity of the pressure-sensitive adhesive layer. When the hydroxyl group-containing monomer is included, the amount of the hydroxyl group-containing monomer to be used is not particularly limited, but usually 0.01% by weight or more, 0.1% by weight or more, based on the total amount of the monomer unit for preparing the (meth)acrylic polymer. It can be 1% by weight or more, 0.5% by weight or more.
　また、本発明の一実施形態において、（メタ）アクリル系ポリマーは、主成分としてのアルキル（メタ）アクリレートに加えて、必要に応じて、粘着剤層の凝集力調整等の目的で、多官能性モノマーを含有してもよい。多官能性モノマーとしては、例えば、エチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールヘキサ（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、１，６－ヘキサンジオールジ（メタ）アクリレート、１，１２－ドデカンジオールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、テトラメチロールメタントリ（メタ）アクリレート、アリル（メタ）アクリレート、ビニル（メタ）アクリレート、ジビニルベンゼン、エポキシアクリレート、ポリエステルアクリレート、ウレタンアクリレート、ブチルジオール（メタ）アクリレート、ヘキシルジオールジ（メタ）アクリレート等が挙げられる。なかでも、トリメチロールプロパントリ（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、ジペンタエリスリトールヘキサ（メタ）アクリレートを好適に使用することができる。多官能性モノマーは、１種を単独でまたは２種以上を組み合わせて使用することができる。多官能性モノマーの使用量は、その分子量や官能基数等により異なるが、通常は、アルキル（メタ）アクリレート（Ａ）を調製するためのモノマー成分全量に対して０．０１重量％～３．０重量％の範囲とすることが適当であり、０．０２重量％～２．０重量％としてもよく、０．０３重量％～１．０重量％としてもよい。 In addition, in one embodiment of the present invention, the (meth)acrylic polymer is, in addition to the alkyl (meth)acrylate as the main component, a polyfunctional polymer for the purpose of adjusting the cohesive force of the pressure-sensitive adhesive layer, if necessary. It may contain a polymerizable monomer. Examples of the polyfunctional monomer include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, Pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,12-dodecane Diol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, allyl(meth)acrylate, vinyl(meth)acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate, butyl Examples thereof include diol (meth)acrylate and hexyl diol di(meth)acrylate. Among them, trimethylolpropane tri(meth)acrylate, 1,6-hexanediol di(meth)acrylate and dipentaerythritol hexa(meth)acrylate can be preferably used. The polyfunctional monomers may be used alone or in combination of two or more. The amount of the polyfunctional monomer used varies depending on the molecular weight, the number of functional groups, etc., but is usually 0.01% by weight to 3.0% by weight based on the total amount of the monomer components for preparing the alkyl (meth)acrylate (A). It is suitable to set it in the range of wt%, and it may be 0.02 wt% to 2.0 wt% or 0.03 wt% to 1.0 wt%.
　（２）極性モノマー（Ｂ）
　本発明の一実施形態において、ベースポリマーは、共重合性モノマー単位として、カルボキシル基含有モノマー（ｂ１）および窒素含有モノマー（ｂ２）からなる群より選択される少なくとも１種の極性モノマー（Ｂ）を更に含むことができる。 (2) Polar monomer (B)
In one embodiment of the present invention, the base polymer contains, as a copolymerizable monomer unit, at least one polar monomer (B) selected from the group consisting of a carboxyl group-containing monomer (b1) and a nitrogen-containing monomer (b2). It can also be included.
　本発明の一実施形態において、上記極性モノマー（Ｂ）は、ベースポリマーの重量を基準として、０～２０重量％で含まれ得る。極性モノマー（Ｂ）は、ベースポリマーの重量を基準として、好ましくは０．１～１７．５重量％であり、より好ましくは１～１５重量％である。 In an embodiment of the present invention, the polar monomer (B) may be included in an amount of 0 to 20% by weight based on the weight of the base polymer. The polar monomer (B) is preferably 0.1 to 17.5% by weight, more preferably 1 to 15% by weight, based on the weight of the base polymer.
　（２－１）カルボキシル基含有モノマー（ｂ１）
　本発明において、ベースポリマーは、共重合性モノマー単位として、カルボキシル基含有モノマー（ｂ１）を含むことができる。カルボキシ基含有モノマー（ｂ１）としては、例えば、アクリル酸、メタクリル酸、カルボキシエチルアクリレート、カルボキシペンチルアクリレート、イタコン酸、マレイン酸、フマル酸、クロトン酸、イソクロトン酸等が挙げられるが、これらに限定されない。本発明の好ましい実施形態において、カルボキシル基含有モノマー（ｂ１）は、アクリル酸、メタクリル酸であってよい。本発明のより好ましい実施形態において、カルボキシル基含有モノマー（ｂ１）は、アクリル酸（ＡＡ）であってよい。 (2-1) Carboxyl group-containing monomer (b1)
In the present invention, the base polymer may contain a carboxyl group-containing monomer (b1) as a copolymerizable monomer unit. Examples of the carboxy group-containing monomer (b1) include, but are not limited to, acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid and the like. .. In a preferred embodiment of the present invention, the carboxyl group-containing monomer (b1) may be acrylic acid or methacrylic acid. In a more preferred embodiment of the present invention, the carboxyl group-containing monomer (b1) may be acrylic acid (AA).
　（２－２）窒素含有モノマー（ｂ２）
　本発明において、ベースポリマーは、共重合性モノマー単位として、窒素含有モノマー（ｂ２）を含むことができる。窒素含有モノマー（ｂ２）としては、例えば、ラクタム環を有するビニル系モノマー（例えば、Ｎ－ビニルピロリドン、メチルビニルピロリドンなどのビニルピロリドン系モノマー、及びβ－ラクタム環、δ－ラクタム環、及びε－ラクタム環などのラクタム環を有するビニルラクタム系モノマーなど）；マレイミド、Ｎ－シクロへキシルマレイミド、Ｎ－フェニルマレイミドなどのマレイミド系モノマー；（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド、Ｎ－ヘキシル（メタ）アクリルアミド、Ｎ－メチル（メタ）アクリルアミド、Ｎ－ブチル（メタ）アクリルアミド、Ｎ－ブチル（メタ）アクリルアミド、Ｎ－メチロール（メタ）アクリルアミド、Ｎ－メチロールプロパン（メタ）アクリルアミドなどの（Ｎ－置換）アミド系モノマー；（メタ）アクリル酸アミノエチル、（メタ）アクリル酸アミノプロピル、（メタ）アクリル酸Ｎ，Ｎ－ジメチルアミノエチル、（メタ）アクリル酸ｔ－ブチルアミノエチル、３－（３－ピリニジル）プロピル（メタ）アクリレートなどの（メタ）アクリル酸アミノアルキル系モノマー；Ｎ－（メタ）アクリロイルオキシメチレンスクシンイミド、Ｎ－（メタ）アクリロイル－６－オキシヘキサメチレンスクシンイミド、Ｎ－（メタ）アクリロイル－８－オキシオクタメチレンスクシンイミドなどのスクシンイミド系モノマー；アクリロニトリル、メタクリロニトリルなどのシアノ（メタ）アクリレート系モノマー；ビニルピリジン、ビニルピペリドン、ビニルピリミジン、ビニルピペラジン、ビニルピラジン、ビニルピロール、ビニルイミダゾール、ビニルオキサゾール、ビニルモルホリン、Ｎ－ビニルカルボン酸アミド類などが挙げられるが、これらに限定されない。本発明の好ましい実施形態において、窒素含有モノマー（ｂ２）は、Ｎ－ビニルピロリドン、メチルビニルピロリドン、Ｎ，Ｎ－ジメチル（メタ）アクリルアミドであってよい。本発明のより好ましい実施形態において、窒素含有モノマー（ｂ２）は、Ｎ－ビニルピロリドンであってよい。 (2-2) Nitrogen-containing monomer (b2)
In the present invention, the base polymer may include a nitrogen-containing monomer (b2) as a copolymerizable monomer unit. Examples of the nitrogen-containing monomer (b2) include vinyl monomers having a lactam ring (for example, vinylpyrrolidone monomers such as N-vinylpyrrolidone and methylvinylpyrrolidone, β-lactam ring, δ-lactam ring, and ε-). Vinyllactam-based monomers having a lactam ring such as lactam ring); Maleimide-based monomers such as maleimide, N-cyclohexylmaleimide, N-phenylmaleimide; (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N , N-diethyl(meth)acrylamide, N-hexyl(meth)acrylamide, N-methyl(meth)acrylamide, N-butyl(meth)acrylamide, N-butyl(meth)acrylamide, N-methylol(meth)acrylamide, N -(N-substituted)amide-based monomers such as methylolpropane (meth)acrylamide; aminoethyl (meth)acrylate, aminopropyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, (meth) Aminoalkyl-based (meth)acrylate monomers such as t-butylaminoethyl acrylate and 3-(3-pyridinyl)propyl(meth)acrylate; N-(meth)acryloyloxymethylenesuccinimide, N-(meth)acryloyl-6 -Succinimide-based monomers such as oxyhexamethylene succinimide and N-(meth)acryloyl-8-oxyoctamethylene succinimide; Cyano (meth)acrylate-based monomers such as acrylonitrile and methacrylonitrile; vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl piperazine , Vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxazole, vinylmorpholine, N-vinylcarboxylic acid amides and the like, but are not limited thereto. In a preferred embodiment of the present invention, the nitrogen-containing monomer (b2) may be N-vinylpyrrolidone, methylvinylpyrrolidone, N,N-dimethyl(meth)acrylamide. In a more preferred embodiment of the present invention, the nitrogen-containing monomer (b2) may be N-vinylpyrrolidone.
　（メタ）アクリル系ポリマーを得る方法は特に限定されず、溶液重合法、エマルション重合法、バルク重合法、懸濁重合法、光重合法等の、アクリル系ポリマーの合成手法として知られている各種の重合方法を適宜採用することができる。いくつかの態様において、溶液重合法を好ましく採用し得る。溶液重合を行う際の重合温度は、使用するモノマーおよび溶媒の種類、重合開始剤の種類等に応じて適宜選択することができ、例えば２０℃～１７０℃程度（典型的には４０℃～１４０℃程度）とすることができる。 The method for obtaining the (meth)acrylic polymer is not particularly limited, and various known methods for synthesizing acrylic polymers, such as solution polymerization method, emulsion polymerization method, bulk polymerization method, suspension polymerization method, and photopolymerization method. The above-mentioned polymerization method can be appropriately adopted. In some embodiments, the solution polymerization method may be preferably adopted. The polymerization temperature at the time of performing solution polymerization can be appropriately selected according to the type of monomer and solvent used, the type of polymerization initiator, etc., and is, for example, about 20°C to 170°C (typically 40°C to 140°C). C.).
　重合に用いる開始剤は、重合方法に応じて、従来既知の熱重合開始剤や光重合開始剤等から適宜選択することができる。重合開始剤は、１種を単独でまたは２種以上を組み合わせて使用することができる。 The initiator used for the polymerization can be appropriately selected from conventionally known thermal polymerization initiators, photopolymerization initiators, etc. according to the polymerization method. The polymerization initiators may be used alone or in combination of two or more.
　熱重合開始剤としては、例えば、アゾ系重合開始剤（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、２，２’－アゾビス（２－メチルプロピオン酸）ジメチル、４，４’－アゾビス－４－シアノバレリアン酸、アゾビスイソバレロニトリル、２，２’－アゾビス（２－アミジノプロパン）ジヒドロクロライド、２，２’－アゾビス［２－（５－メチル－２－イミダゾリン－２－イル）プロパン］ジヒドロクロライド、２，２’－アゾビス（２－メチルプロピオンアミジン）二硫酸塩、２，２’－アゾビス（Ｎ，Ｎ’－ジメチレンイソブチルアミジン）ジヒドロクロライド等）；過硫酸カリウム等の過硫酸塩；過酸化物系重合開始剤（例えば、ジベンゾイルペルオキシド、ｔ－ブチルペルマレエート、過酸化ラウロイル等）；レドックス系重合開始剤等が挙げられる。熱重合開始剤の使用量は、特に制限されないが、例えば、アクリル系ポリマーの調製に用いられるモノマー成分１００重量部に対して０．０１重量部～５重量部、好ましくは０．０５重量部～３重量部の範囲内の量とすることができる。 Examples of the thermal polymerization initiator include azo polymerization initiators (eg, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobis( 2-methylpropionic acid)dimethyl, 4,4′-azobis-4-cyanovaleric acid, azobisisovaleronitrile, 2,2′-azobis(2-amidinopropane)dihydrochloride, 2,2′-azobis[2 -(5-Methyl-2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis(2-methylpropionamidine)disulfate, 2,2'-azobis(N,N'-dimethylene Isobutylamidine) dihydrochloride, etc.); Persulfate such as potassium persulfate; Peroxide type polymerization initiator (eg, dibenzoyl peroxide, t-butyl permaleate, lauroyl peroxide, etc.); Redox type polymerization initiator, etc. Is mentioned. The amount of the thermal polymerization initiator used is not particularly limited, but is, for example, 0.01 parts by weight to 5 parts by weight, preferably 0.05 parts by weight to 100 parts by weight of the monomer component used for preparing the acrylic polymer. The amount can be within the range of 3 parts by weight.
　光重合開始剤としては、特に制限されないが、例えば、ベンゾインエーテル系光重合開始剤、アセトフェノン系光重合開始剤、α－ケトール系光重合開始剤、芳香族スルホニルクロリド系光重合開始剤、光活性オキシム系光重合開始剤、ベンゾイン系光重合開始剤、ベンジル系光重合開始剤、ベンゾフェノン系光重合開始剤、ケタール系光重合開始剤、チオキサントン系光重合開始剤、アシルフォスフィンオキサイド系光重合開始剤等を用いることができる。光重合開始剤の使用量は、特に制限されないが、例えば、アクリル系ポリマーの調製に用いられるモノマー成分１００重量部に対して０．０１重量部～５重量部、好ましくは０．０５重量部～３重量部の範囲内の量とすることができる。 The photopolymerization initiator is not particularly limited, and examples thereof include benzoin ether photopolymerization initiators, acetophenone photopolymerization initiators, α-ketol photopolymerization initiators, aromatic sulfonyl chloride photopolymerization initiators, and photoactivators. Oxime photopolymerization initiator, benzoin photopolymerization initiator, benzyl photopolymerization initiator, benzophenone photopolymerization initiator, ketal photopolymerization initiator, thioxanthone photopolymerization initiator, acylphosphine oxide photopolymerization initiator Agents and the like can be used. The amount of the photopolymerization initiator used is not particularly limited, but for example, 0.01 part by weight to 5 parts by weight, preferably 0.05 part by weight to 100 parts by weight of the monomer component used for the preparation of the acrylic polymer. The amount can be within the range of 3 parts by weight.
　本発明の一実施形態において、（メタ）アクリル系ポリマーは、上述のようなモノマー成分に重合開始剤を配合した混合物に、重合溶媒として、例えば、酢酸エチル、トルエン等が用い、溶液重合にて（メタ）アクリル系ポリマーを得ることができる。溶液重合例としては、反応は窒素等の不活性ガス気流下で、重合開始剤を加え、通常、５０～７０℃程度で、５～３０時間程度の反応条件で行われる。本明細書において開示される粘着剤層は、例えば、上記（メタ）アクリル系ポリマーと後述するシリコーンオリゴマーＰｓ、その他添加剤とを含む粘着剤組成物を用いて形成され得る。 In one embodiment of the present invention, the (meth)acrylic polymer is obtained by solution polymerization using a mixture of a monomer component as described above and a polymerization initiator, for example, ethyl acetate or toluene as a polymerization solvent. A (meth)acrylic polymer can be obtained. As an example of solution polymerization, the reaction is usually carried out under a stream of an inert gas such as nitrogen with a polymerization initiator at about 50 to 70° C. for about 5 to 30 hours. The pressure-sensitive adhesive layer disclosed in the present specification can be formed using, for example, a pressure-sensitive adhesive composition containing the (meth)acrylic polymer, the silicone oligomer Ps described below, and other additives.
　本発明において、上述のベースポリマーの重量平均分子量Ｍｗは５０万～２５０万であってよい。本発明の一実施形態において、ベースポリマーの重量平均分子量Ｍｗは、好ましくは、７０万～２７０万であり、より好ましくは、８０万～２５０万であり得る。 In the present invention, the weight average molecular weight Mw of the above-mentioned base polymer may be 500,000 to 2,500,000. In one embodiment of the present invention, the weight average molecular weight Mw of the base polymer may be preferably 700,000 to 2.7 million, more preferably 800,000 to 2.5 million.
　＜シリコーンオリゴマーＰｓ＞
　本発明において、粘着剤層はシリコーンオリゴマーＰｓを含む。シリコーンオリゴマーＰｓは、シロキサン構造の低極性および運動性によって、初期粘着力の抑制および粘着力上昇比の向上に寄与する粘着力上昇遅延剤として機能し得る。シリコーンオリゴマーＰｓとしては、側鎖にシロキサン構造を有するポリマーが好ましく用いられ得る。 <Silicone Oligomer Ps>
In the present invention, the pressure-sensitive adhesive layer contains silicone oligomer Ps. Silicone oligomer Ps can function as a tackiness increase retarder that contributes to suppression of initial tackiness and improvement of tackiness increase ratio due to the low polarity and mobility of the siloxane structure. As the silicone oligomer Ps, a polymer having a siloxane structure in its side chain can be preferably used.
　本発明において用いられるシリコーンオリゴマーＰｓは、そのガラス転移温度（Ｔｇ）が－５０℃以上１００℃以下の範囲のものである。本発明の一実施形態において、シリコーンオリゴマーＰｓのＴｇは、好ましくは－３０℃以上７０℃以下であり、より好ましくは、－２０℃以上６０℃以下であってよい。シリコーンオリゴマーＰｓのＴｇが上記範囲内であると、初期の低粘着性と使用時の粘着力の上昇（強粘着性）とを高レベルで両立することができる。 The silicone oligomer Ps used in the present invention has a glass transition temperature (Tg) in the range of -50°C to 100°C. In one embodiment of the present invention, the Tg of the silicone oligomer Ps may preferably be -30°C or higher and 70°C or lower, and more preferably -20°C or higher and 60°C or lower. When the Tg of the silicone oligomer Ps is in the above range, it is possible to achieve both a low initial tackiness and an increase in tackiness during use (strong tackiness) at a high level.
　本発明において用いられるシリコーンオリゴマーＰｓは、その重量平均分子量Ｍｗが１００００以上３０００００以下の範囲のものである。本発明の一実施形態において、シリコーンオリゴマーＰｓの重量平均分子量Ｍｗは、好ましくは１２５００以上２５０００００以下であり、より好ましくは１５０００以上２００００００以下であってよい。シリコーンオリゴマーＰｓの重量平均分子量Ｍｗが上記範囲内であると、粘着剤層内における相溶性や移動性を適度な範囲に調節しやすく、初期の低粘着性と使用時の強粘着性とを高レベルで両立する粘着シートを実現しやすくなる。 The silicone oligomer Ps used in the present invention has a weight average molecular weight Mw of 10,000 or more and 300,000 or less. In one embodiment of the present invention, the weight average molecular weight Mw of the silicone oligomer Ps may be preferably 12,500 or more and 2500000 or less, more preferably 15000 or more and 2000000 or less. When the weight average molecular weight Mw of the silicone oligomer Ps is within the above range, it is easy to adjust the compatibility and mobility in the pressure-sensitive adhesive layer to an appropriate range, and the initial low tackiness and strong tackiness during use are high. It becomes easier to realize a pressure-sensitive adhesive sheet that is compatible at both levels.
　本発明の好ましい実施形態において、シリコーンオリゴマーＰｓは、Ｔｇが－７０℃以上３０℃以下であり、側鎖のシリコーン官能基当量が１０００～２００００ｇ／ｍｏｌであり、重量平均分子量Ｍｗが１００００以上３０００００以下であってよい。 In a preferred embodiment of the present invention, the silicone oligomer Ps has a Tg of −70° C. or higher and 30° C. or lower, a side chain silicone functional group equivalent of 1000 to 20000 g/mol, and a weight average molecular weight Mw of 10,000 to 300,000. May be
　本発明の一実施形態において、シリコーンオリゴマーＰｓは、ポリオルガノシロキサン骨格を有するモノマーＳ１と、ホモポリマーのガラス転移温度が－７０℃以上１８０℃以下のモノマーとをモノマー単位として含み得る。 In one embodiment of the present invention, the silicone oligomer Ps may include a monomer S1 having a polyorganosiloxane skeleton and a monomer having a homopolymer glass transition temperature of −70° C. or higher and 180° C. or lower as monomer units.
　（１）ポリオルガノシロキサン骨格を有するモノマーＳ１
　本発明のシリコーンオリゴマーＰｓに用いることができるポリオルガノシロキサン骨格を有するモノマーＳ１は、特に限定されず、ポリオルガノシロキサン骨格を有する任意のモノマーを用いることができる。ポリオルガノシロキサン骨格としては、例えば、トリメチルシロキサン（ＴＭ）、ジメチルシロキサン（ＤＭ）、ポリオキシエチルメチルシロキサン（ＥＯＭ）などが挙げられるが、これらに限定されない。 (1) Monomer S1 having a polyorganosiloxane skeleton
The monomer S1 having a polyorganosiloxane skeleton that can be used in the silicone oligomer Ps of the present invention is not particularly limited, and any monomer having a polyorganosiloxane skeleton can be used. Examples of the polyorganosiloxane skeleton include, but are not limited to, trimethylsiloxane (TM), dimethylsiloxane (DM), polyoxyethylmethylsiloxane (EOM), and the like.
　ポリオルガノシロキサン骨格を有するモノマーＳ１としては、例えば、下記一般式（１）または（２）で表される化合物を用いることができる。より具体的には、信越化学工業株式会社製の片末端反応性シリコーンオイルとして、Ｘ－２２－１７４ＡＳＸ、Ｘ－２２－２４２６、Ｘ－２２－２４７５、ＫＦ－２０１２、Ｘ－２２－１７４ＢＸ、Ｘ－２２－２４０４などが挙げられる。ポリオルガノシロキサン骨格を有するモノマーＳ１は、１種を単独でまたは２種以上を組み合わせて使用することができる。
Figure JPOXMLDOC01-appb-C000001
  
Figure JPOXMLDOC01-appb-C000002
  
　ここで、上記一般式（１），（２）中のＲ３は水素またはメチルであり、Ｒ４はメチル基または１価の有機基であり、ｍおよびｎは０以上の整数である。 As the monomer S1 having a polyorganosiloxane skeleton, for example, a compound represented by the following general formula (1) or (2) can be used. More specifically, as one-end reactive silicone oil manufactured by Shin-Etsu Chemical Co., Ltd., X-22-174ASX, X-22-2426, X-22-2475, KF-2012, X-22-174BX, X -22-2404 and the like. The monomer S1 having a polyorganosiloxane skeleton may be used alone or in combination of two or more.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000002
Here, R 3 in the general formulas (1) and (2) is hydrogen or methyl, R 4 is a methyl group or a monovalent organic group, and m and n are integers of 0 or more.
　本発明において用いられるシリコーンオリゴマーＰｓは、その側鎖のシリコーン官能基当量が１０００～２００００ｇ／ｍｏｌである。本発明の一実施形態において、シリコーンオリゴマーＰｓの側鎖のシリコーン官能基当量は、好ましくは１２００～１８０００ｇ／ｍｏｌであり、より好ましくは１５００～１５０００ｇ／ｍｏｌであってよい。シリコーンオリゴマーＰｓの側鎖のシリコーン官能基当量が上記範囲内であると、粘着剤層内における相溶性（例えば、ベースポリマーとの相溶性）や移動性を適度な範囲に調節しやすく、初期の低粘着性と使用時の強粘着性とを高レベルで両立する粘着シートを実現しやすくなる。 The silicone oligomer Ps used in the present invention has a silicone functional group equivalent of its side chain of 1000 to 20000 g/mol. In one embodiment of the present invention, the silicone functional group equivalent of the side chain of the silicone oligomer Ps may be preferably 1200 to 18000 g/mol, more preferably 1500 to 15000 g/mol. When the silicone functional group equivalent of the side chain of the silicone oligomer Ps is within the above range, it is easy to adjust the compatibility (for example, the compatibility with the base polymer) and the mobility in the pressure-sensitive adhesive layer to an appropriate range and It becomes easy to realize a pressure-sensitive adhesive sheet that achieves both low tackiness and strong tackiness during use at a high level.
　ここで、「官能基当量」とは、官能基１個当たりに結合している主骨格（例えばポリジメチルシロキサン）の重量を意味する。標記単位ｇ／ｍｏｌに関しては、官能基１ｍｏｌと換算している。ポリオルガノシロキサン骨格を有するモノマーＳ１の官能基当量は、例えば、核磁気共鳴（ＮＭＲ）に基づく１Ｈ－ＮＭＲ（プロトンＮＭＲ）のスペクトル強度から算出することができる。１Ｈ－ＮＭＲのスペクトル強度に基づく、ポリオルガノシロキサン骨格を有するモノマーＳ１の官能基当量（ｇ／ｍｏｌ）の算出は、１Ｈ－ＮＭＲスペクトル解析に係る一般的な構造解析手法に基づいて、必要であれば日本国特許第５９５１１５３号公報の記載を参照して行うことができる。 Here, the “functional group equivalent” means the weight of the main skeleton (for example, polydimethylsiloxane) bonded to each functional group. The unit of g/mol is converted to 1 mol of the functional group. The functional group equivalent of the monomer S1 having a polyorganosiloxane skeleton can be calculated from the spectrum intensity of 1 H-NMR (proton NMR) based on nuclear magnetic resonance (NMR), for example. Calculation of the functional group equivalent (g/mol) of the monomer S1 having a polyorganosiloxane skeleton based on the 1 H-NMR spectrum intensity is required based on a general structural analysis method related to 1 H-NMR spectrum analysis. In that case, it can be performed by referring to the description of Japanese Patent No. 5915153.
　なお、ポリオルガノシロキサン骨格を有するモノマーＳ１として官能基当量が異なる２種類以上のモノマーを用いる場合、モノマーＳ１の官能基当量としては、算術平均値を用いることができる。すなわち、官能基当量が異なるｎ種類のモノマー（モノマーＳ１１，モノマーＳ１２・・・モノマーＳ１ｎ）からなるモノマーＳ１の官能基当量は、下記式により計算することができる。
　モノマーＳ１の官能基当量（ｇ／ｍｏｌ）＝（モノマーＳ１１の官能基当量×モノマーＳ１１の配合量＋モノマーＳ１２の官能基当量×モノマーＳ１２の配合量＋・・・＋モノマーＳ１ｎの官能基当量×モノマーＳ１ｎの配合量）／（モノマーＳ１１の配合量＋モノマーＳ１２の配合量＋・・・＋モノマーＳ１ｎの配合量） When two or more kinds of monomers having different functional group equivalents are used as the monomer S1 having a polyorganosiloxane skeleton, an arithmetic average value can be used as the functional group equivalent of the monomer S1. That is, the functional group equivalent of the monomer S1 composed of n kinds of monomers (monomer S1 1 , monomer S1 2 ... Monomer S1 n ) having different functional group equivalents can be calculated by the following formula.
Functional group equivalent of the monomer S1 (g / mol) = (monomer S1 1 functional group equivalent × monomer S1 1 of the amount + monomer S1 2 functional group equivalent × monomer S1 2 of the amount + ... + monomer S1 n Functional group equivalent×monomer S1 n blending amount)/(monomer S1 1 blending amount+monomer S1 2 blending amount+...+monomer S1 n blending amount)
　ポリオルガノシロキサン骨格を有するモノマーＳ１の含有量は、シリコーンオリゴマーＰｓを調製するための全モノマー成分に対して、例えば５重量％以上であってよく、粘着力上昇遅延剤としての効果をよりよく発揮する観点から１０重量％以上とすることが好ましく、１５重量％以上としてもよい。いくつかの態様において、上記モノマーＳ１の含有量は、例えば２０重量％以上であってもよい。また、ポリオルガノシロキサン骨格を有するモノマーＳ１の含有量は、重合反応性や相溶性の観点から、シリコーンオリゴマーＰｓを調製するための全モノマー成分に対して、６０重量％以下とすることが適当であり、５０重量％以下としてもよく、４０重量％以下としてもよく、３０重量％以下としてもよい。ポリオルガノシロキサン骨格を有するモノマーＳ１の含有量が上記範囲内にあると、初期の低粘着性と使用時の粘着力の上昇（強粘着性）とを高レベルで両立する粘着シートを実現しやすくなる。 The content of the monomer S1 having a polyorganosiloxane skeleton may be, for example, 5% by weight or more based on the total monomer components for preparing the silicone oligomer Ps, and the effect as a tackiness increase retarder can be better exhibited. From the viewpoint of the above, the amount is preferably 10% by weight or more, and may be 15% by weight or more. In some embodiments, the content of the monomer S1 may be, for example, 20% by weight or more. From the viewpoint of polymerization reactivity and compatibility, the content of the monomer S1 having a polyorganosiloxane skeleton is appropriately 60% by weight or less based on the total monomer components for preparing the silicone oligomer Ps. Yes, it may be 50% by weight or less, 40% by weight or less, or 30% by weight or less. When the content of the monomer S1 having a polyorganosiloxane skeleton is within the above range, it is easy to realize a pressure-sensitive adhesive sheet that achieves a high level of both low initial tackiness and increase in tackiness (strong tackiness) during use. Become.
　（２）ホモポリマーのガラス転移温度が－７０℃以上１８０℃以下のモノマー
　本発明のシリコーンオリゴマーＰｓは、上記ポリオルガノシロキサン骨格を有するモノマーＳ１と共重合可能な（メタ）アクリル系モノマーまたは他の共重合性モノマーを含む。本発明のシリコーンオリゴマーＰｓに用いることができる共重合可能な（メタ）アクリル系モノマーまたは他の共重合性モノマーとしては、ホモポリマーのガラス転移温度が－７０℃以上１８０℃以下のモノマーを用いることができ、例えば、（メタ）アクリル酸アルキルエステル、脂環式炭化水素基を有する（メタ）アクリル酸エステルが挙げられるが、これらに限定されない。（メタ）アクリル酸アルキルエステルとしては、メチルメタクリレート（ＭＭＡ）、ブチルメタクリレート（ＢＭＡ）、２－エチルヘキシルメタクリレート（２－ＥＨＭＡ）、ブチルアクリレート（ＢＡ）、２－エチルヘキシルアクリレート（２－ＥＨＡ）が挙げられ、脂環式炭化水素基を有する（メタ）アクリル酸エステルとしては、２－（（３－ヒドロキシメチル）－アダマンタン－１－イル）メトキシ－２－オキソエチル メタクリレート（２ＥＨＡＭＡ）、シクロペンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、１－アダマンチル（メタ）アクリレートなどが挙げられるが、これらに限定されない。本発明の一実施形態において、２－（（３－ヒドロキシメチル）－アダマンタン－１－イル）メトキシ－２－オキソエチル メタクリレート（２ＥＨＡＭＡ）、およびイソボルニル メタクリレート（ＩＢＸＭＡ）から選択される少なくとも１種をモノマー単位として含有し得る。本発明の別の実施形態において、ジシクロペンタニルメタクリレート、イソボルニルメタクリレートおよびシクロヘキシルメタクリレートから選択される少なくとも１種をモノマー単位として含有し得る。これらのモノマーは、１種を単独でまたは２種以上を組み合わせて使用することができる。 (2) Monomer whose homopolymer has a glass transition temperature of −70° C. or higher and 180° C. or lower The silicone oligomer Ps of the present invention is a (meth)acryl-based monomer or another monomer copolymerizable with the monomer S1 having the polyorganosiloxane skeleton. It contains a copolymerizable monomer. As the copolymerizable (meth)acrylic monomer or other copolymerizable monomer that can be used in the silicone oligomer Ps of the present invention, a homopolymer having a glass transition temperature of −70° C. to 180° C. is used. Examples thereof include, but are not limited to, (meth)acrylic acid alkyl ester and (meth)acrylic acid ester having an alicyclic hydrocarbon group. Examples of the (meth)acrylic acid alkyl ester include methyl methacrylate (MMA), butyl methacrylate (BMA), 2-ethylhexyl methacrylate (2-EHMA), butyl acrylate (BA), and 2-ethylhexyl acrylate (2-EHA). Examples of the (meth)acrylic acid ester having an alicyclic hydrocarbon group include 2-((3-hydroxymethyl)-adamantan-1-yl)methoxy-2-oxoethyl methacrylate (2EHAMA), cyclopentyl (meth)acrylate, Examples thereof include, but are not limited to, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, 1-adamantyl (meth)acrylate, and the like. In one embodiment of the present invention, at least one selected from 2-((3-hydroxymethyl)-adamantan-1-yl)methoxy-2-oxoethyl methacrylate (2EHAMA) and isobornyl methacrylate (IBXMA) is a monomer unit. Can be included as In another embodiment of the present invention, it may contain at least one selected from dicyclopentanyl methacrylate, isobornyl methacrylate and cyclohexyl methacrylate as a monomer unit. These monomers may be used alone or in combination of two or more.
　上記（メタ）アクリル酸アルキルエステルおよび上記脂環式炭化水素基を有する（メタ）アクリル酸エステルの使用量は、シリコーンオリゴマーＰｓを調製するための全モノマー成分に対して、例えば１０重量％以上９５重量％以下であってよく、２０重量％以上９５重量％以下であってもよく、３０重量％以上９０重量％以下であってもよく、４０重量％以上９０重量％以下であってもよく、５０重量％以上８５重量％以下であってもよい。 The amount of the above-mentioned (meth)acrylic acid alkyl ester and the above-mentioned (meth)acrylic acid ester having an alicyclic hydrocarbon group used is, for example, 10% by weight or more and 95% by weight or more based on all the monomer components for preparing the silicone oligomer Ps. May be 20% by weight or more, 95% by weight or less, 30% by weight or more and 90% by weight or less, or 40% by weight or more and 90% by weight or less, It may be 50% by weight or more and 85% by weight or less.
　シリコーンオリゴマーＰｓを構成するモノマー単位としてモノマーＳ１とともに含まれ得るモノマーの他の例として、アルキル（メタ）アクリレート（Ａ）に用いられ得るモノマーとして上記で例示したカルボキシル基含有モノマー、酸無水物基含有モノマー、水酸基含有モノマー、エポキシ基含有モノマー、シアノ基含有モノマー、イソシアネート基含有モノマー、アミド基含有モノマー、窒素原子含有環を有するモノマー、スクシンイミド骨格を有するモノマー、マレイミド類、イタコンイミド類、（メタ）アクリル酸アミノアルキル類、ビニルエステル類、ビニルエーテル類、オレフィン類、芳香族炭化水素基を有する（メタ）アクリル酸エステル、複素環含有（メタ）アクリレート、ハロゲン原子含有（メタ）アクリレート、テルペン化合物誘導体アルコールから得られる（メタ）アクリル酸エステル等が挙げられる。 As another example of the monomer that can be included together with the monomer S1 as a monomer unit constituting the silicone oligomer Ps, a carboxyl group-containing monomer and an acid anhydride group-containing monomer exemplified above as the monomer that can be used in the alkyl (meth)acrylate (A) are included. Monomer, hydroxyl group-containing monomer, epoxy group-containing monomer, cyano group-containing monomer, isocyanate group-containing monomer, amide group-containing monomer, nitrogen atom-containing ring-containing monomer, succinimide skeleton-containing monomer, maleimides, itaconimides, (meth)acrylic Acid aminoalkyls, vinyl esters, vinyl ethers, olefins, aromatic hydrocarbon group-containing (meth)acrylic acid esters, heterocycle-containing (meth)acrylates, halogen atom-containing (meth)acrylates, terpene compound derivative alcohols The (meth)acrylic acid ester etc. which are obtained are mentioned.
　シリコーンオリゴマーＰｓを構成するモノマー単位としてモノマーＳ１とともに含まれ得るモノマーのさらに他の例として、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート等のオキシアルキレンジ（メタ）アクリレート；ポリオキシアルキレン骨格を有するモノマー、例えばポリエチレングリコールやポリプロピレングリコール等のポリオキシアルキレン鎖の一方の末端に（メタ）アクリロイル基、ビニル基、アリル基等の重合性官能基を有し、他方の末端にエーテル構造（アルキルエーテル、アリールエーテル、アリールアルキルエーテル等）を有する重合性ポリオキシアルキレンエーテル；（メタ）アクリル酸メトキシエチル、（メタ）アクリル酸エトキシエチル、（メタ）アクリル酸プロポキシエチル、（メタ）アクリル酸ブトキシエチル、（メタ）アクリル酸エトキシプロピル等の（メタ）アクリル酸アルコキシアルキル；（メタ）アクリル酸アルカリ金属塩等の塩；トリメチロールプロパントリ（メタ）アクリル酸エステル等の多価（メタ）アクリレート：塩化ビニリデン、（メタ）アクリル酸－２－クロロエチル等のハロゲン化ビニル化合物；２－ビニル－２－オキサゾリン、２－ビニル－５－メチル－２－オキサゾリン、２－イソプロペニル－２－オキサゾリン等のオキサゾリン基含有モノマー；（メタ）アクリロイルアジリジン、（メタ）アクリル酸－２－アジリジニルエチル等のアジリジン基含有モノマー；（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、ラクトン類と（メタ）アクリル酸－２－ヒドロキシエチルとの付加物等の水酸基含有ビニルモノマー；フッ素置換（メタ）アクリル酸アルキルエステル等の含フッ素ビニルモノマー；２－クロルエチルビニルエーテル、モノクロロ酢酸ビニル等の反応性ハロゲン含有ビニルモノマー；ビニルトリメトキシシラン、γ－（メタ）アクリロキシプロピルトリメトキシシラン、アリルトリメトキシシラン、トリメトキシシリルプロピルアリルアミン、２－メトキシエトキシトリメトキシシランのような有機ケイ素含有ビニルモノマー；その他、ビニル基を重合したモノマー末端にラジカル重合性ビニル基を有するマクロモノマー類；等を挙げることができる。これらは、１種を単独であるいは組み合わせてモノマーＳ１と共重合させることができる。 As still another example of the monomer that can be included together with the monomer S1 as a monomer unit constituting the silicone oligomer Ps, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di Oxyalkylene di(meth)acrylates such as (meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate; monomers having a polyoxyalkylene skeleton, for example polyethylene Polyoxyalkylene chain such as glycol or polypropylene glycol has a polymerizable functional group such as (meth)acryloyl group, vinyl group or allyl group at one end and an ether structure (alkyl ether, aryl ether, aryl) at the other end. Polymerizable polyoxyalkylene ether having alkyl ether, etc.; methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, propoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, (meth)acrylic acid Alkoxyalkyl (meth)acrylates such as ethoxypropyl; salts such as alkali metal salts of (meth)acrylic acid; polyvalent (meth)acrylates such as trimethylolpropane tri(meth)acrylic acid ester: vinylidene chloride, (meth)acrylic Halogenated vinyl compounds such as acid-2-chloroethyl; 2-vinyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline and other oxazoline group-containing monomers; (meth) Aziridine group-containing monomers such as acryloyl aziridine and 2-aziridinylethyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, lactones and (meth) Hydroxyl group-containing vinyl monomer such as adduct with 2-hydroxyethyl acrylate; Fluorine-containing vinyl monomer such as fluorine-substituted (meth)acrylic acid alkyl ester; Reactive halogen-containing vinyl such as 2-chloroethyl vinyl ether and monochlorovinyl acetate Monomers: vinyltrimethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, allyltrimethoxysilane, trimethoxysilylpropylallylamine, 2-methoxyethoxytrimethoxysilane Silicon-containing vinyl monomers; other macromonomers having a radically polymerizable vinyl group at the terminal of a vinyl group-polymerized monomer; and the like. These can be copolymerized alone or in combination with the monomer S1.
　シリコーンオリゴマーＰｓの調製に用いられるモノマー成分がモノマーＳ１および（メタ）アクリル系モノマーを含む態様において、上記モノマー成分全体に占めるモノマーＳ１と（メタ）アクリル系モノマーとの合計量は、例えば５０重量％以上であってよく、７０重量％以上でもよく、８５重量％以上でもよく、９０重量％以上でもよく、９５重量％以上でもよく、実質的に１００重量％でもよい。 In an embodiment in which the monomer component used for the preparation of the silicone oligomer Ps includes the monomer S1 and the (meth)acrylic monomer, the total amount of the monomer S1 and the (meth)acrylic monomer in the entire monomer component is, for example, 50% by weight. The amount may be 70% by weight or more, 85% by weight or more, 90% by weight or more, 95% by weight or more, or substantially 100% by weight.
　上記モノマー成分に含まれる（メタ）アクリル系モノマーの組成は、例えば、当該（メタ）アクリル系モノマーの組成に基づくガラス転移温度Ｔｍ１が０℃より高くなるように設定することができる。ここで、（メタ）アクリル系モノマーの組成に基づくガラス転移温度Ｔｍ１とは、シリコーンオリゴマーＰｓの調製に用いられるモノマー成分のうち（メタ）アクリル系モノマーのみの組成に基づいて、Ｆｏｘの式により求められるＴｇをいう。Ｔｍ１は、シリコーンオリゴマーＰｓの調製に用いられるモノマー成分のうち（メタ）アクリル系モノマーのみを対象として、上述したＦｏｘの式を適用し、各（メタ）アクリル系モノマーのホモポリマーのガラス転移温度と、当該（メタ）アクリル系モノマーの合計量に占める各（メタ）アクリル系モノマー重量分率とから算出することができる。ガラス転移温度Ｔｍ１が０℃より高いシリコーンオリゴマーＰｓによると、初期粘着力が抑制されやすい。また、ガラス転移温度Ｔｍ１が０℃より高いシリコーンオリゴマーＰｓを用いることにより、粘着力上昇比の大きい粘着シートが得られやすい。 The composition of the (meth)acrylic monomer contained in the monomer component can be set such that the glass transition temperature T m1 based on the composition of the (meth)acrylic monomer is higher than 0° C., for example. Here, the glass transition temperature T m1 based on the composition of the (meth)acrylic monomer is based on the composition of only the (meth)acrylic monomer among the monomer components used for the preparation of the silicone oligomer Ps, and according to the Fox equation. Refers to the required Tg. T m1 is the glass transition temperature of the homopolymer of each (meth)acrylic monomer, which is obtained by applying the above-described Fox equation to only the (meth)acrylic monomer among the monomer components used for the preparation of the silicone oligomer Ps. And the weight fraction of each (meth)acrylic monomer in the total amount of the (meth)acrylic monomer. According to the silicone oligomer Ps having a glass transition temperature T m1 higher than 0° C., the initial adhesive force is easily suppressed. Further, by using the silicone oligomer Ps having a glass transition temperature T m1 higher than 0° C., it is easy to obtain a pressure-sensitive adhesive sheet having a large adhesive force increase ratio.
　いくつかの態様において、Ｔｍ１は、－２０℃以上でもよく、－１０℃以上でもよく、０℃以上でもよく、１０℃以上でもよい。Ｔｍ１が高くなると、貼付け初期の粘着力は、概して、よりよく抑制される傾向にある。また、Ｔｍ１は、例えば９０℃以下でもよく、８０℃以下でもよく、７０℃以下または７０℃未満でもよい。Ｔｍ１が低くなると、加熱による粘着力上昇が容易化する傾向にある。ここに開示される技術は、Ｔｍ１が、例えば－２０℃～９０℃、または－１０℃～８０℃、また０℃～７０℃の範囲にあるシリコーンオリゴマーＰｓを用いて好ましく実施され得る。 In some embodiments, T m1 may be −20° C. or higher, −10° C. or higher, 0° C. or higher, or 10° C. or higher. At higher T m1, the adhesive strength in the early stage of application generally tends to be better suppressed. Further, T m1 may be, for example, 90° C. or lower, 80° C. or lower, 70° C. or lower, or lower than 70° C. When T m1 is low, increase in adhesive strength due to heating tends to be facilitated. The technique disclosed herein can be preferably carried out using a silicone oligomer Ps having T m1 in the range of, for example, −20° C. to 90° C., or −10° C. to 80° C., and 0° C. to 70° C.
　シリコーンオリゴマーＰｓは、例えば、上述したモノマーを、溶液重合法、エマルション重合法、バルク重合法、懸濁重合法、光重合法等の既知の手法により重合させることで作製することができる。 The silicone oligomer Ps can be produced, for example, by polymerizing the above-mentioned monomer by a known method such as a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, or a photopolymerization method.
　シリコーンオリゴマーＰｓの分子量を調整するために連鎖移動剤を用いることができる。使用する連鎖移動剤の例としては、オクチルメルカプタン、ラウリルメルカプタン、ｔ－ノニルメルカプタン、ｔ－ドデシルメルカプタン、メルカプトエタノール、α－チオグリセロール等のメルカプト基を有する化合物；チオグリコール酸、チオグリコール酸メチル、チオグリコール酸エチル、チオグリコール酸プロピル、チオグリコール酸ブチル、チオグリコール酸ｔ－ブチル、チオグリコール酸２－エチルヘキシル、チオグリコール酸オクチル、チオグリコール酸イソオクチル、チオグリコール酸デシル、チオグリコール酸ドデシル、エチレングリコールのチオグリコール酸エステル、ネオペンチルグリコールのチオグリコール酸エステル、ペンタエリスリトールのチオグリコール酸エステル等のチオグリコール酸エステル類；α－メチルスチレンダイマー；等が挙げられる。 A chain transfer agent can be used to adjust the molecular weight of the silicone oligomer Ps. Examples of the chain transfer agent to be used include compounds having a mercapto group such as octyl mercaptan, lauryl mercaptan, t-nonyl mercaptan, t-dodecyl mercaptan, mercaptoethanol and α-thioglycerol; thioglycolic acid, methyl thioglycolate, Ethyl thioglycolate, propyl thioglycolate, butyl thioglycolate, t-butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate, isooctyl thioglycolate, decyl thioglycolate, dodecyl thioglycolate, ethylene Examples thereof include thioglycolic acid esters such as thioglycolic acid ester of glycol, thioglycolic acid ester of neopentyl glycol, and thioglycolic acid ester of pentaerythritol; α-methylstyrene dimer; and the like.
　連鎖移動剤の使用量としては、特に制限されないが、通常、モノマー１００重量部に対して、連鎖移動剤を０．０５重量部～２０重量部、好ましくは、０．１重量部～１５重量部、さらに好ましくは０．２重量部～１０重量部含有する。このように連鎖移動剤の添加量を調整することで、好適な分子量のシリコーンオリゴマーＰｓを得ることができる。なお、連鎖移動剤は、１種を単独でまたは２種以上を組み合わせて使用することができる。 The amount of the chain transfer agent used is not particularly limited, but is usually 0.05 to 20 parts by weight, preferably 0.1 to 15 parts by weight with respect to 100 parts by weight of the monomer. And more preferably 0.2 to 10 parts by weight. By adjusting the addition amount of the chain transfer agent in this way, a silicone oligomer Ps having a suitable molecular weight can be obtained. The chain transfer agents may be used alone or in combination of two or more.
　本発明の一実施形態において、シリコーンオリゴマーＰｓは、上述の（メタ）アクリル系ポリマー１００重量部に対し、０．１～２０重量部で含まれ得る。本発明の実施形態において、シリコーンオリゴマーＰｓは、上述の（メタ）アクリル系ポリマー１００重量部に対し、好ましくは、０．２５～１０重量部で含まれ、より好ましくは、０．５～５重量部で含まれ得る。粘着剤層に含まれるシリコーンオリゴマーＰｓの含量が上記の範囲内であると、初期粘着力を抑制することができ、より高い加熱後粘着力を得ることができる。 In an embodiment of the present invention, the silicone oligomer Ps may be included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the (meth)acrylic polymer. In the embodiment of the present invention, the silicone oligomer Ps is preferably contained in an amount of 0.25 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the above-mentioned (meth)acrylic polymer. May be included in the section. When the content of the silicone oligomer Ps contained in the adhesive layer is within the above range, the initial adhesive force can be suppressed and a higher adhesive force after heating can be obtained.
　なお、上述のようなシリコーンオリゴマーＰｓは、粘着剤層に配合されることで、粘着力上昇遅延剤として好ましく機能し得る。ここに開示される粘着シートは、粘着剤層を構成する粘着剤がベースポリマーおよび粘着力上昇遅延剤を含み、該粘着力上昇遅延剤がシリコーンオリゴマーＰｓを含む態様で好ましく実施され得る。ここで、シリコーンオリゴマーＰｓが粘着力上昇遅延剤として機能するのは、被着体への貼付け前から貼付け初期の粘着シートにおいては粘着剤層の表面に存在するシリコーンオリゴマーＰｓによって初期粘着力が抑制され、貼付け後の経時や加熱等により粘着剤が流動することで粘着剤層表面におけるシリコーンオリゴマーＰｓの存在量が減少してシリコーンオリゴマーＰｓが粘着剤と相溶し、粘着力が上昇するためと考えられる。したがって、ここに開示される技術における上記粘着力上昇遅延剤としては、シリコーンオリゴマーＰｓに代えて、あるいはシリコーンオリゴマーＰｓと組み合わせて、同種の機能を発揮し得る他の材料が用いられ得る。そのような材料の非限定的な例として、分子内にポリオキシアルキレン構造を有するポリマー（以下「ポリマーＰｏ」ともいう。）が挙げられる。ポリマーＰｏは、例えば、ポリオキシアルキレン骨格を有するモノマーに由来するモノマー単位を含む重合体であり得る。具体例としては、上述のようなポリオキシアルキレン骨格を有するモノマーのいずれか１種の単独重合体や２種以上の共重合体、ポリオキシアルキレン骨格を有するモノマーの１種または２種以上と他のモノマー（例えば、（メタ）アクリル系モノマー）との共重合体等をポリマーＰｏとして使用し得る。ポリオキシアルキレン骨格を有するモノマーの使用量は、特に限定されないが、例えば、上述したシリコーンオリゴマーＰｓにおけるモノマーＳ１の使用量を、ポリマーＰｏにおけるポリオキシアルキレン骨格を有するモノマーの使用量にも適用することができる。また、粘着剤層におけるポリマーＰｏの使用量は、特に限定されないが、例えば、上述したベースポリマーに対するシリコーンオリゴマーＰｓの使用量を、ベースポリマーに対するポリマーＰｏの使用量にも適用することができる。あるいは、上述したベースポリマーに対するシリコーンオリゴマーＰｓの使用量のうち一部（例えば、シリコーンオリゴマーＰｓの全使用量のうち５重量％～９５重量％程度、または１５重量％～８５重量％程度、または３０重量％～７０重量％程度）をポリマーＰｏに置き換えてもよい。 Incidentally, the silicone oligomer Ps as described above can function favorably as an agent for increasing the adhesive strength by being mixed in the adhesive layer. The pressure-sensitive adhesive sheet disclosed herein can be preferably implemented in a mode in which the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer contains a base polymer and a pressure-sensitive adhesive force increase retarder, and the pressure-sensitive adhesive force increase retarder contains a silicone oligomer Ps. Here, the silicone oligomer Ps functions as an adhesive force increase retarder because the initial adhesive force is suppressed by the silicone oligomer Ps existing on the surface of the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet from before attachment to the adherend and in the initial stage of attachment. As a result, the amount of the silicone oligomer Ps present on the surface of the pressure-sensitive adhesive layer decreases due to the pressure-sensitive adhesive flowing due to the passage of time after application, heating, etc., and the silicone oligomer Ps is compatible with the pressure-sensitive adhesive, increasing the adhesive strength. Conceivable. Therefore, as the above-mentioned adhesive force increase retarder in the technology disclosed herein, other materials capable of exhibiting the same kind of function may be used instead of the silicone oligomer Ps or in combination with the silicone oligomer Ps. A non-limiting example of such a material is a polymer having a polyoxyalkylene structure in the molecule (hereinafter, also referred to as “polymer Po”). The polymer Po can be, for example, a polymer including a monomer unit derived from a monomer having a polyoxyalkylene skeleton. Specific examples thereof include homopolymers or copolymers of any one of the above-mentioned monomers having a polyoxyalkylene skeleton, and one or more of monomers having a polyoxyalkylene skeleton and others. A copolymer with the monomer (eg, a (meth)acrylic monomer) or the like can be used as the polymer Po. The amount of the monomer having a polyoxyalkylene skeleton is not particularly limited, but for example, the amount of the monomer S1 used in the silicone oligomer Ps described above may be applied to the amount of the monomer having a polyoxyalkylene skeleton in the polymer Po. You can The amount of the polymer Po used in the pressure-sensitive adhesive layer is not particularly limited. For example, the amount of the silicone oligomer Ps used for the base polymer described above can be applied to the amount of the polymer Po used for the base polymer. Alternatively, a part of the amount of the silicone oligomer Ps used with respect to the above-mentioned base polymer (for example, about 5% by weight to 95% by weight, or about 15% by weight to 85% by weight of the total amount of the silicone oligomer Ps used, or 30 % To about 70% by weight) may be replaced with the polymer Po.
　本発明の一実施形態において、シリコーンオリゴマーＰｓの溶融温度は、－２０～１２０℃であってよい。本発明の別の実施形態において、シリコーンオリゴマーＰｓの溶融温度は、－１０～９０℃、０～８０℃であってよい。 In one embodiment of the present invention, the melting temperature of the silicone oligomer Ps may be -20 to 120°C. In another embodiment of the present invention, the melting temperature of the silicone oligomer Ps may be −10 to 90° C., 0 to 80° C.
　＜その他の成分＞
　（架橋剤）
　本明細書に開示される粘着剤層には、凝集力の調整等の目的で、架橋剤が用いられ得る。架橋剤は、通常用いる架橋剤を使用することができ、例えば、エポキシ系架橋剤、イソシアネート系架橋剤、シリコーン系架橋剤、オキサゾリン系架橋剤、アジリジン系架橋剤、シラン系架橋剤、アルキルエーテル化メラミン系架橋剤、金属キレート系架橋剤等を挙げることができる。特に、イソシアネート系架橋剤、エポキシ系架橋剤、金属キレート系架橋剤を好適に使用することができる。架橋剤は、１種を単独でまたは２種以上を組み合わせて用いることができる。 <Other ingredients>
(Crosslinking agent)
A crosslinking agent may be used in the pressure-sensitive adhesive layer disclosed in the present specification for the purpose of adjusting cohesive force and the like. As the cross-linking agent, a commonly used cross-linking agent can be used, and examples thereof include epoxy cross-linking agents, isocyanate cross-linking agents, silicone cross-linking agents, oxazoline cross-linking agents, aziridine cross-linking agents, silane cross-linking agents, alkyl etherifications. Examples thereof include a melamine-based crosslinking agent and a metal chelate-based crosslinking agent. In particular, an isocyanate cross-linking agent, an epoxy cross-linking agent, and a metal chelate cross-linking agent can be preferably used. The cross-linking agents can be used alone or in combination of two or more.
　具体的には、イソシアネート系架橋剤の例としては、トリレンジイソシアネート、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、キシリレンジイソシアネート、水添キシリレンジイソシアネート、ジフェニルメタンジイソシアネート、水添ジフェニルメタンジイソシアネート、テトラメチルキシリレンジイソシアネート、ナフタリ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、ポリメチレンポリフェニルイソシアネート、および、これらとトリメチロールプロパン等のポリオールとのアダクト体を挙げることができる。あるいは、１分子中に少なくとも１つ以上のイソシアネート基と、１つ以上の不飽和結合を有する化合物、具体的には、２－イソシアナートエチル（メタ）アクリレートなどもイソシアネート系架橋剤として使用することができる。これらは１種を単独でまたは２種以上を組み合わせて用いることができる。 Specifically, examples of the isocyanate cross-linking agent include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene. Examples thereof include diisocyanate, triphenylmethane triisocyanate, polymethylene polyphenyl isocyanate, and adducts of these with polyols such as trimethylolpropane. Alternatively, a compound having at least one or more isocyanate group and one or more unsaturated bond in one molecule, specifically 2-isocyanatoethyl (meth)acrylate, etc., should also be used as an isocyanate cross-linking agent. You can These may be used alone or in combination of two or more.
　エポキシ系架橋剤としては、ビスフェノールＡ、エピクロルヒドリン型のエポキシ系樹脂、エチレングリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル、１,６－ヘキサンジオールグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ジグリシジルアニリン、ジアミングリシジルアミン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラグリシジル－ｍ－キシリレンジアミンおよび１，３－ビス（Ｎ，Ｎ－ジグリシジルアミノメチル）シクロヘキサン等を挙げることができる。これらは１種を単独でまたは２種以上を組み合わせて用いることができる。 Epoxy crosslinking agents include bisphenol A, epichlorohydrin type epoxy resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol glycidyl ether, trimethylolpropane tri Glycidyl ether, diglycidyl aniline, diamine glycidyl amine, N,N,N',N'-tetraglycidyl-m-xylylenediamine and 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane You can These may be used alone or in combination of two or more.
　金属キレート化合物としては、金属成分としてアルミニウム、鉄、スズ、チタン、ニッケルなど、キレート成分としてアセチレン、アセト酢酸メチル、乳酸エチルなどが挙げられる。これらは１種を単独でまたは２種以上を組み合わせて用いることができる。 Examples of the metal chelate compound include aluminum, iron, tin, titanium and nickel as metal components, and acetylene, methyl acetoacetate and ethyl lactate as chelate components. These may be used alone or in combination of two or more.
　架橋剤の使用量は、ベースポリマー１００重量部に対して、例えば０．０１重量部以上とすることができ、０．０５重量部以上とすることが好ましい。架橋剤の使用量の増大により、より高い凝集力が得られる傾向にある。いくつかの態様において、ベースポリマー１００重量部に対する架橋剤の使用量は、０．１重量部以上であってもよく、０．５重量部以上であってもよく、１重量部以上であってもよい。一方、過度な凝集力向上によるタックの低下を避ける観点から、ベースポリマー１００重量部に対する架橋剤の使用量は、通常、１５重量部以下とすることが適当であり、１０重量部以下としてもよく、５重量部以下としてもよい。シリコーンオリゴマーＰｓまたは他の粘着力上昇遅延剤を含む組成の粘着剤では、架橋剤の使用量が多過ぎないことは、粘着剤の流動性を利用して粘着力上昇遅延剤の使用効果をよりよく発現させる観点からも有利となり得る。 The amount of the crosslinking agent used can be, for example, 0.01 part by weight or more, and preferably 0.05 part by weight or more, based on 100 parts by weight of the base polymer. A higher cohesive force tends to be obtained by increasing the amount of the crosslinking agent used. In some embodiments, the amount of the cross-linking agent used may be 0.1 part by weight or more, 100 parts by weight or more, 0.5 parts by weight or more, and 1 part by weight or more. Good. On the other hand, from the viewpoint of avoiding a decrease in tack due to excessive improvement in cohesive force, the amount of the cross-linking agent to be used is usually 15 parts by weight or less, preferably 10 parts by weight or less, based on 100 parts by weight of the base polymer. It may be 5 parts by weight or less. In the PSA having a composition containing the silicone oligomer Ps or the other PSA retarder, the use amount of the crosslinking agent is not too large. It may be advantageous from the viewpoint of good expression.
　本明細書に開示される技術は、架橋剤として少なくともイソシアネート系架橋剤を用いる態様で好ましく実施され得る。加熱後凝集力が高く、かつ粘着力上昇比が大きい粘着シートを実現しやすくする観点から、いくつかの態様において、ベースポリマー１００重量部に対するイソシアネート系架橋剤の使用量は、例えば５重量部以下とすることができ、３重量部以下としてもよく、１重量部以下としてもよく、０．７重量部以下としてもよく、０．５重量部以下としてもよい。 The technique disclosed in the present specification can be preferably carried out in a mode in which at least an isocyanate cross-linking agent is used as the cross-linking agent. From the viewpoint of facilitating the realization of a pressure-sensitive adhesive sheet having a high cohesive force after heating and a high adhesive force increase ratio, in some embodiments, the amount of the isocyanate-based cross-linking agent based on 100 parts by weight of the base polymer is, for example, 5 parts by weight or less. It may be 3 parts by weight or less, 1 part by weight or less, 0.7 parts by weight or less, and 0.5 parts by weight or less.
　上述したいずれかの架橋反応をより効果的に進行させるために、架橋触媒を用いてもよい。架橋触媒としては、例えばスズ系触媒（特にジラウリン酸ジオクチルスズ）を好ましく用いることができる。架橋触媒の使用量は特に制限されないが、例えば、ベースポリマー１００重量部に対して凡そ０．０００１重量部～１重量部とすることができる。 A cross-linking catalyst may be used in order to more effectively promote any of the above-mentioned cross-linking reactions. As the crosslinking catalyst, for example, a tin-based catalyst (particularly dioctyltin dilaurate) can be preferably used. The amount of the crosslinking catalyst used is not particularly limited, but can be, for example, approximately 0.0001 parts by weight to 1 part by weight with respect to 100 parts by weight of the base polymer.
　（シランカップリング剤）
　本明細書に開示される粘着剤層には、さらに、シランカップリング剤を含有することできる。シランカップリング剤を用いることにより、耐久性を向上させることができる。シランカップリング剤としては、任意の適切な官能基を有するものを用いることができる。具体的には、官能基としては、例えば、ビニル基、エポキシ基、アミノ基、メルカプト基、（メタ）アクリロキシ基、アセトアセチル基、イソシアネート基、スチリル基、ポリスルフィド基等が挙げられる。具体的には、例えば、ビニルトリエトキシシラン、ビニルトリプロポキシシラン、ビニルトリイソプロポキシシラン、ビニルトリブトキシシラン等のビニル基含有シランカップリング剤；γ－グリシドキシプロピルトリメトキシシラン、γ－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エトキシシラン、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などのエポキシ基含有シランカップリング剤；γ－アミノプロピルトリメトキシシラン、Ｎ－β－（アミノエチル）－γ－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－アミノプロピルメチルジメトキシシラン、γ－トリエトキシシリル－Ｎ－（１，３－ジメチルブチリデン）プロピルアミン、Ｎ－フェニル－γ－アミノプロピルトリメトキシシラン等のアミノ基含有シランカップリング剤；γ－メルカプトプロピルメチルジメトキシシランなどのメルカプト基含有シランカップリング剤；ｐ－スチリルトリメトキシシラン等のスチリル基含有シランカップリング剤；γ－アクリロキシプロピルトリメトキシシラン、γ－メタクリロキシプロピルトリエトキシランなどの（メタ）アクリル基含有シランカップリング剤；３－イソシアネートプロピルトリエトキシシランなどのイソシアネート基含有シランカップリング剤；ビス（トリエトキシシリルプロピル）テトラスルフィド等のポリスルフィド基含有シランカップリング剤などが挙げられる。シランカップリング剤は、例えば、γ－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルトリエトキシシラン、γ－メルカプトプロピルメチルジメトキシシランを好適に用いることができる。 (Silane coupling agent)
The pressure-sensitive adhesive layer disclosed in the present specification may further contain a silane coupling agent. The durability can be improved by using the silane coupling agent. As the silane coupling agent, one having any appropriate functional group can be used. Specific examples of the functional group include a vinyl group, an epoxy group, an amino group, a mercapto group, a (meth)acryloxy group, an acetoacetyl group, an isocyanate group, a styryl group, and a polysulfide group. Specifically, for example, vinyl group-containing silane coupling agents such as vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, and vinyltributoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycine Epoxy group-containing silane coupling agents such as cidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane, γ-triethoxysilyl-N-(1,3-dimethylbutylidene) Amino group-containing silane coupling agents such as propylamine and N-phenyl-γ-aminopropyltrimethoxysilane; mercapto group-containing silane coupling agents such as γ-mercaptopropylmethyldimethoxysilane; p-styryltrimethoxysilane and other styryls Group-containing silane coupling agent; (meth)acryl group-containing silane coupling agent such as γ-acryloxypropyltrimethoxysilane and γ-methacryloxypropyltriethoxysilane; isocyanate group-containing silane such as 3-isocyanatepropyltriethoxysilane Coupling agents; polysulfide group-containing silane coupling agents such as bis(triethoxysilylpropyl) tetrasulfide and the like. As the silane coupling agent, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane and γ-mercaptopropylmethyldimethoxysilane are preferably used. You can
　前記シランカップリング剤は、単独で使用してもよく、また２種以上を混合して使用してもよいが、全体としての含有量は、ベースポリマー１００重量部に対し、前記シランカップリング剤０．００１～５重量部が好ましく、さらには０．０１～１重量部が好ましく、さらには０．０２～１重量部がより好ましく、さらには０．０５～０．６重量部が好ましい。 The silane coupling agent may be used alone or in combination of two or more kinds, but the total content is 100 parts by weight of the base polymer and the silane coupling agent. The amount is preferably 0.001 to 5 parts by weight, more preferably 0.01 to 1 part by weight, further preferably 0.02 to 1 part by weight, further preferably 0.05 to 0.6 part by weight.
　その他、ここに開示される技術における粘着剤層は、本発明の効果が著しく妨げられない範囲で、粘着付与剤、レベリング剤、可塑剤、軟化剤、着色剤（染料、顔料等）、充填剤、帯電防止剤、老化防止剤、紫外線吸収剤、酸化防止剤、光安定剤、防腐剤等の、粘着剤に使用され得る公知の添加剤を必要に応じて含んでいてもよい。 In addition, the pressure-sensitive adhesive layer in the technique disclosed herein is a tackifier, a leveling agent, a plasticizer, a softening agent, a colorant (a dye, a pigment, etc.), a filler, etc. within a range that does not significantly impair the effects of the present invention. If necessary, known additives such as antistatic agents, antiaging agents, ultraviolet absorbers, antioxidants, light stabilizers and preservatives that can be used for pressure-sensitive adhesives may be included.
　（粘着剤層の形成）
　粘着剤層を形成する方法としては、例えば、前記粘着剤組成物を剥離処理したセパレータ等に塗布し、重合溶剤等を乾燥除去して粘着剤層を形成した後に偏光フィルムに転写する方法、または偏光フィルムに前記粘着剤組成物を塗布し、重合溶剤等を乾燥除去して粘着剤層を偏光フィルムに形成する方法等により作製される。なお、粘着剤の塗布にあたっては、適宜に、重合溶剤以外の一種以上の溶剤を新たに加えてもよい。 (Formation of adhesive layer)
As a method for forming a pressure-sensitive adhesive layer, for example, a method in which the pressure-sensitive adhesive composition is applied to a release-treated separator or the like, and a polymerization solvent or the like is dried and removed to form a pressure-sensitive adhesive layer, and then transferred to a polarizing film, or It is prepared by a method of applying the above-mentioned pressure-sensitive adhesive composition to a polarizing film, drying and removing a polymerization solvent and the like to form an adhesive layer on the polarizing film. When applying the pressure-sensitive adhesive, one or more solvents other than the polymerization solvent may be newly added as appropriate.
　剥離処理したセパレータとしては、シリコーン剥離ライナーが好ましく用いられる。このようなライナー上に本発明の接着剤組成物を塗布、乾燥させて粘着剤層を形成する工程において、粘着剤を乾燥させる方法としては、目的に応じて、適宜、適切な方法が採用され得る。好ましくは、上記塗布膜を加熱乾燥する方法が用いられる。加熱乾燥温度は、好ましくは４０℃～２００℃であり、さらに好ましくは、５０℃～１８０℃であり、特に好ましくは７０℃～１７０℃である。加熱温度を上記の範囲とすることによって、優れた粘着特性を有する粘着剤を得ることができる。 A silicone release liner is preferably used as the release-treated separator. In the step of forming the pressure-sensitive adhesive layer by applying the adhesive composition of the present invention on such a liner, and drying the pressure-sensitive adhesive layer, as a method for drying the pressure-sensitive adhesive, an appropriate method is appropriately adopted depending on the purpose. obtain. Preferably, a method of heating and drying the above coating film is used. The heat drying temperature is preferably 40°C to 200°C, more preferably 50°C to 180°C, and particularly preferably 70°C to 170°C. By setting the heating temperature in the above range, a pressure-sensitive adhesive having excellent pressure-sensitive adhesive properties can be obtained.
　乾燥時間は、適宜、適切な時間が採用され得る。上記乾燥時間は、好ましくは５秒間～２０分間、さらに好ましくは５秒間～１０分間、特に好ましくは、１０秒間～５分間である。 As for the drying time, an appropriate time can be adopted as appropriate. The drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and particularly preferably 10 seconds to 5 minutes.
　また、偏光フィルムの表面に、アンカー層を形成したり、コロナ処理、プラズマ処理等の各種易接着処理を施した後に粘着剤層を形成したりすることができる。また、粘着剤層の表面には易接着処理をおこなってもよい。 Also, an anchor layer can be formed on the surface of the polarizing film, or an adhesive layer can be formed after various types of easy adhesion treatment such as corona treatment and plasma treatment. Further, the surface of the pressure-sensitive adhesive layer may be subjected to easy adhesion treatment.
　粘着剤層の形成方法としては、各種方法が用いられる。具体的には、例えば、ロールコート、キスロールコート、グラビアコート、リバースコート、ロールブラッシュ、スプレーコート、ディップロールコート、バーコート、ナイフコート、エアーナイフコート、カーテンコート、リップコート、ダイコーター等による押出しコート法等の方法が挙げられる。 Various methods are used to form the adhesive layer. Specifically, for example, roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, die coater, etc. Examples of the method include an extrusion coating method.
　粘着剤層の厚さは、特に制限されず、例えば、１～１００μｍ程度である。好ましくは、２～５０μｍ、より好ましくは２～４０μｍであり、さらに好ましくは、５～３５μｍである。 The thickness of the adhesive layer is not particularly limited and is, for example, about 1 to 100 μm. The thickness is preferably 2 to 50 μm, more preferably 2 to 40 μm, and further preferably 5 to 35 μm.
　前記粘着剤層が露出する場合には、実用に供されるまで剥離処理したシート（セパレータ）で粘着剤層を保護してもよい。 When the pressure-sensitive adhesive layer is exposed, the pressure-sensitive adhesive layer may be protected with a release-treated sheet (separator) until practical use.
　セパレータの構成材料としては、例えば、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート、ポリエステルフィルム等のプラスチックフィルム、紙、布、不織布等の多孔質材料、ネット、発泡シート、金属箔、およびこれらのラミネート体等の適宜な薄葉体等を挙げることができるが、表面平滑性に優れる点からプラスチックフィルムが好適に用いられる。 As a constituent material of the separator, for example, polyethylene, polypropylene, polyethylene terephthalate, a plastic film such as a polyester film, a porous material such as paper, cloth, non-woven fabric, a net, a foamed sheet, a metal foil, and a laminated body thereof are appropriately used. Examples thereof include plastic thin films, and plastic films are preferably used because they have excellent surface smoothness.
　そのプラスチックフィルムとしては、前記粘着剤層を保護し得るフィルムであれば特に限定されず、例えば、ポリエチレンフィルム、ポリプロピレンフィルム、ポリブテンフィルム、ポリブタジエンフィルム、ポリメチルペンテンフイルム、ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム、ポリエチレンテレフタレートフィルム、ポリブチレンテレフタレートフィルム、ポリウレタンフィルム、エチレン－酢酸ビニル共重合体フィルム等が挙げられる。 The plastic film is not particularly limited as long as it is a film capable of protecting the pressure-sensitive adhesive layer, and examples thereof include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film and vinyl chloride. Examples thereof include polymer films, polyethylene terephthalate films, polybutylene terephthalate films, polyurethane films, ethylene-vinyl acetate copolymer films and the like.
　前記セパレータの厚みは、通常５～２００μｍ、好ましくは５～１００μｍ程度である。前記セパレータには、必要に応じて、シリコーン系、フッ素系、長鎖アルキル系もしくは脂肪酸アミド系の離型剤、シリカ粉等による離型および防汚処理や、塗布型、練り込み型、蒸着型等の帯電防止処理もすることもできる。特に、前記セパレータの表面にシリコーン処理、長鎖アルキル処理、フッ素処理等の剥離処理を適宜おこなうことにより、前記粘着剤層からの剥離性をより高めることができる。 The thickness of the separator is usually 5 to 200 μm, preferably about 5 to 100 μm. In the separator, if necessary, a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent, release and antifouling treatment with silica powder or the like, coating type, kneading type, vapor deposition type It is also possible to perform antistatic treatment such as. Particularly, by appropriately performing a peeling treatment such as a silicone treatment, a long-chain alkyl treatment, or a fluorine treatment on the surface of the separator, the peelability from the pressure-sensitive adhesive layer can be further enhanced.
　なお、上記の粘着剤層付き偏光フィルムの作製にあたって用いた、剥離処理したシートは、そのまま粘着剤層付き偏光フィルムのセパレータとして用いることができ、工程面における簡略化ができる。 The release-treated sheet used in the production of the pressure-sensitive adhesive layer-attached polarizing film can be used as it is as a separator for the pressure-sensitive adhesive layer-attached polarizing film, which simplifies the process.
　以下に、本発明について実施例を挙げて説明するが、本発明は以下に示した実施例に制限されるものではない。なお、各例中の部および％はいずれも重量基準である。以下に特に規定のない室温放置条件は全て２３℃６５％ＲＨである。 The present invention will be described below with reference to examples, but the present invention is not limited to the examples shown below. In addition, all parts and% in each example are based on weight. Unless otherwise specified below, the room temperature standing condition is 23° C. and 65% RH.
　なお、下記の各ポリマーの重量平均分子量Ｍｗは、ＧＰＣ装置（東ソー社製、ＨＬＣ－８２２０ＧＰＣ）を用いて下記の条件で測定を行い、ポリスチレン換算により求めた。
　・サンプル濃度：０．２ｗｔ％（テトラヒドロフラン（ＴＨＦ）溶液）
　・サンプル注入量：１０μｌ
　・溶離液：ＴＨＦ・流速：０．６ｍｌ／ｍｉｎ
　・測定温度：４０℃ The weight average molecular weight Mw of each of the following polymers was determined by using a GPC device (manufactured by Tosoh Corporation, HLC-8220GPC) under the following conditions, and calculated in terms of polystyrene.
-Sample concentration: 0.2 wt% (tetrahydrofuran (THF) solution)
・Sample injection volume: 10 μl
・Eluent: THF ・Flow rate: 0.6 ml/min
・Measuring temperature: 40℃
　＜偏光子の作製＞
　平均重合度２４００、ケン化度９９．９モル％の厚み７５μｍのポリビニルアルコールフィルムを、３０℃の温水中に６０秒間浸漬し膨潤させた。次いで、ヨウ素／ヨウ化カリウム（重量比＝０．５／８）の濃度０．３％の水溶液に浸漬し、３．５倍まで延伸させながらフィルムを染色した。その後、６５℃のホウ酸エステル水溶液中で、トータルの延伸倍率が６倍となるように延伸を行った。延伸後に、４０℃のオーブンにて３分間乾燥を行い、ＰＶＡ系偏光子（ＳＰ値３２．８、厚み２３μｍ）を得た。水分率は１４重量％であった。 <Production of polarizer>
A polyvinyl alcohol film having an average polymerization degree of 2400 and a saponification degree of 99.9 mol% and a thickness of 75 μm was dipped in warm water at 30° C. for 60 seconds to be swollen. Next, the film was immersed in an aqueous solution of iodine/potassium iodide (weight ratio=0.5/8) having a concentration of 0.3%, and the film was dyed while stretching up to 3.5 times. Then, stretching was performed in a boric acid ester aqueous solution at 65° C. so that the total stretching ratio was 6 times. After stretching, it was dried in an oven at 40° C. for 3 minutes to obtain a PVA-based polarizer (SP value 32.8, thickness 23 μm). The water content was 14% by weight.
　＜透明保護フィルムの作製＞
　厚み４０μｍ、透湿度６０ｇ／ｍ２／２４ｈのアクリル系樹脂フィルム（ＳＰ値２２．２）の易接着処理面にコロナ処理を施して用いた。 <Preparation of transparent protective film>
The acrylic resin film (SP value 22.2) having a thickness of 40 μm and a water vapor transmission rate of 60 g/m 2/24 h was subjected to corona treatment before use.
　＜活性エネルギー線＞
　活性エネルギー線として、
　・紫外線照射装置（ガリウム封入メタルハライドランプ）：Ｆｕｓｉｏｎ　ＵＶ　Ｓｙｓｔｅｍｓ，Ｉｎｃ社製Ｌｉｇｈｔ　ＨＡＭＭＥＲ１０
　・バルブ：Ｖバルブ
　・ピーク照度：１６００ｍＷ／ｃｍ２、
　・積算照射量１０００／ｍＪ／ｃｍ２（波長３８０～４４０ｎｍ）を使用した。なお、紫外線の照度は、Ｓｏｌａｔｅｌｌ社製Ｓｏｌａ－Ｃｈｅｃｋシステムを使用して測定した。 <Active energy ray>
As active energy rays,
・Ultraviolet irradiation device (gallium-encapsulated metal halide lamp): Fusion UV Systems, Inc. Light HAMMER10
・Valve: V valve ・Peak illuminance: 1600 mW/cm 2 ,
An integrated dose of 1000/mJ/cm 2 (wavelength 380 to 440 nm) was used. The illuminance of ultraviolet rays was measured using a Sola-Check system manufactured by Solatell.
　＜活性エネルギー線硬化型接着剤の調製＞
　ラジカル重合性化合物（Ａ）として、Ｎ－ヒドロキシエチルアクリルアミド（ＳＰ値２９．６，ホモポリマーのＴｇ１２３℃，興人社製）を３８．３部、　ラジカル重合性化合物（Ｂ）として、トリプロピレングリコールジアクリレート（商品名：アロニックスＭ－２２０，ＳＰ値１９．０，ホモポリマーのＴｇ６９℃，東亞合成社製）を１９．１部、　ラジカル重合性化合物（Ｃ）として、アクリロイルモルホリン（ＳＰ値２２．９，ホモポリマーのＴｇ１５０℃，興人社製）を３８．３部、および　光重合開始剤（商品名：ＫＡＹＡＣＵＲＥ　ＤＥＴＸ－Ｓ，ジエチルチオキサントン，日本化薬社製）１．４部を混合して５０℃で１時間撹拌して活性エネルギー線硬化型接着剤を得た。 <Preparation of active energy ray-curable adhesive>
38.3 parts of N-hydroxyethylacrylamide (SP value 29.6, homopolymer Tg123° C., manufactured by Kojinsha) as the radically polymerizable compound (A), and tripropylene glycol as the radically polymerizable compound (B). 19.1 parts of diacrylate (trade name: Aronix M-220, SP value 19.0, homopolymer Tg 69° C., manufactured by Toagosei Co., Ltd.), and acryloylmorpholine (SP value 22.50) as a radically polymerizable compound (C). 9, 38.3 parts of homopolymer Tg 150° C., manufactured by Kojin Co., Ltd., and 1.4 parts of a photopolymerization initiator (trade name: KAYACURE DETX-S, diethylthioxanthone, manufactured by Nippon Kayaku Co., Ltd.) were mixed. The mixture was stirred at 50° C. for 1 hour to obtain an active energy ray-curable adhesive.
　＜偏光フィルムＡの作製＞
　上記アクリル系樹脂フィルム上に、厚さ０．５μｍのウレタン系易接着剤層を形成した後に、当該易接着剤層に、上記活性エネルギー線硬化型接着剤を、ＭＣＤコーター（富士機械社製）（セル形状：ハニカム、グラビアロール線数：１０００本／ｉｎｃｈ、回転速度１４０％／対ライン速）を用いて、接着剤層の厚みが０．５μｍになるように塗工した。次いで、前記接着剤を介して、前記アクリル系樹脂フィルムを、視認側および／パネル側の透明保護フィルムとして、上記偏光子の両面にロール機で貼り合わせた。その後、貼り合わせたアクリル系樹脂フィルムの両側から、ＩＲヒーターを用いて５０℃に加温し、上記紫外線を両面に照射して、活性エネルギー線硬化型接着剤を硬化させた。さらに、７０℃で３分間熱風乾燥して、偏光子の両面に透明保護フィルムを有する偏光フィルムを得た（表１）。貼り合わせのライン速度は２５ｍ／ｍｉｎで行った。
Figure JPOXMLDOC01-appb-T000003
   <Production of Polarizing Film A>
After forming a urethane-based easy-adhesive layer having a thickness of 0.5 μm on the acrylic resin film, the active energy ray-curable adhesive was applied to the easy-adhesive layer by an MCD coater (manufactured by Fuji Machine Co., Ltd.). (Cell shape: honeycomb, gravure roll number of lines: 1000/inch, rotation speed 140%/vs line speed) was used to coat the adhesive layer to a thickness of 0.5 μm. Then, the acrylic resin film was bonded to both sides of the above-mentioned polarizer with a roll machine as a transparent protective film on the viewing side and/or the panel side via the adhesive. Then, the both sides of the bonded acrylic resin film were heated to 50° C. using an IR heater, and both sides were irradiated with the above-mentioned ultraviolet rays to cure the active energy ray-curable adhesive. Further, it was dried with hot air at 70° C. for 3 minutes to obtain a polarizing film having transparent protective films on both sides of the polarizer (Table 1). The bonding line speed was 25 m/min.
Figure JPOXMLDOC01-appb-T000003
　＜粘着剤の調製＞
　（ポリマー溶液Ａの調製）
　冷却管、窒素導入管、温度計及び撹拌装置を備えた反応容器に、アクリル酸ブチル１００部、アクリル酸５部、アクリル酸２－ヒドロキシエチル０．０７５部および２，２’－アゾビスイソブチロニトリル０．３部を酢酸エチルと共に加えて溶液を調製した。次いで、この溶液に窒素ガスを吹き込みながら撹拌して、６０℃で４時間反応させて、重量平均Ｍｗが２２０万のアクリル系ポリマーを含有する溶液を得た。さらに、このアクリル系ポリマーを含有する溶液に、酢酸エチルを加えて固形分濃度を３０％に調整したアクリル系ポリマー溶液Ａを得た。 <Preparation of adhesive>
(Preparation of polymer solution A)
In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer, 100 parts of butyl acrylate, 5 parts of acrylic acid, 0.075 parts of 2-hydroxyethyl acrylate and 2,2'-azobisisobutyrate. A solution was prepared by adding 0.3 part of ronitrile together with ethyl acetate. Next, this solution was stirred while blowing nitrogen gas and reacted at 60° C. for 4 hours to obtain a solution containing an acrylic polymer having a weight average Mw of 2,200,000. Further, ethyl acetate was added to the solution containing the acrylic polymer to obtain an acrylic polymer solution A in which the solid content concentration was adjusted to 30%.
　前記アクリル系ポリマー溶液Ａの固形分１００部に対して、架橋剤として、０．６部のイソシアネート基を有する化合物を主成分とする架橋剤（日本ポリウレタン（株）製，商品名「コロネートＬ」）と、シランカップリング剤として、０．０７５部のγ－グリシドキシプロピルトリメトキシシラン（信越化学工業（株）製，商品名「ＫＢＭ－４０３」）とをこの順に配合して、粘着剤ポリマー溶液Ａを調製した。 As a cross-linking agent, based on 100 parts of the solid content of the acrylic polymer solution A, a cross-linking agent containing 0.6 part of a compound having an isocyanate group as a main component (manufactured by Nippon Polyurethane Co., Ltd., trade name "Coronate L") ) And 0.075 part of γ-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-403”) as a silane coupling agent in this order, and the adhesive agent Polymer solution A was prepared.
　（ポリマー溶液Ｂの調製）
　冷却管、窒素導入管、温度計及び撹拌装置を備えた反応容器に、２－エチルヘキシルアクリレート（２ＥＨＡ）９４部、アクリル酸６部および２，２’－アゾビスイソブチロニトリル０．３部を酢酸エチルと共に加えて溶液を調製した。次いで、この溶液に窒素ガスを吹き込みながら撹拌して、６０℃で４時間反応させて、重量平均分子量Ｍｗが２２０万のアクリル系ポリマーを含有する溶液を得た。さらに、このアクリル系ポリマーを含有する溶液に、酢酸エチルを加えて固形分濃度を３０％に調整したアクリル系ポリマー溶液（Ｂ）を得た。 (Preparation of polymer solution B)
In a reaction vessel equipped with a cooling tube, a nitrogen introducing tube, a thermometer and a stirrer, 94 parts of 2-ethylhexyl acrylate (2EHA), 6 parts of acrylic acid and 0.3 parts of 2,2′-azobisisobutyronitrile are added. A solution was prepared by adding together with ethyl acetate. Then, the solution was stirred while blowing nitrogen gas and reacted at 60° C. for 4 hours to obtain a solution containing an acrylic polymer having a weight average molecular weight Mw of 2.2 million. Further, ethyl acetate was added to the solution containing the acrylic polymer to obtain an acrylic polymer solution (B) in which the solid content concentration was adjusted to 30%.
　前記アクリル系ポリマー溶液（Ｂ）の固形分１００部に対して、架橋剤として、０．６部のイソシアネート基を有する化合物を主成分とする架橋剤（日本ポリウレタン（株）製，商品名「コロネートＬ」）と、シランカップリング剤として、０．０７５部のγ－グリシドキシプロピルトリメトキシシラン（信越化学工業（株）製，商品名「ＫＢＭ－４０３」）とをこの順に配合して、粘着剤ポリマー溶液Ｂを調製した。 As a cross-linking agent, a cross-linking agent containing 0.6 part of a compound having an isocyanate group as a main component based on 100 parts of the solid content of the acrylic polymer solution (B) (manufactured by Nippon Polyurethane Co., Ltd., trade name "Coronate") L”) and 0.075 part of γ-glycidoxypropyltrimethoxysilane (trade name “KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent in this order, An adhesive polymer solution B was prepared.
　アクリル系ポリマー溶液（Ａ）（ポリマーＡ）およびアクリル系ポリマー溶液（Ｂ）（ポリマーＢ）の組成を下記表２に示す。
Figure JPOXMLDOC01-appb-T000004
   The compositions of the acrylic polymer solution (A) (polymer A) and the acrylic polymer solution (B) (polymer B) are shown in Table 2 below.
Figure JPOXMLDOC01-appb-T000004
　（シリコーンオリゴマーＡの調製）
　撹拌羽根、温度計、窒素ガス導入管、冷却器、滴下ロートを備えた４つ口フラスコに、酢酸エチル１００部、ＭＭＡ４０部、ｎ－ブチルメタクリレート（ＢＭＡ）２０部、２－エチルヘキシルメタクリレート（２ＥＨＭＡ）２０部、官能基当量が９００ｇ／ｍｏｌのポリオルガノシロキサン骨格含有メタクリレートモノマー（商品名：Ｘ－２２－１７４ＡＳＸ、信越化学工業株式会社製）８．７部、官能基当量が４６００ｇ／ｍｏｌのポリオルガノシロキサン骨格含有メタクリレートモノマー（商品名：ＫＦ－２０１２、信越化学工業株式会社製）１１．３部および連鎖移動剤としてチオグリコール酸メチル０．２部を投入した。そして、７０℃にて窒素雰囲気下で１時間撹拌した後、熱重合開始剤として２，２’－アゾビスイソブチロニトリル０．２部を投入し、７０℃で２時間反応させた後に、熱重合開始剤として２，２’－アゾビスイソブチロニトリル０．１部を投入し、続いて８０℃で３時間反応させた。このようにしてシリコーンオリゴマーの溶液を得た。このシリコーンオリゴマーの重量平均分子量Ｍｗは１８０００であった。 (Preparation of Silicone Oligomer A)
A 4-neck flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, a condenser, and a dropping funnel, 100 parts of ethyl acetate, 40 parts of MMA, 20 parts of n-butyl methacrylate (BMA), and 2-ethylhexyl methacrylate (2EHMA). 20 parts, polyorganosiloxane skeleton-containing methacrylate monomer having a functional group equivalent of 900 g/mol (trade name: X-22-174ASX, manufactured by Shin-Etsu Chemical Co., Ltd.) 8.7 parts, polyorgano having a functional group equivalent of 4600 g/mol. 11.3 parts of a siloxane skeleton-containing methacrylate monomer (trade name: KF-2012, manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.2 part of methyl thioglycolate as a chain transfer agent were added. Then, after stirring at 70° C. under a nitrogen atmosphere for 1 hour, 0.2 part of 2,2′-azobisisobutyronitrile was added as a thermal polymerization initiator, and after reacting at 70° C. for 2 hours, As a thermal polymerization initiator, 0.1 part of 2,2′-azobisisobutyronitrile was added, and the reaction was continued at 80° C. for 3 hours. Thus, a solution of silicone oligomer was obtained. The weight average molecular weight Mw of this silicone oligomer was 18,000.
　（その他のシリコーンオリゴマーＢ～Ｆの調製）
　シリコーンオリゴマーＢ～Ｆについては、モノマー組成および質量部を表３に記載の構成成分に変更したこと以外は、シリコーンオリゴマーＡと同様にして作製した。 (Preparation of other silicone oligomers B to F)
Silicone Oligomer B to F were produced in the same manner as Silicone Oligomer A except that the monomer composition and parts by weight were changed to the constituent components shown in Table 3.
Figure JPOXMLDOC01-appb-T000005
  
Figure JPOXMLDOC01-appb-T000005
  
　（粘着剤溶液の調製）
　上記調製した粘着剤ポリマー溶液Ａに、１部のシリコーンオリゴマーＡを配合して、実施例１で用いるアクリル系粘着剤溶液を調製した。同様にして、下記表４に記載された粘着剤ポリマー溶液とシリコーンオリゴマーとを用いて、実施例２～１９で用いるアクリル系粘着剤溶液を調製した。 (Preparation of adhesive solution)
The acrylic polymer solution A prepared above was mixed with 1 part of the silicone oligomer A to prepare an acrylic adhesive solution used in Example 1. Similarly, acrylic adhesive solutions used in Examples 2 to 19 were prepared using the adhesive polymer solutions and silicone oligomers shown in Table 4 below.
　（粘着剤層付き偏光フィルムの作製）
　［実施例１］～［実施例１９］
　次いで、上記アクリル系粘着剤溶液を、シリコーン系剥離剤で処理されたポリエチレンテレフタレートフィルム（セパレータフィルム）の表面に均一に塗工し、１５５℃の空気循環式恒温オーブンで２分間乾燥し、セパレータフィルムの表面に厚さ２０μｍの粘着剤層を形成した。上記偏光フィルムの片面に、粘着剤層を形成したセパレータを移着させ、粘着剤層付き偏光フィルムを作製した。 (Production of polarizing film with adhesive layer)
[Example 1] to [Example 19]
Then, the acrylic pressure-sensitive adhesive solution is uniformly applied to the surface of a polyethylene terephthalate film (separator film) treated with a silicone-based release agent, and dried for 2 minutes in an air circulation type constant temperature oven at 155° C. to form a separator film. An adhesive layer having a thickness of 20 μm was formed on the surface of. A separator having an adhesive layer formed thereon was transferred to one surface of the above polarizing film to prepare a polarizing film with an adhesive layer.
　［比較例１］
　比較例１において、シリコーンオリゴマーＡを除いたこと以外は実施例１と同じようにして、粘着剤層付き偏光フィルムを作製した。 [Comparative Example 1]
A polarizing film with a pressure-sensitive adhesive layer was produced in the same manner as in Example 1 except that the silicone oligomer A was removed in Comparative Example 1.
　［比較例２］～［比較例５］
　比較例２～５において、シリコーンオリゴマーＡの代わりにエーテル基含有ポリシロキサン（信越化学工業株式会社製、商品名「変性シリコーンオイル　ＫＦ－３５３」）を用い、配合量を表４に示すように変えたこと以外は実施例１と同じようにして、粘着剤層付き偏光フィルムを作製した。 [Comparative Example 2] to [Comparative Example 5]
In Comparative Examples 2 to 5, ether group-containing polysiloxane (trade name "modified silicone oil KF-353" manufactured by Shin-Etsu Chemical Co., Ltd.) was used in place of the silicone oligomer A, and the compounding amount was changed as shown in Table 4. A polarizing film with an adhesive layer was produced in the same manner as in Example 1 except for the above.
　［参考例１］
　参考例１において、シリコーンオリゴマーＡの代わりに別のリワーク向上剤（カネカ社製、商品名「ＳＡＴ１０」）を用い、配合量を表４に示すように変えたこと以外は実施例１と同じようにして、粘着剤層付き偏光フィル
ムを作製した。 [Reference Example 1]
Same as Example 1 except that another rework improver (Kaneka Corporation, trade name "SAT10") was used in place of the silicone oligomer A in Reference Example 1, and the compounding amount was changed as shown in Table 4. Then, a polarizing film with an adhesive layer was produced.
　上記実施例１～１９、比較例１～５、および参考例１で得られた粘着剤層付き偏光フィルムについて、下記評価を行った。結果を表４に示す。 The following evaluation was carried out on the polarizing film with the pressure-sensitive adhesive layer obtained in the above Examples 1 to 19, Comparative Examples 1 to 5 and Reference Example 1. The results are shown in Table 4.
　＜耐久性の評価＞
　粘着剤層付偏光フィルム（３７インチ）のセパレータフィルムを剥がし、厚さ０．７ｍｍの無アルカリガラス（コーニング社製，ＥＧ－ＸＧ）にラミネーターを用いて貼着した。次いで、５０℃、０．５ＭＰaで、１５分間のオートクレーブ処理を行って、前記偏光フィルムを完全に無アルカリガラスに密着させた。次いで、これを、８０℃の加熱オーブン（加熱）条件下にそれぞれ投入して、５００時間後の偏光板の剥がれの有無を、下記基準で評価した。
　Ａ：全く剥がれが認められなかった。
　Ｂ：目視で確認できない程度の発泡が認められた。
　Ｃ：目視では確認できない程度の剥がれが認められた。
　Ｄ：目視で確認できる小さな発泡または剥がれが認められた。
　Ｅ：明らかな発泡または剥がれが認められた。 <Evaluation of durability>
The separator film of the pressure-sensitive adhesive layer-attached polarizing film (37 inches) was peeled off and adhered to a 0.7 mm-thick non-alkali glass (EG-XG, manufactured by Corning Incorporated) using a laminator. Then, autoclave treatment was carried out at 50° C. and 0.5 MPa for 15 minutes to completely adhere the polarizing film to the alkali-free glass. Next, this was put into a heating oven (heating) condition of 80° C., and the presence or absence of peeling of the polarizing plate after 500 hours was evaluated based on the following criteria.
A: No peeling was observed at all.
B: Foaming was recognized to the extent that it could not be visually confirmed.
C: Peeling that could not be visually confirmed was observed.
D: Small bubbles or peeling that can be visually confirmed were observed.
E: Clear foaming or peeling was recognized.
　＜粘着力の評価＞
　（１）初期粘着力の測定
　２３℃、５０％ＲＨの標準環境下にて、作製した粘着剤層付偏光フィルムを、縦１２０ｍｍ×横２５ｍｍに裁断したものをサンプルとした。当該サンプルを、厚さ０．７ｍｍの無アルカリガラス板（コーニング社製、ＥＧ－ＸＧ）に、２ｋｇのローラーを１往復させて圧着した後、当該サンプルの粘着力を測定した。粘着力は、当該サンプルを引張り試験機（オートグラフSHIMAZU AG-1 1OKN）にて、剥離角度９０°、剥離速度３００ｍｍ／ｍｉｎで引き剥がす際の粘着力（Ｎ／２５ｍｍ、測定長８０ｍｍ）を測定することにより求めた。測定は、１回／０．５ｓの間隔で２００回サンプリングし、その平均値を測定値とした。検体数は３検体で行った。それらの平均値を初期粘着力として表４の「２ｋｇローラー」の欄に示した。そして粘着力の水準からリワーク性を下記基準で判断した。
　Ａ：４Ｎ／２５ｍｍ以下、リワークは９０％成功する。
　Ｂ：４Ｎ／２５ｍｍ超５Ｎ／２５ｍｍ以下、リワークは８０％以上成功する。
　Ｃ：５Ｎ／２５ｍｍ超６Ｎ／２５ｍｍ以下、リワークは７０％以上成功する。
　Ｄ：６Ｎ／２５ｍｍ超７Ｎ／２５ｍｍ以下、リワークは６０％以上成功する。
　Ｅ：７Ｎ／２５ｍｍ超、リワークは４０％より多く失敗する。 <Evaluation of adhesive strength>
(1) Measurement of initial adhesive strength A polarizing film with an adhesive layer produced was cut into a sample having a length of 120 mm and a width of 25 mm under a standard environment of 23° C. and 50% RH as a sample. The sample was pressure-bonded to a 0.7 mm-thick non-alkali glass plate (EG-XG, manufactured by Corning Inc.) by reciprocating a 2 kg roller once, and then the adhesive force of the sample was measured. The adhesive force is measured by a tensile tester (Autograph SHIMAZU AG-1 1OKN) at a peeling angle of 90° and a peeling speed of 300 mm/min. (N/25 mm, measuring length 80 mm) Was obtained by doing. The measurement was performed 200 times at intervals of 1 time/0.5 s, and the average value was used as the measured value. The number of samples was three. The average value thereof is shown in the column of "2 kg roller" in Table 4 as the initial adhesive strength. Then, the reworkability was judged based on the level of adhesive strength according to the following criteria.
A: 4 N/25 mm or less, rework is 90% successful.
B: More than 4 N/25 mm and 5 N/25 mm or less, and rework succeeds 80% or more.
C: More than 5N/25mm and 6N/25mm or less, and rework succeeds 70% or more.
D: More than 6 N/25 mm and 7 N/25 mm or less, and rework succeeds 60% or more.
E: Over 7 N/25 mm, rework fails more than 40%.
　（２）加熱後粘着力の測定
　作製した粘着剤層付偏光フィルムを、縦１２０ｍｍ×横２５ｍｍに裁断したものをサンプルとした。当該サンプルを、厚さ０．７ｍｍの無アルカリガラス板（コーニング社製、ＥＧ－ＸＧ）に、ラミネーターを用いて貼り付け、次いで５０℃、５ａｔｍで１５分間オートクレーブ処理して完全に密着させた後、当該サンプルの粘着力を測定した。粘着力は、当該サンプルを引張り試験機（オートグラフSHIMAZU AG-1 1OKN）にて、剥離角度９０°、剥離速度３００ｍｍ／ｍｉｎで引き剥がす際の粘着力（Ｎ／２５ｍｍ、測定長８０ｍｍ）を測定することにより求めた。測定は、１回／０．５ｓの間隔で２００回サンプリングし、その平均値を測定値とした。検体数は３検体で行った。表４中、「６０℃×２ｈ」および「６０℃×２４ｈ」は、６０℃でそれぞれ２時間および２４時間放置した後の粘着力を示す。 (2) Measurement of adhesive strength after heating The produced polarizing film with an adhesive layer was cut into a length of 120 mm and a width of 25 mm to obtain a sample. The sample was attached to a 0.7 mm-thick non-alkali glass plate (EG-XG, manufactured by Corning Incorporated) using a laminator, and then autoclaved at 50° C. and 5 atm for 15 minutes for complete adhesion. The adhesive strength of the sample was measured. The adhesive force is measured by a tensile tester (Autograph SHIMAZU AG-1 1OKN) at a peeling angle of 90° and a peeling speed of 300 mm/min. (N/25 mm, measuring length 80 mm) Was obtained by doing. The measurement was performed 200 times at intervals of 1 time/0.5 s, and the average value was used as the measured value. The number of samples was three. In Table 4, “60° C.×2 h” and “60° C.×24 h” indicate the adhesive force after standing at 60° C. for 2 hours and 24 hours, respectively.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　以上の通り、本発明によれば、高耐久性とリワーク性とを兼ね備えた粘着剤層付き偏光フィルムを提供することができる。 As described above, according to the present invention, it is possible to provide a polarizing film with an adhesive layer that has both high durability and reworkability.
　１　　　　　　偏光子
　２、２’　　　保護フィルム
　３　　　　　　偏光フィルム
　４　　　　　　粘着剤層
　５　　　　　　セパレータ
　１０　　　　　粘着剤層付き偏光フィルム 1 Polarizer 2, 2'Protective film 3 Polarizing film 4 Adhesive layer 5 Separator 10 Polarizing film with adhesive layer

Claims (6)

  1. 　偏光フィルムと、
    　粘着剤層とを備える、粘着剤層付き偏光フィルムであって、
    　前記粘着剤層は、ベースポリマーと、シリコーンオリゴマーＰｓとを含み、
    　前記ベースポリマーは、（メタ）アクリル系ポリマーであり、
    　前記シリコーンオリゴマーＰｓは、前記（メタ）アクリル系ポリマー１００重量部に対し、０．１～２０重量部で含まれ、
    　前記シリコーンオリゴマーＰｓは、Ｔｇが－５０℃以上１００℃以下であり、側鎖のシリコーン官能基当量が１０００～２００００ｇ／ｍｏｌであり、重量平均分子量Ｍｗが１００００以上３０００００以下である、粘着剤層付き偏光フィルム。     A polarizing film,
    A polarizing film with an adhesive layer, comprising an adhesive layer,
    The pressure-sensitive adhesive layer includes a base polymer and a silicone oligomer Ps,
    The base polymer is a (meth)acrylic polymer,
    The silicone oligomer Ps is included in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the (meth)acrylic polymer.
    The silicone oligomer Ps has a Tg of −50° C. or higher and 100° C. or lower, a side chain silicone functional group equivalent of 1000 to 20000 g/mol, and a weight average molecular weight Mw of 10,000 or more and 300,000 or less. Polarizing film.
  2. 　前記シリコーンオリゴマーＰｓが、ポリオルガノシロキサン骨格を有するモノマーＳ１と、ホモポリマーのガラス転移温度が－７０℃以上１８０℃以下のモノマーとをモノマー単位として含む、請求項１に記載の粘着剤層付き偏光フィルム。 The polarized light with the pressure-sensitive adhesive layer according to claim 1, wherein the silicone oligomer Ps contains, as a monomer unit, a monomer S1 having a polyorganosiloxane skeleton and a monomer having a homopolymer glass transition temperature of −70° C. or higher and 180° C. or lower. the film.
  3. 　前記ベースポリマーのモノマー単位として、ホモポリマーのガラス転移温度が－８０℃以上０℃以下であるアルキル（メタ）アクリレート（Ａ）を８０重量％以上で含有する、請求項１または２に記載の粘着剤層付き偏光フィルム。 The pressure-sensitive adhesive according to claim 1 or 2, which contains, as a monomer unit of the base polymer, 80% by weight or more of an alkyl (meth)acrylate (A) having a homopolymer glass transition temperature of −80° C. or higher and 0° C. or lower. Polarizing film with agent layer.
  4. 　前記ベースポリマーのモノマー単位として、カルボキシル基含有モノマー（ｂ１）および窒素含有モノマー（ｂ２）からなる群より選択される少なくとも１種の極性モノマー（Ｂ）を０～２０重量％で更に含有する、請求項３に記載の粘着剤層付き偏光フィルム。 The base polymer further comprises, as a monomer unit, at least one polar monomer (B) selected from the group consisting of a carboxyl group-containing monomer (b1) and a nitrogen-containing monomer (b2) in an amount of 0 to 20% by weight. Item 3. A polarizing film with an adhesive layer according to item 3.
  5. 　前記ベースポリマーの重量平均分子量Ｍｗが５０～２５０万である、請求項１～４のいずれか１項に記載の粘着剤層付き偏光フィルム。 The polarizing film with an adhesive layer according to any one of claims 1 to 4, wherein the weight average molecular weight Mw of the base polymer is 500 to 2,500,000.
  6. 　前記シリコーンオリゴマーＰｓの溶融温度が－２０～１２０℃である、請求項１～５のいずれか１項に記載の粘着剤層付き偏光フィルム。 The polarizing film with an adhesive layer according to any one of claims 1 to 5, wherein the melting temperature of the silicone oligomer Ps is -20 to 120°C.
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