WO2015141379A1 - Composition d'adhésif pour plaque de polarisation, feuille adhésive, et plaque de polarisation avec couche adhésive - Google Patents

Composition d'adhésif pour plaque de polarisation, feuille adhésive, et plaque de polarisation avec couche adhésive Download PDF

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Publication number
WO2015141379A1
WO2015141379A1 PCT/JP2015/054774 JP2015054774W WO2015141379A1 WO 2015141379 A1 WO2015141379 A1 WO 2015141379A1 JP 2015054774 W JP2015054774 W JP 2015054774W WO 2015141379 A1 WO2015141379 A1 WO 2015141379A1
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Prior art keywords
sensitive adhesive
pressure
meth
polarizing plate
adhesive composition
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PCT/JP2015/054774
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English (en)
Japanese (ja)
Inventor
佐知 室井
雄太 紺野
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綜研化学株式会社
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Priority to KR1020167025362A priority Critical patent/KR20160135198A/ko
Priority to JP2016508611A priority patent/JPWO2015141379A1/ja
Priority to CN201580013889.XA priority patent/CN106103626A/zh
Publication of WO2015141379A1 publication Critical patent/WO2015141379A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
    • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
    • C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
    • C08G18/8029—Masked aromatic polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • 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
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • 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
    • 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
    • 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
    • G02F2202/00—Materials and properties
    • G02F2202/28—Adhesive materials or arrangements

Definitions

  • the present invention relates to a pressure-sensitive adhesive composition for polarizing plates.
  • the liquid crystal cell has a structure in which a liquid crystal layer is sandwiched between two substrates (eg, a glass plate), and a polarizing plate is attached to the surface of the substrate via an adhesive layer.
  • a polarizing plate is likely to be thermally contracted in a high temperature and high humidity environment, so that it lacks dimensional stability and may cause warpage in a liquid crystal cell.
  • the thinning of liquid crystal cells eg, thinning of the substrate constituting the liquid crystal cell
  • the thinning of the polarizing plate the warpage of the liquid crystal cell under a high temperature and high humidity environment has become a larger problem.
  • the pressure-sensitive adhesive layer cannot follow the thermal contraction (dimensional change) of the polarizing plate, and the stress relaxation property of the pressure-sensitive adhesive layer is low.
  • Patent Document 1 discloses a method for forming a pressure-sensitive adhesive layer by crosslinking a pressure-sensitive adhesive for an optical film containing a specific (meth) acrylic polymer, a peroxide and an isocyanate compound.
  • a cross-linking method using a thermal decomposition cross-linking reaction with a peroxide and a cross-linking method using a urethane bond formation with an isocyanate-based compound are used in combination, so that stress associated with dimensional change of an optical film can be reduced.
  • high durability can be maintained while maintaining sufficient stress relaxation characteristics.
  • the subject of this invention is the adhesive composition for polarizing plates which can suppress the curvature (bending) of a liquid crystal cell, and can form the adhesive layer excellent in durability,
  • the adhesive formed from the said composition It is providing the adhesive sheet for polarizing plates which has a layer, and the polarizing plate with an adhesive layer which has the said adhesive layer.
  • the present invention includes, for example, the following [1] to [8].
  • [1] (A) Gel permeation chromatography method / multi-angle laser obtained by copolymerizing a monomer component containing an alkyl group (meth) acrylic acid alkyl ester having 4 to 18 carbon atoms and a hydroxyl group-containing monomer
  • a pressure-sensitive adhesive for a polarizing plate comprising a (meth) acrylic copolymer having a degree of branching of 0.55 or less measured by a light scattering detector (GPC-MALS) and
  • GPC-MALS light scattering detector
  • an isocyanate compound Agent composition (B)
  • the weight average molecular weight (Mw) measured by the gel permeation chromatography method (GPC method) of the (meth) acrylic copolymer (A) is 200,000 to 1,500,000, [1] Or the adhesive composition for polarizing plates as described in [2].
  • a pressure-sensitive adhesive sheet for polarizing plates comprising a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition for polarizing plates according to any one of [1] to [6].
  • the adhesive composition for polarizing plates which can suppress the curvature (bending) of a liquid crystal cell and can form the adhesive layer excellent in durability,
  • the adhesive formed from the said composition The adhesive sheet for polarizing plates which has a layer, and the polarizing plate with an adhesive layer which has the said adhesive layer can be provided.
  • the pressure-sensitive adhesive composition for polarizing plates the pressure-sensitive adhesive sheet for polarizing plates, and the polarizing plate with a pressure-sensitive adhesive layer of the present invention will be described.
  • the pressure-sensitive adhesive composition for polarizing plates of the present invention is also simply referred to as “pressure-sensitive adhesive composition”
  • the pressure-sensitive adhesive sheet for polarizing plates of the present invention is also simply referred to as “pressure-sensitive adhesive sheet”.
  • the pressure-sensitive adhesive composition for polarizing plates of the present invention contains a (meth) acrylic copolymer (A) and an isocyanate compound (B).
  • the pressure-sensitive adhesive composition may contain at least one selected from a silane coupling agent (C), an antistatic agent (D), and an organic solvent (E) as necessary.
  • the (meth) acrylic copolymer (A) is a copolymer obtained by copolymerizing a monomer component containing a (meth) acrylic acid alkyl ester having an alkyl group having 4 to 18 carbon atoms and a hydroxyl group-containing monomer. is there.
  • the monomer component of the copolymer (A) include polar group-containing monomers other than hydroxyl group-containing monomers, and other monomers other than these.
  • acrylic and methacryl are collectively referred to as “(meth) acryl”.
  • structural unit derived from a certain monomer a contained in the polymer is also referred to as “monomer a unit”.
  • the (meth) acrylic copolymer (A) has a degree of branching of 0.55 or less, preferably 0 as measured by gel permeation chromatography / multi-angle laser light scattering detector (GPC-MALS). .10 to 0.54, more preferably 0.20 to 0.53, and particularly preferably 0.30 to 0.53. Details of measurement conditions for the degree of branching are described in the examples.
  • the degree of branching is an index indicating a branched polymer when it is 0.55 or less and a linear polymer when it exceeds 0.55.
  • a branched polymer when the degree of branching is small, it indicates that the polymer molecule has many branches and has a high degree of branching, and when the degree of branching is large, the polymer molecule has little branching and low degree of branching. It shows having.
  • the (meth) acrylic copolymer (A) having a degree of branching in the above range (1) is often entangled due to the branched chain between polymer molecules at about room temperature, resulting in the molecular weight of the polymer and the pressure-sensitive adhesive.
  • Adhesive layer with excellent storability such as adhesive properties, processability such as punching out the adhesive layer, and less deformation and protrusion of the adhesive layer, even in designs with a low gel fraction of the layer (2)
  • a high temperature eg, 60 ° C.
  • the entanglement between the polymer molecules is partially relaxed, so that the pressure-sensitive adhesive layer exhibits excellent flexibility, and is excellent in suppressing warping (bending) of the polarizing plate, Due to the remaining entanglement, the pressure-sensitive adhesive layer exhibits excellent durability.
  • the reason why the warpage of the polarizing plate is suppressed is as follows.
  • a case where a glass plate is used as the adherend will be described as an example.
  • the polarizing plate and the glass plate have different heat shrinkage rates, and the polarizing plate usually has a larger heat shrinkage rate (dimensional change) than the glass plate.
  • the pressure-sensitive adhesive layer lacks flexibility under a high-temperature, high-humidity heat environment, the pressure-sensitive adhesive layer cannot follow the dimensional change of the polarizing plate, and the pressure-sensitive adhesive layer cannot relieve stress. Stress concentrates on the glass plate, which causes warpage of the glass plate.
  • the pressure-sensitive adhesive layer formed using the pressure-sensitive adhesive composition of the present invention contains a highly branched polymer, and the above-mentioned entanglement is partially loosened in a high temperature / high humidity environment. Since the agent layer can follow, no stress is generated and no stress is concentrated on the glass plate. Further, the polarizing plate can also be thermally contracted uniformly without anisotropy, and does not induce birefringence of the polarizing plate. As described above, in the present invention, the pressure-sensitive adhesive layer can absorb and relieve the stress accompanying the dimensional change of the polarizing plate, and therefore, no excessive stress (load) is applied to the glass plate. It is presumed that this will lead to suppression of warpage of the plate.
  • the pressure-sensitive adhesive composition of the present invention has the above properties, it is suitable for use in bonding a substrate constituting a liquid crystal cell and a polarizing plate.
  • the thickness of the glass plate constituting the thinned liquid crystal cell is as small as about 0.1 to 1.0 mm, it is suitable for bonding the substrate and the polarizing plate.
  • (Meth) acrylic acid alkyl ester As the (meth) acrylic acid alkyl ester, a (meth) acrylic acid alkyl ester having an alkyl group having 4 to 18 carbon atoms (CH 2 ⁇ CR 1 —COOR 2 ; R 1 is a hydrogen atom or a methyl group, R 2 Is an alkyl group having 4 to 18 carbon atoms), and the alkyl group preferably has 4 to 12 carbon atoms.
  • Examples of the (meth) acrylic acid alkyl ester having 4 to 18 carbon atoms in the alkyl group include, for example, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, Hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undeca (meth) acrylate, Examples include lauryl (meth) acrylate, stearyl (meth) acrylate, and isostearyl (meth) acrylate. These may be used alone or in combination of two or more.
  • the total amount of the alkyl (meth) acrylic acid alkyl ester having 4 to 18 carbon atoms in the alkyl group is good adhesive strength and durability. From the viewpoint of expression, it is preferably 99.8 to 20% by mass, more preferably 99.5 to 30% by mass, and still more preferably 99 to 50% by mass.
  • a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 3 carbon atoms (CH 2 ⁇ CR 3 —COOR 4 ; R 3 is a hydrogen atom or methyl And R 4 is an alkyl group having 1 to 3 carbon atoms).
  • Examples of the (meth) acrylic acid alkyl ester having 1 to 3 carbon atoms in the alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate. . These may be used alone or in combination of two or more.
  • the amount of (meth) acrylic acid alkyl ester having 1 to 3 carbon atoms in the alkyl group is preferably 60% by mass or less, more preferably 50% by mass or less in 100% by mass of the monomer component from the viewpoint of stress relaxation characteristics. More preferably, it is 40 mass% or less.
  • hydroxyl group-containing monomer examples include a hydroxyl group-containing (meth) acrylate, and specific examples include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. And hydroxyalkyl (meth) acrylates such as 6-hydroxyhexyl (meth) acrylate and 8-hydroxyoctyl (meth) acrylate.
  • the number of carbon atoms of the hydroxyalkyl group in the hydroxyalkyl (meth) acrylate is usually 2 to 8, preferably 2 to 6.
  • the hydroxyl group contained in the hydroxyl group-containing monomer functions as a crosslinkable functional group with the isocyanate group contained in the isocyanate compound (B).
  • the amount of the hydroxyl group-containing monomer used is preferably 0.01 to 15% by mass, more preferably 0.05 to 10% by mass, and still more preferably 0.1 to 5% by mass in 100% by mass of the monomer component.
  • the amount of the hydroxyl group-containing monomer is less than or equal to the above upper limit, the crosslink density formed by the (meth) acrylic copolymer (A) and the isocyanate compound (B) does not become too high, and the stress relaxation characteristics are excellent.
  • An adhesive layer is obtained.
  • the amount of the hydroxyl group-containing monomer used is equal to or more than the lower limit, a crosslinked structure is effectively formed, and a pressure-sensitive adhesive layer having an appropriate strength at room temperature can be obtained.
  • the monomer component forming the (meth) acrylic copolymer (A) can further contain a polar group-containing monomer in addition to the monomer.
  • a polar group-containing monomer it is preferable to use a monomer having a polar group (crosslinkable functional group) capable of reacting with the isocyanate group of the isocyanate compound (B).
  • Examples of the polar group-containing monomer include an acid group-containing monomer, an amino group-containing monomer, an amide group-containing monomer, a nitrogen-based heterocyclic ring-containing monomer, and a cyano group-containing monomer.
  • examples of the acid group include a carboxyl group, an acid anhydride group, a phosphoric acid group, and a sulfuric acid group.
  • carboxyl group-containing monomer examples include ⁇ -carboxyethyl (meth) acrylate, 5-carboxypentyl (meth) acrylate, mono (meth) acryloyloxyethyl ester succinate, and ⁇ -carboxypolycaprolactone mono (meth) acrylate.
  • Carboxyl group-containing (meth) acrylates such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, and maleic acid.
  • acid anhydride group-containing monomer examples include maleic anhydride and itaconic anhydride.
  • Examples of the phosphate group-containing monomer include (meth) acrylic monomers having a phosphate group in the side chain, and examples of the sulfate group-containing monomer include (meth) acrylic monomers having a sulfate group in the side chain.
  • Examples of the amino group-containing monomer include amino group-containing (meth) acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate.
  • Examples of the amide group-containing monomer include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, and N-hexyl (meth) acrylamide.
  • Examples of the nitrogen heterocycle-containing monomer include vinyl pyrrolidone, acryloyl morpholine, and vinyl caprolactam.
  • Examples of the cyano group-containing monomer include cyano (meth) acrylate and (meth) acrylonitrile.
  • a polar group containing monomer may be used individually by 1 type, and may use 2 or more types.
  • the total use amount of the polar group-containing monomer in the copolymerization is preferably 20% by mass or less, more preferably 10% by mass or less, in 100% by mass of the monomer component.
  • the acid value of the (meth) acrylic copolymer (A) is preferably 10.0 mgKOH / g or less, more preferably 5.0 mgKOH / g or less.
  • the monomer component that forms the (meth) acrylic copolymer (A) is a range that does not impair the physical properties of the (meth) acrylic copolymer (A).
  • Other (meth) acrylic esters such as mono (meth) acrylates, alicyclic groups or aromatic ring-containing (meth) acrylates can be included.
  • alkoxyalkyl (meth) acrylate examples include methoxymethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl ( And (meth) acrylate, 4-methoxybutyl (meth) acrylate, and 4-ethoxybutyl (meth) acrylate.
  • alkoxypolyalkylene glycol mono (meth) acrylate examples include methoxydiethylene glycol mono (meth) acrylate, methoxydipropylene glycol mono (meth) acrylate, ethoxytriethylene glycol mono (meth) acrylate, ethoxydiethylene glycol mono (meth) acrylate, And methoxytriethylene glycol mono (meth) acrylate.
  • Examples of the alicyclic group or aromatic ring-containing (meth) acrylate include cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and phenyl (meth) acrylate.
  • the total amount of the other (meth) acrylic acid ester used is preferably 60% by mass or less, more preferably 40% by mass or less, in 100% by mass of the monomer component.
  • the physical properties of the (meth) acrylic copolymer (A) are not impaired, for example, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene and octylstyrene.
  • Styrenic monomers such as alkyl styrene, fluoro styrene, chloro styrene, bromo styrene, dibromo styrene, iodinated styrene, nitro styrene, acetyl styrene and methoxy styrene, etc .; copolymerizable monomers such as vinyl acetate can also be used it can.
  • the total amount of the copolymerizable monomer used in the copolymerization is preferably 40% by mass or less, more preferably 20% by mass or less, in 100% by mass of the monomer component.
  • Other monomers may be used alone or in combination of two or more.
  • the (meth) acrylic copolymer (A) is preferably a copolymer obtained by the above copolymerization in the presence of a peroxide polymerization initiator. That is, by using a peroxide polymerization initiator as the polymerization initiator, a copolymer having a degree of branching in the above range tends to be obtained.
  • the (meth) acrylic copolymer (A) can be produced by, for example, a conventionally known polymerization method such as a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, a suspension polymerization method, etc. Legal is preferred. Specifically, a polymerization solvent and a monomer component are charged into a reaction vessel, a polymerization initiator is added in an inert gas atmosphere such as nitrogen gas, and the reaction start temperature is usually 40 to 100 ° C., preferably 50 to 80 ° C. The reaction system is maintained at a temperature of usually 50 to 90 ° C., preferably 70 to 90 ° C., and allowed to react for 4 to 20 hours.
  • a conventionally known polymerization method such as a solution polymerization method, a bulk polymerization method, an emulsion polymerization method, a suspension polymerization method, etc. Legal is preferred.
  • a polymerization solvent and a monomer component are charged into a reaction vessel,
  • a peroxide polymerization initiator for example, Di (2-tert-butylperoxyisopropyl) benzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butylcumyl peroxide, di-tert-hexyl Dialkyl peroxides such as peroxide and di-tert-butyl peroxide (eg, compounds represented by R—O—O—R, wherein each R is independently an alkyl group or an aryl group-substituted alkyl group) A compound represented by R—O—O—A—O—O—R, wherein each R is independently an alkyl group or an aryl group-substituted alkyl group, and A is a divalent hydrocarbon group) ; Diisobutyryl peroxide, di (3,5,5-trimethylhexanoyl) peroxide, dil
  • peroxide-based polymerization initiators peroxyesters are preferred because highly branched (meth) acrylic copolymers are obtained, and peroxide-based polymerization initiation represented by the following formula (1) An agent is more preferable.
  • R A to R F are each independently a hydrogen atom, an alkyl group or an aryl group, and since a highly branched copolymer is obtained, preferably an alkyl group having 1 to 10 carbon atoms, It is a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, still more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably an alkyl group having 1 to 2 carbon atoms.
  • tert-butyl peroxypivalate, tert-hexyl peroxypivalate, tert-butyl peroxyneodecanoate, tert-butyl peroxyneo Heptanoate, tert-butylperoxy-2-ethylhexanoate, and cumylperoxyneodecanoate are preferred, and a highly branched copolymer can be obtained, so that tert-butylperoxypivalate, tert- Hexyl peroxypivalate, tert-butyl peroxyneodecanoate, tert-butyl peroxyneoheptanoate, tert-butyl peroxy-2-ethylhexanoate are particularly preferred.
  • One peroxide polymerization initiator may be used alone, or two or more peroxide polymerization initiators may be used. Moreover, adding a peroxide polymerization initiator a plurality of times during the polymerization is not limited. As a polymerization initiator, an azo initiator may be used together with a peroxide initiator as long as the degree of branching is in the above range.
  • azo initiator examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2- Cyclopropylpropionitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbohydrate) Nitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′- Azobis (N, N'-dimethyleneisobutylamidine), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], 2,2'-azo (Isobutylamide) dihydrate, 4,4′-
  • the peroxide polymerization initiator is usually 0.001 to 5 parts by mass, preferably 0.005 to 3 parts by mass with respect to 100 parts by mass of the monomer component forming the (meth) acrylic copolymer (A). Used in amounts within the range of Moreover, it is preferable not to use an azo initiator, and the amount used is preferably 0.5 parts by mass or less, more preferably 0.2 parts by mass or less, with respect to 100 parts by mass of the peroxide polymerization initiator. More preferably, it is 0 parts by mass. However, use for the purpose of reducing the residual monomer in the latter half of the reaction is not limited. Moreover, you may add suitably a polymerization initiator, a chain transfer agent, a monomer component, and a polymerization solvent during the said polymerization reaction.
  • polymerization solvent used for the solution polymerization examples include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane and n-octane; cyclopentane, Cycloaliphatic hydrocarbons such as cyclohexane, cycloheptane, cyclooctane; ethers such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, dibutyl ether, tetrahydrofuran, dioxane, anisole, phenylethyl ether, diphenyl ether; chloroform, Halogenated hydrocarbons such as carbon tetrachloride, 1,2-dichloroethane, chlorobenzene; esters such as ethyl acetate, propyl acetate, butyl a
  • the activation energy in the reaction R is the gas constant (8.314 J / mol ⁇ K), T is the absolute temperature (K), and t is the reaction time.
  • the frequency factor (A) and the activation energy ( ⁇ E) have been determined.
  • the values described in the NOF Corporation organic peroxide catalog (10th edition) Can be used.
  • ⁇ E 119.1 kJ / mol
  • A 6.93 ⁇ 10 17 hr ⁇ 1
  • A 6.45 ⁇ 10 17 hr ⁇ 1
  • the residual rate (%) of the peroxide polymerization initiator after the reaction for t hours at the predetermined temperature can be calculated according to the above formula. Therefore, the remaining amount of the peroxide-based polymerization initiator contained in the pressure-sensitive adhesive composition can be calculated by the amount of the peroxide-based polymerization initiator used in the copolymerization ⁇ the remaining rate (%).
  • the weight average molecular weight (Mw) measured by the GPC method of the (meth) acrylic copolymer (A) is usually 200,000 to 1,500,000, preferably 400,000 to 1,300,000, more preferably in terms of polystyrene. Is between 500,000 and 1.1 million. Since the copolymer (A) has highly branched chains even when Mw is in the above range, the copolymer (A) chains can be appropriately entangled with each other, and the durability of the pressure-sensitive adhesive layer And workability does not deteriorate. In particular, when the Mw is 400,000 or more, a highly cohesive pressure-sensitive adhesive layer can be obtained.
  • the molecular weight distribution (Mw / Mn) measured by the GPC method of the (meth) acrylic copolymer (A) is usually 50 or less, preferably 30 or less, more preferably 20 or less.
  • the glass transition temperature (Tg) of the (meth) acrylic copolymer (A) can be calculated by, for example, the Fox formula from the monomer units constituting the polymer and the content ratio thereof.
  • the (meth) acrylic copolymer (A) is synthesized so that the glass transition temperature (Tg) determined by the Fox equation is usually ⁇ 70 to 0 ° C., preferably ⁇ 60 to ⁇ 30 ° C. Can do.
  • Tg is a glass transition temperature of the (meth) acrylic copolymer (A)
  • Tg 1 , Tg 2 ,..., Tg m are glass transition temperatures of homopolymers composed of the respective monomers
  • W 1 , W 2 ,..., W m are weight fractions of the structural units derived from the respective monomers in the copolymer (A).
  • glass transition temperature of the homopolymer composed of each monomer in the Fox formula for example, a value described in Polymer Handbook Fourth Edition (Wiley-Interscience 1999) can be used.
  • the content of the (meth) acrylic copolymer (A) in the pressure-sensitive adhesive composition of the present invention is usually 50 to 99.99 in 100% by mass of the solid content excluding the organic solvent (E) in the composition. % By mass, more preferably 60 to 99.95% by mass, particularly preferably 80 to 99.90% by mass. When the content of the (meth) acrylic copolymer (A) is in the above range, the performance as an adhesive is balanced and the adhesive properties are excellent.
  • isocyanate compound (B) As the isocyanate compound (B), an isocyanate compound having two or more isocyanate groups in one molecule is usually used.
  • a crosslinked body (network polymer) can be formed by crosslinking the (meth) acrylic copolymer (A) with the isocyanate compound (B).
  • the number of isocyanate groups in the isocyanate compound (B) is usually 2 or more, preferably 2 to 8, and more preferably 3 to 6. When the number of isocyanate groups is within the above range, it is preferable from the viewpoint of the crosslinking reaction efficiency between the (meth) acrylic copolymer (A) and the isocyanate compound (B) and the flexibility of the pressure-sensitive adhesive layer.
  • diisocyanate compound having 2 isocyanate groups in one molecule examples include aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate.
  • Aliphatic diisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, 2,2,4-trimethyl
  • aliphatic diisocyanates having 4 to 30 carbon atoms such as -1,6-hexamethylene diisocyanate.
  • alicyclic diisocyanates examples include alicyclic rings having 7 to 30 carbon atoms such as isophorone diisocyanate, cyclopentyl diisocyanate, cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated tetramethylxylylene diisocyanate.
  • Group diisocyanates examples include alicyclic rings having 7 to 30 carbon atoms such as isophorone diisocyanate, cyclopentyl diisocyanate, cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated tetramethylxylylene diisocyanate.
  • aromatic diisocyanate examples include aromatic diisocyanates having 8 to 30 carbon atoms such as phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, diphenyl ether diisocyanate, diphenylmethane diisocyanate, and diphenylpropane diisocyanate.
  • isocyanate compound having 3 or more isocyanate groups in one molecule examples include aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate. Specific examples include 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, and 4,4 ', 4 "-triphenylmethane triisocyanate.
  • isocyanate compound (B) examples include multimers (for example, dimers or trimers, biurets, isocyanurates), derivatives (for example, many) of the above isocyanate compounds having 2 or 3 or more isocyanate groups. Addition reaction product of a dihydric alcohol and two or more molecules of a diisocyanate compound), and a polymer.
  • polyhydric alcohol in the derivative examples include trivalent or higher alcohols such as trimethylolpropane, glycerin and pentaerythritol as low molecular weight polyhydric alcohols; high molecular weight polyhydric alcohols such as polyether polyols, Examples include polyester polyol, acrylic polyol, polybutadiene polyol, and polyisoprene polyol.
  • isocyanate compounds include diphenylmethane diisocyanate trimer, polymethylene polyphenyl polyisocyanate, hexamethylene diisocyanate or tolylene diisocyanate biuret or isocyanurate, trimethylolpropane and tolylene diisocyanate or xylylene diisocyanate.
  • Reaction product for example, a trimolecular adduct of tolylene diisocyanate or xylylene diisocyanate
  • reaction product of trimethylolpropane and hexamethylene diisocyanate for example, a trimolecular adduct of hexamethylene diisocyanate
  • polyether polyisocyanate for example, a polyether polyisocyanate
  • Polyester polyisocyanate is mentioned.
  • isocyanate compounds (B) a reaction product of trimethylolpropane and tolylene diisocyanate or xylylene diisocyanate (L-45, Soken Chemical Co., Ltd., Soken Chemical Co., Ltd.) can be improved in aging properties and light leakage performance.
  • TD-75 manufactured by KK isocyanurate of hexamethylene diisocyanate or tolylene diisocyanate (TSE-100 manufactured by Asahi Kasei Kogyo Co., Ltd., 2050 manufactured by Nippon Polyurethane Co., Ltd.).
  • An isocyanate compound (B) may be used individually by 1 type, and may use 2 or more types.
  • the content of the isocyanate compound (B) is usually 0.01 to 5 parts by mass, more preferably 0, relative to 100 parts by mass of the (meth) acrylic copolymer (A). 0.05 to 2.5 parts by mass, more preferably 0.1 to 1 part by mass. When the content is within the above range, it is preferable in terms of easy balance between durability and stress relaxation characteristics.
  • the pressure-sensitive adhesive composition for polarizing plates of the present invention preferably further contains a silane coupling agent (C).
  • a silane coupling agent (C) contributes to the point which adheres an adhesive layer firmly to adherends, such as a glass plate, and prevents peeling in a high-humidity heat environment.
  • silane coupling agent (C) examples include polymerizable unsaturated group-containing silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, and methacryloxypropyltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane Epoxy groups such as 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Containing silane coupling agent; amino such as 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane Group-containing silane coupling Grayed
  • the content of the silane coupling agent (C) in the pressure-sensitive adhesive composition for polarizing plates of the present invention is usually 1 part by mass or less, preferably 0 with respect to 100 parts by mass of the (meth) acrylic copolymer (A). 0.01 to 1 part by mass, more preferably 0.05 to 0.5 part by mass. When the content is in the above range, peeling of the polarizing plate in a high humidity environment and bleeding of the silane coupling agent (C) in a high temperature environment tend to be prevented.
  • An antistatic agent (D) can be used in order to reduce the surface resistance value of the adhesive composition for polarizing plates of this invention, for example.
  • examples of the antistatic agent (D) include a surfactant, an ionic compound, and a conductive polymer.
  • surfactant examples include cationic surfactants having cationic groups such as quaternary ammonium salts, amide quaternary ammonium salts, pyridium salts, primary to tertiary amino groups; sulfonate groups, sulfate esters Anionic surfactants having an anionic group such as a base or a phosphate ester base; amphoteric surfactants such as alkylbetaines, alkylimidazolinium betaines, alkylamine oxides, amino acid sulfates, glycerin fatty acid esters
  • Nonionic surfactants such as sorbitan fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene alkylamine fatty acid esters, N-hydroxyethyl-N-2-hydroxyalkylamines and alkyldiethanolamides It is done.
  • a reactive emulsifier having a polymerizable group is also exemplified as the surfactant, and a polymer surfactant obtained by increasing the molecular weight of the monomer component containing the above surfactant or reactive emulsifier can also be used.
  • the ionic compound is composed of a cation part and an anion part, and may be either solid or liquid at room temperature (23 ° C./50% RH).
  • the cation portion constituting the ionic compound may be either an inorganic cation or an organic cation, or both.
  • the inorganic cation alkali metal ions and alkaline earth metal ions are preferable, and Li + , Na + and K + having excellent antistatic properties are more preferable.
  • organic cation examples include pyridinium cation, piperidinium cation, pyrrolidinium cation, pyrroline cation, pyrrole cation, imidazolium cation, tetrahydropyrimidinium cation, dihydropyrimidinium cation, pyrazolium cation, and pyrazolinium.
  • examples include cations, tetraalkylammonium cations, trialkylsulfonium cations, tetraalkylphosphonium cations, and derivatives thereof.
  • the anion moiety constituting the ionic compound is not particularly limited as long as it can form an ionic compound by ionic bonding with the cation moiety.
  • Examples of the ionic compound include lithium bis (trifluoromethanesulfonyl) imide, lithium bis (difluorosulfonyl) imide, lithium tris (trifluoromethanesulfonyl) methane, potassium bis (trifluoromethanesulfonyl) imide, potassium bis (difluorosulfonyl) imide, 1 -Ethylpyridinium hexafluorophosphate, 1-butylpyridinium hexafluorophosphate, 1-hexyl-4-methylpyridinium hexafluorophosphate, 1-octyl-4-methylpyridinium hexafluorophosphate, 1-octyl-4-methylpyridinium bis (fluoro Sulfonyl) imide, 1-octyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imide, (N, N-die) -N
  • the conductive polymer examples include polythiophene, polyaniline, polypyrrole, and derivatives thereof.
  • the content of the antistatic agent (D) in the pressure-sensitive adhesive composition for polarizing plates of the present invention is usually 3 parts by mass or less, preferably 0.8 parts per 100 parts by mass of the (meth) acrylic copolymer (A). The amount is from 01 to 3 parts by mass, more preferably from 0.05 to 2.5 parts by mass.
  • the pressure-sensitive adhesive composition of the present invention preferably contains an organic solvent (E) in order to adjust its coatability.
  • an organic solvent the polymerization solvent demonstrated in the column of the (meth) acrylic-type copolymer (A) is mentioned.
  • the pressure-sensitive adhesive composition can be prepared by mixing the polymer solution containing the (meth) acrylic copolymer (A) and the polymerization solvent obtained by the above copolymerization and the isocyanate compound (B). it can.
  • the content of the organic solvent is usually 50 to 90% by mass, preferably 60 to 85% by mass.
  • solid content refers to all components excluding the organic solvent (E) among the components contained in the pressure-sensitive adhesive composition
  • solid content concentration refers to the pressure-sensitive adhesive composition 100. The ratio of the said solid content with respect to the mass% is said.
  • the pressure-sensitive adhesive composition of the present invention does not contain a peroxide (peroxide-based crosslinking agent) as a crosslinking agent.
  • the peroxide content including the remaining amount of the peroxide polymerization initiator used during the synthesis of the (meth) acrylic copolymer (A), is (meth) acrylic copolymer (A) 100.
  • it is 0.1 mass part or less with respect to a mass part, More preferably, it is 0.05 mass part or less, More preferably, it is 0.01 mass part or less.
  • the pressure-sensitive adhesive composition of the present invention includes an antioxidant, a light stabilizer, a metal corrosion inhibitor, a tackifier, a plasticizer, a crosslinking accelerator, You may contain the 1 type (s) or 2 or more types selected from the (meth) acrylic-type polymer and rework agents other than A).
  • the pressure-sensitive adhesive composition for polarizing plates of the present invention is obtained by mixing a (meth) acrylic copolymer (A), an isocyanate compound (B), and other components as required, by a conventionally known method. Can be prepared. For example, an isocyanate compound (B) and, if necessary, other components may be blended in the polymer solution containing the polymer obtained when the (meth) acrylic copolymer (A) is synthesized. It is done.
  • the gel fraction of the pressure-sensitive adhesive formed from the pressure-sensitive adhesive composition of the present invention is preferably 20 to 70% by mass, more preferably 24 to 60% by mass, and further preferably 30 to 55% by mass.
  • the said gel fraction is a value measured about the adhesive extract
  • the pressure-sensitive adhesive layer of the present invention specifically crosslinks the (meth) acrylic copolymer (A) with the isocyanate compound (B) by, for example, advancing the crosslinking reaction in the above-mentioned pressure-sensitive adhesive composition. Is obtained.
  • the conditions for forming the pressure-sensitive adhesive layer are, for example, as follows.
  • the pressure-sensitive adhesive composition of the present invention is applied on a support and varies depending on the type of solvent, but is usually 50 to 150 ° C., preferably 60 to 100 ° C., usually 1 to 10 minutes, preferably 2 to 7 minutes. Then, the solvent is removed and a coating film is formed.
  • the film thickness of the dried coating film is usually 5 to 75 ⁇ m, preferably 10 to 50 ⁇ m.
  • the pressure-sensitive adhesive layer is preferably formed under the following conditions. After applying the pressure-sensitive adhesive composition of the present invention on a support and applying a cover film on the coating film formed under the above conditions, usually 3 days or more, preferably 7 to 10 days, usually 5 to 60 ° C., It is preferably cured in an environment of 15 to 40 ° C., usually 30 to 70% RH, preferably 40 to 70% RH. When crosslinking is performed under the aging conditions as described above, a crosslinked body (network polymer) can be efficiently formed.
  • a predetermined thickness is obtained by a known method such as spin coating, knife coating, roll coating, bar coating, blade coating, die coating, or gravure coating.
  • a method of applying and drying can be used.
  • polyester films such as polyethylene terephthalate (PET); plastic films such as polyolefin films such as polyethylene, polypropylene, and ethylene-vinyl acetate copolymer.
  • PET polyethylene terephthalate
  • plastic films such as polyolefin films such as polyethylene, polypropylene, and ethylene-vinyl acetate copolymer.
  • the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention preferably has a gel fraction of 20 to 70% by mass, more preferably from the viewpoints of distortion suppression, cohesive strength, adhesive strength, and removability of the polarizing plate. Is 24 to 60% by mass, more preferably 30 to 55% by mass. Even if the gel fraction is in the above range, the (meth) acrylic copolymer (A) has highly branched chains, so that the branched chains of the copolymer (A) may be appropriately entangled with each other. The durability and workability of the pressure-sensitive adhesive layer are not deteriorated. In particular, when the gel fraction is 30% by mass or more, a highly cohesive pressure-sensitive adhesive layer is obtained. When the gel fraction exceeds the above range, the pressure-sensitive adhesive layer may not be able to sufficiently absorb or relax the stress caused by the dimensional change of the polarizing plate under a high temperature / high humidity heat environment.
  • the pressure-sensitive adhesive sheet for polarizing plates of the present invention has a pressure-sensitive adhesive layer formed from the above-mentioned pressure-sensitive adhesive composition for polarizing plates.
  • the pressure-sensitive adhesive sheet include a double-sided pressure-sensitive adhesive sheet having only the pressure-sensitive adhesive layer, a base material, and a double-sided pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer formed on both surfaces of the base material, the base material, and one of the base materials.
  • Examples thereof include a single-sided pressure-sensitive adhesive sheet having the above-mentioned pressure-sensitive adhesive layer formed on the surface, and a pressure-sensitive adhesive sheet having a peel-treated cover film attached to the surface of the pressure-sensitive adhesive sheet that is not in contact with the base material.
  • polyester films such as polyethylene terephthalate (PET); plastic films such as polyolefin films such as polyethylene, polypropylene, and ethylene-vinyl acetate copolymer.
  • PET polyethylene terephthalate
  • plastic films such as polyolefin films such as polyethylene, polypropylene, and ethylene-vinyl acetate copolymer.
  • the conditions for forming the pressure-sensitive adhesive layer are the same as the conditions described in the [Pressure-sensitive adhesive layer] column.
  • the thickness of the pressure-sensitive adhesive layer is usually 5 to 75 ⁇ m, preferably 10 to 50 ⁇ m, from the viewpoint of maintaining adhesive performance.
  • the film thickness of the substrate and the cover film is not particularly limited, but is usually 10 to 125 ⁇ m, preferably 25 to 75 ⁇ m.
  • the polarizing plate with a pressure-sensitive adhesive layer of the present invention comprises a polarizing plate and a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition for a polarizing plate of the present invention on at least one surface of the polarizing plate.
  • polarizing plate is used to include “polarizing film”.
  • a conventionally known polarizing film can be used as the polarizing plate.
  • a multilayer film having a stretched film obtained by adding a polarizing component to a film made of a polyvinyl alcohol-based resin and stretching, and a protective film disposed on the stretched film can be mentioned.
  • the polyvinyl alcohol-based resin include polyvinyl alcohol, polyvinyl formal, polyvinyl acetal, and a saponified product of an ethylene / vinyl acetate copolymer.
  • the polarization component include iodine or a dichroic dye.
  • the protective film include cellulose films such as triacetyl cellulose, polycarbonate films, and polyethersulfone films.
  • the thickness of the polarizing plate is usually 30 to 250 ⁇ m, preferably 50 to 200 ⁇ m.
  • the adhesive sheet for polarizing plates of this invention has A method of transferring the pressure-sensitive adhesive layer to the surface of the polarizing plate and aging is mentioned.
  • the conditions for drying and aging, the range of the gel fraction, and the like are the same as the conditions described in the [Adhesive layer] column.
  • the thickness of the pressure-sensitive adhesive layer formed on the polarizing plate is usually 5 to 75 ⁇ m, preferably 10 to 50 ⁇ m in terms of dry film thickness.
  • the adhesive layer should just be formed in at least one surface of a polarizing plate, the aspect in which an adhesive layer is formed only in the single side
  • the layer which has other functions such as a protective layer, a glare-proof layer, a phase difference layer, a viewing angle improvement layer, for example may be laminated
  • a liquid crystal element is produced by providing the polarizing plate with the pressure-sensitive adhesive layer of the present invention obtained as described above on the substrate surface of the liquid crystal cell.
  • the liquid crystal cell has a structure in which a liquid crystal layer is sandwiched between two substrates.
  • the substrate of the liquid crystal cell examples include a glass plate.
  • the thickness of the substrate is usually 0.1 to 1 mm, preferably 0.15 to 0.8 mm.
  • substrate can be suppressed by using the said adhesive composition. Therefore, even when the thickness of the substrate is small (eg, 0.8 mm or less, preferably 0.15 to 0.7 mm), the above-mentioned pressure-sensitive adhesive composition is suitably used for bonding the polarizing plate and the substrate. be able to.
  • GPC and GPC-MALS For the (meth) acrylic copolymer, the gel permeation chromatography method (GPC method) is used to determine the weight average molecular weight (Mw) and the number average molecular weight (Mn) under the following conditions. The degree of branching was determined using a laser light scattering detector (GPC-MALS) under the following conditions.
  • HLC-8320GPC manufactured by Tosoh Corporation
  • -GPC column configuration The following four columns (all manufactured by Tosoh Corporation) (1) TSKgel HxL-H (guard column) (2) TSKgel GMHxL (3) TSKgel GMHxL (4) TSKgel G2500HxL ⁇ Flow rate: 1.0 mL / min -Column temperature: 40 ° C Sample concentration: 1.5% (w / v) (diluted with tetrahydrofuran) ⁇ Mobile phase solvent: Tetrahydrofuran ⁇ Detector: DAWN HELEOS (MALS detector) + Optilab rEX (RI detector) ⁇ Standard polystyrene conversion (when measuring Mw and Mn)
  • the obtained (meth) acrylic copolymer A has a weight average molecular weight (Mw) of 400,000, a molecular weight distribution (Mw / Mn) of 7.2, a degree of branching of 0.52, and an acid value.
  • Mw weight average molecular weight
  • Mw / Mn molecular weight distribution
  • degree of branching 0.52
  • an acid value 0 mg KOH / g.
  • Example 1 (1) Preparation of pressure-sensitive adhesive composition (meth) acrylic polymer solution obtained in Synthesis Example 1 (solid content concentration: 30% by mass) and 100 parts (meth) acrylic polymer contained in the solution (solid content) In contrast, 0.19 parts (solid content) of “TD-75” (solid content: 75 mass%, ethyl acetate solution) manufactured by Soken Chemical Co., Ltd. as an isocyanate compound, and Shin-Etsu Chemical Co., Ltd. as a silane coupling agent "KBM-403" (solid content 100%) 0.2 parts made by Daiichi Kogyo Seiyaku Co., Ltd. "AS-804" (solid content 100%) 1 part was mixed as an antistatic agent An agent composition was obtained.
  • the pressure-sensitive adhesive composition obtained in (1) above was applied onto a polyethylene terephthalate film (PET film) subjected to a release treatment using a doctor blade, It dried at 90 degreeC for 3 minute (s), and obtained the sheet
  • the sheet and the polarizing plate (thickness: 110 ⁇ m, layer structure: triacetyl cellulose film / polyvinyl alcohol film / triacetyl cellulose film) were bonded together so that the coating film and the polarizing plate were in contact with each other, and 23 ° C./50%.
  • the plate was allowed to stand and matured for 7 days under the conditions of RH to obtain a polarizing plate with a pressure-sensitive adhesive layer having a PET film, a pressure-sensitive adhesive layer having a thickness of 20 ⁇ m, and a polarizing plate.
  • Example 1 [Examples 2 to 9, Comparative Example 1]
  • the (meth) acrylic polymer solution was changed to the polymer solution obtained in Synthesis Examples 2 to 10 and the composition was changed as described in Table 2 in the same manner as in Example 1. Then, a pressure-sensitive adhesive composition, a pressure-sensitive adhesive sheet and a polarizing plate with a pressure-sensitive adhesive layer were obtained.
  • the polarizing plate with a pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was cut into a width of 10 mm and a length of 100 mm, and the peeled PET film was peeled off. And it bonded together so that the said adhesive layer might contact the said glass plate and it might become a bonding area of 10 mm x 10 mm on the alkali treatment glass plate, and the adhesion processing polarizing plate test piece for evaluation was obtained.
  • the adhesion processing polarizing plate test piece for evaluation, it autoclaved (50 degreeC, 5 atm), and left still for 24 hours in 23 degreeC / 50% RH atmosphere.
  • the test piece was set in a chamber BOX of a minute creep measuring machine with a fixing chuck portion having a length of 15 mm.
  • the evaluation-treated pressure-sensitive adhesive polarizing plate in the test piece was pulled in parallel with the adhesive surface between the polarizing plate and the glass and in the length direction of the polarizing plate.
  • the distance ( ⁇ m) of the misalignment between the glass plate and the polarizing plate in the piece was measured as a creep value.
  • a polarizing plate with a pressure-sensitive adhesive layer obtained in Examples and Comparative Examples (a laminate comprising PET film / pressure-sensitive adhesive layer / polarizing plate) was cut into a size of 70 mm ⁇ 25 mm to prepare a test piece.
  • the PET film was peeled from the test piece, and a laminate composed of the pressure-sensitive adhesive layer / polarizing plate was attached to one side of a 2 mm thick glass plate so that the pressure-sensitive adhesive layer and the glass plate were in contact with each other using a laminator roll. .
  • the obtained laminate was held in an autoclave adjusted to 50 ° C./5 atm for 20 minutes.
  • the end of the polarizing plate was pulled at a rate of 300 mm / min in the 90 ° direction with respect to the glass plate surface, and the adhesive strength (peel strength) was measured.
  • a test piece was prepared by cutting the polarizing plate with the pressure-sensitive adhesive layer (PET film / pressure-sensitive adhesive layer / laminate comprising the polarizing plate) obtained in Examples and Comparative Examples into a size of 35 mm ⁇ 400 mm (stretching axis direction). did.
  • the PET film is peeled off from the test piece, and the laminate composed of the pressure-sensitive adhesive layer / polarizing plate is laminated on one side of a glass plate having a thickness of 0.7 mm and 40 mm ⁇ 410 mm using a laminator roll. Affixed to touch.
  • the obtained laminate was allowed to stand in a 23 ° C./50% RH environment for 24 hours, and then held in an oven at 60 ° C. for 72 hours. One end was fixed to a wall surface perpendicular to the floor surface, and the amount of lifting at the opposite end was measured with a ruler. Measurements were taken immediately after removal from the oven and after 24 hours.
  • a polarizing plate with a pressure-sensitive adhesive layer obtained in Examples and Comparative Examples (a laminate comprising PET film / pressure-sensitive adhesive layer / polarizing plate) was cut into a size of 150 mm ⁇ 250 mm to prepare a test piece.
  • the PET film was peeled from the test piece, and a laminate composed of the pressure-sensitive adhesive layer / polarizing plate was attached to one side of a 2 mm thick glass plate so that the pressure-sensitive adhesive layer and the glass plate were in contact with each other using a laminator roll. .
  • the obtained laminate was held in an autoclave adjusted to 50 ° C./5 atm for 20 minutes to prepare a test plate. Two similar test plates were prepared.
  • test plate is allowed to stand for 500 hours under conditions of a temperature of 80 ° C. (heat resistance) or a temperature of 60 ° C./humidity of 90% RH (humid heat resistance), and the occurrence of foaming and tearing is observed according to the following criteria. evaluated. Foaming occurs when cohesion is insufficient, and tearing occurs when stress relaxation is insufficient.
  • (Foam) -AA Foaming is not seen at all.
  • -BB The area of foaming is less than 1% of the whole.
  • -CC The area of foaming is 1% or more and less than 5% of the whole.
  • -DD The area of foaming is 5% or more of the whole.
  • (Rupture) -AA No tear is seen at all.
  • -BB The area of a tear is less than 1% of the whole.
  • -CC The area of a fracture is 1% or more and less than 5% of the whole.
  • DD The area of the tear is 5% or more of the whole.
  • Comparative Example 1 since a (meth) acrylic copolymer having a branching degree of 0.59 is used, the bending evaluation after 24 hours is poor (5.0 mm or more), and foaming is recognized in the durability evaluation. Although it was not, many tears occurred. Since the copolymer in Comparative Example 1 is a linear polymer, the expression of cohesive force depends only on the bond between the crosslinking agent and the functional group in the copolymer. Therefore, it is necessary to set the gel fraction high in order to maintain the cohesive force. However, when the gel fraction is high, the stress relaxation characteristics are lowered in the system of Comparative Example 1, and thus bending and durability (breaking resistance) are deteriorated.

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Abstract

L'invention fournit une composition d'adhésif pour plaque de polarisation permettant d'empêcher le gauchissement (pliage) d'une cellule de cristaux liquides, et permettant de former une couche adhésive d'une excellente durabilité. Cette composition d'adhésif pour plaque de polarisation est caractéristique en ce qu'elle comprend : (A) un copolymère (méth)acrylique qui est obtenu par copolymérisation d'un ester alkylique d'acide (méth)acrylique dont le nombre d'atomes de carbone d'un groupe alkyle est compris entre 4 et 18, et d'un composant monomère contenant un monomère comprenant un groupe hydroxyle, et qui présente un degré de ramification mesuré par un procédé de chromatographie par perméation de gel (GPC) à l'aide d'un détecteur de diffusion de la lumière multi-angles (MALS), inférieur ou égal à 0,55 ; et (B) un composé isocyanate.
PCT/JP2015/054774 2014-03-18 2015-02-20 Composition d'adhésif pour plaque de polarisation, feuille adhésive, et plaque de polarisation avec couche adhésive WO2015141379A1 (fr)

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KR1020167025362A KR20160135198A (ko) 2014-03-18 2015-02-20 편광판용 점착제 조성물, 점착 시트 및 점착제층 부착 편광판
JP2016508611A JPWO2015141379A1 (ja) 2014-03-18 2015-02-20 偏光板用粘着剤組成物、粘着シートおよび粘着剤層付き偏光板
CN201580013889.XA CN106103626A (zh) 2014-03-18 2015-02-20 偏振片用粘合剂组合物、粘合片以及带粘合剂层的偏振片

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KR20230026238A (ko) 2020-06-30 2023-02-24 토요잉크Sc홀딩스주식회사 점착제, 및 점착 시트

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JP7070981B2 (ja) * 2018-09-14 2022-05-18 日本カーバイド工業株式会社 偏光板用粘着剤組成物及び粘着剤層付偏光板
JP7270366B2 (ja) * 2018-11-26 2023-05-10 日東電工株式会社 偏光板のセット

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JP2017193601A (ja) * 2016-04-18 2017-10-26 綜研化学株式会社 光硬化型粘着剤前駆体組成物、光硬化型粘着剤、及び光硬化型粘着剤の製造方法
KR20230026238A (ko) 2020-06-30 2023-02-24 토요잉크Sc홀딩스주식회사 점착제, 및 점착 시트

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