WO2022145369A1 - 偏光板 - Google Patents
偏光板 Download PDFInfo
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- WO2022145369A1 WO2022145369A1 PCT/JP2021/048234 JP2021048234W WO2022145369A1 WO 2022145369 A1 WO2022145369 A1 WO 2022145369A1 JP 2021048234 W JP2021048234 W JP 2021048234W WO 2022145369 A1 WO2022145369 A1 WO 2022145369A1
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- WIPO (PCT)
- Prior art keywords
- cationic polymerization
- polarizing plate
- protective film
- adhesive
- film
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- Legal status (The legal status 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 status listed.)
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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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
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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]
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
Definitions
- the present invention relates to a polarizing plate in which a protective film is bonded to both sides of a polarizing film via an adhesive layer.
- a polarizing plate widely used in an image display device represented by a liquid crystal display device usually has a structure in which a protective film is laminated on both sides of a polarizing film.
- An adhesive is usually used for bonding the polarizing film and the protective film.
- a water-based adhesive and an active energy ray-curable adhesive are known.
- Patent Document 1 describes (A) a compound containing an ester group and having two or more alicyclic epoxy groups in the molecule, (B) a fluoroalkylfluorophosphate anion or a penta.
- a polarizing plate made of an ester is described.
- a polarizing plate is manufactured as a long object (polarizing plate roll) by a roll-to-roll method, and then cut into a polarizing plate sheet having a size corresponding to, for example, the screen size of an applied image display device. It is incorporated into an image display device by being attached to an image display element.
- the polarizing plate may be stored or transported for a certain period after being cut into a single-wafer body and before being incorporated into an image display device. In this case, the storage / transportation environment is relatively high humidity. May become. Polarized-plate single-wafers exposed to high-humidity environments are prone to curl.
- An object of the present invention is to provide a polarizing plate in which protective films are bonded to both sides of a polarizing film, which is less likely to cause curl or has a small degree of curl even when placed in a high humidity environment. be.
- the present invention provides the following polarizing plates.
- a polarizing plate containing a first protective film, a first adhesive layer, a polarizing film, a second adhesive layer, and a second protective film in this order.
- the first adhesive layer is a cured product layer of the first cationic polymerization type adhesive containing one or more kinds of cationic polymerization initiators.
- the second adhesive layer is a cured product layer of a second cationic polymerization type adhesive containing one or more kinds of cationic polymerization initiators.
- the one or more kinds of cationic polymerization initiators contained in the first cationic polymerization type adhesive include the first cationic polymerization initiator.
- the first cationic polymerization initiator has a cationic component and the following formula (i):
- Y indicates an aryl group having 6 to 30 carbon atoms or a heterocyclic group having 4 to 30 carbon atoms, or a halogen atom, which may have a substituent (excluding a group containing a halogen atom).
- Phf represents a phenyl group in which at least one of the hydrogen atoms is substituted with at least one selected from a perfluoroalkyl group, a perfluoroalkoxy group, and a halogen atom.
- K is an integer of 0 to 4. be.
- It is a borate salt composed of an anion component represented by.
- a polarizing plate having a molecular weight of the first cationic polymerization initiator larger than the molecular weight of one or more kinds of cationic polymerization initiators contained in the second cationic polymerization type adhesive [2] The polarizing plate according to [1], wherein the cation component is an aryl sulfonium ion. [3] The first cationically polymerizable adhesive and the second cationically polymerizable adhesive further contain a cationically polymerizable compound.
- the content of the one or more cationic polymerization initiators contained in the first cationic polymerization type adhesive and the content of the one or more kinds of cationic polymerization initiators contained in the second cationic polymerization type adhesive are as described above.
- a polarizing plate in which protective films are bonded to both sides of a polarizing film, which is less likely to cause curl or has a small degree of curl even when placed in a high humidity environment.
- polarizing plate according to the present invention (hereinafter, also simply referred to as “polarizing plate”) will be described in detail.
- the polarizing plate includes a first protective film 10, a first adhesive layer 15, a polarizing film 30, a second adhesive layer 25, and a second protective film 20. Include in order. That is, the first protective film 10 is laminated on one surface of the polarizing film 30 via the first adhesive layer 15, and the second protective film 20 is laminated on one surface of the polarizing film 30 via the second adhesive layer 25. It is laminated on.
- the first adhesive layer 15 is preferably in contact with the first protective film 10 and the polarizing film 30.
- the second adhesive layer 25 is preferably in contact with the polarizing film 30 and the second protective film 20.
- the polarizing plate can include layers other than the above.
- other layers include, for example, a pressure-sensitive adhesive layer laminated on the outer surface of the first protective film 10 and / or the second protective film 20; a separate film laminated on the outer surface of the pressure-sensitive adhesive layer (“peeling). Also referred to as "film”); a protective film laminated on the outer surface of the first protective film 10 and / or the second protective film 20 (also referred to as "surface protective film”); first protective film 10 and / or second protective.
- the polarizing plate according to the present invention may be less likely to cause curl or have a small degree of curl even when placed in a high humidity environment.
- the difficulty of curling is also referred to as “curl resistance”
- the difficulty of curling or the small degree of curling is also referred to as “good curl resistance”.
- the polarizing plate may be a long object of the polarizing plate having the above-mentioned layer structure, a winding roll thereof, or a single-wafered body.
- the single-wafer body refers to a long object or a body cut out from the winding roll to a predetermined size, and usually has a rectangular shape such as a rectangle or a square.
- the curl resistance means the curl resistance of the long object or the single-wafer cut from the winding roll.
- the curl resistance means the curl resistance of the single-wafer body or a smaller-sized single-wafer body cut from the single-wafer body.
- the polarizing film 30 is a film having a function of selectively transmitting linear polarization in one direction from natural light.
- an iodine-based polarizing film in which iodine is adsorbed and oriented on a polyvinyl alcohol-based resin film a dye-based polarizing film in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol-based resin film, and a dichroic dye in a Riotrovic liquid crystal state.
- examples thereof include a coating type polarizing film coated with, oriented and immobilized. These polarizing films are called absorption type polarizing films because they selectively transmit linear polarization in one direction from natural light and absorb linear polarization in the other direction.
- the polarizing film 30 is not limited to the absorption type polarizing film, but is a reflective polarizing film that selectively transmits linear polarization in one direction from natural light and reflects the linear polarization in the other direction, or linear polarization in the other direction.
- a scattering type polarizing film that scatters the particles may be used, but an absorption type polarizing film is preferable from the viewpoint of excellent visibility. Of these, an iodine-based polarizing film having excellent degree of polarization and transmittance is more preferable.
- the polarizing film 30 is a step of uniaxially stretching a polyvinyl alcohol-based resin film; a step of adsorbing a bicolor dye by dyeing the polyvinyl alcohol-based resin film with a bicolor dye; polyvinyl alcohol on which the bicolor dye is adsorbed. It can be produced by a method including a step of treating (cross-linking) the based resin film with an aqueous boric acid solution; and a step of washing with water after the treatment with the aqueous boric acid solution.
- the draw ratio is usually about 3 to 8 times.
- a drying treatment is performed to obtain a polarizing film 30.
- the drying process can be performed using a hot air dryer or a far-infrared heater.
- a polarizing plate can be obtained by adhering a protective film on both sides of the polarizing film 30 using an adhesive.
- the thickness of the polarizing film 30 can be 40 ⁇ m or less, preferably 30 ⁇ m or less (for example, 20 ⁇ m or less). According to the methods described in JP-A-2000-338329 and JP-A-2012-159778, the thin-film polarizing film 30 can be manufactured more easily, and the thickness of the polarizing film 30 is, for example, 20 ⁇ m or less. Further, it can be 10 ⁇ m or less. The thickness of the polarizing film 30 is usually 2 ⁇ m or more. Reducing the thickness of the polarizing film 30 is advantageous for reducing the thickness of the polarizing plate and eventually the image display device.
- the first protective film 10 and the second protective film 20 are each translucent (preferably optically transparent) thermoplastic resin, for example, a chain polyolefin resin (polypropylene resin or the like).
- a chain polyolefin resin polypropylene resin or the like.
- Polyolefin-based resins such as cyclic polyolefin-based resins (norbornen-based resins, etc.); Cellulosic ester-based resins such as triacetyl cellulose and diacetyl cellulose; Polyester-based resins such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate; It can be a resin film made of a based resin; a (meth) acrylic resin; or a mixture thereof, a copolymer, or the like.
- the first protective film 10 and the second protective film 20 are each composed of a resin selected from the group consisting of a polyester resin, a polycarbonate resin, a polyolefin resin, a (meth) acrylic resin and a cellulose ester resin.
- a resin selected from the group consisting of a polyester resin, a polycarbonate resin, a polyolefin resin, a (meth) acrylic resin and a cellulose ester resin.
- (meth) acrylic means methacrylic and / or acrylic
- (meth) in the case of "(meth) acrylate” or the like has the same meaning.
- the first protective film 10 and the second protective film 20 may be either an unstretched film or a uniaxially or biaxially stretched film, respectively.
- the biaxial stretching may be simultaneous biaxial stretching in which the two stretching directions are simultaneously stretched, or sequential biaxial stretching in which the stretching is performed in a predetermined direction and then in the other direction.
- the first protective film 10 and / or the second protective film 20 may be a protective film having an optical function such as a retardation film.
- the retardation film is an optical functional film used for the purpose of compensating for the phase difference by a liquid crystal cell which is an image display element.
- a retardation film to which an arbitrary retardation value is imparted by stretching a film made of the thermoplastic resin (uniaxial stretching or biaxial stretching, etc.) or forming a liquid crystal layer or the like on the film. can be.
- chain polyolefin resin examples include homopolymers of chain olefins such as polyethylene resin and polypropylene resin, and copolymers composed of two or more kinds of chain olefins.
- Cyclic polyolefin resin is a general term for resins containing norbornene, tetracyclododecene (also known as dimethanooctahydronaphthalene) or a cyclic olefin typified by a derivative thereof as a polymerization unit.
- Specific examples of the cyclic polyolefin resin include a ring-opened (co) polymer of a cyclic olefin and a hydrogenated product thereof, an addition polymer of a cyclic olefin, a cyclic olefin and a chain olefin such as ethylene and propylene, or a vinyl group.
- a copolymer with an aromatic compound having, and a modified (co) polymer obtained by modifying these with an unsaturated carboxylic acid or a derivative thereof is preferably used as the cyclic olefin.
- the cellulose ester resin is a resin in which at least a part of the hydroxyl group in cellulose is esterified with acetate, and even if it is a mixed ester in which a part is esterified with acetate and a part is esterified with another acid. good.
- the cellulose ester-based resin is preferably an acetyl cellulose-based resin. Specific examples of the acetyl cellulose-based resin include triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate and the like.
- the polyester-based resin is a resin other than the above-mentioned cellulose ester-based resin having an ester bond, and is generally composed of a polyvalent carboxylic acid or a derivative thereof and a polycondensate of a polyhydric alcohol.
- Specific examples of the polyester-based resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polycyclohexanedimethylterephthalate, and polycyclohexanedimethylnaphthalate. Of these, polyethylene terephthalate is preferable.
- the polyethylene terephthalate means a resin in which 80 mol% or more of the repeating unit is composed of ethylene terephthalate.
- the polycarbonate resin is a polyester formed from carbonic acid and glycol or bisphenol.
- the (meth) acrylic resin can be a polymer containing a methacrylic acid ester as a main monomer (containing 50% by mass or more), and a small amount of other copolymerization components are copolymerized with the polymer. It is preferably a polymer.
- the (meth) acrylic resin is more preferably a copolymer of methyl methacrylate and methyl acrylate, and a third monofunctional monomer may be further copolymerized.
- Examples of the third monofunctional monomer include methacrylic acid such as ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, and 2-hydroxyethyl methacrylate.
- methacrylic acid such as ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, and 2-hydroxyethyl methacrylate.
- Methacrylic acid esters other than methyl acrylic acid esters such as ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate; 2- Hydroxyalkylacrylic acid esters such as methyl (hydroxymethyl) acrylate, methyl 2- (1-hydroxyethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate, butyl 2- (hydroxymethyl) acrylate; methacrylic.
- Unsaturated acids such as acids, acrylic acids; halogenated styrenes such as chlorostyrene and bromostyrene; substituted styrenes such as vinyltoluene and ⁇ -methylstyrene; unsaturated nitriles such as acrylonitrile and methacrylic acid.
- Acrylic acid anhydrides, unsaturated acid anhydrides such as citraconic acid anhydride; unsaturated imides such as phenylmaleimide and cyclohexylmaleimide can be mentioned.
- As the third monofunctional monomer only one kind may be used alone, or two or more kinds may be used in combination.
- the (meth) acrylic resin may be further copolymerized with a polyfunctional monomer.
- the polyfunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and nonaethylene glycol di (meth). Esteration of both terminal hydroxyl groups of ethylene glycol or its oligomer such as acrylate, tetradecaethylene glycol di (meth) acrylate with (meth) acrylic acid; both terminal hydroxyl groups of propylene glycol or its oligomer is (meth) acrylic acid.
- (meth) acrylic acid Esterated with (meth) acrylic acid; the hydroxyl group of a dihydric alcohol such as neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate, butanediol di (meth) acrylate; Bisphenol A, an alkylene oxide adduct of Bisphenol A, or esterified of both terminal hydroxyl groups of these halogen substituents with (meth) acrylic acid; polyhydric alcohols such as trimethylolpropane, pentaerythritol (meth) acrylic.
- a dihydric alcohol such as neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate, butanediol di (meth) acrylate
- Bisphenol A an alkylene oxide adduct of Bisphenol A, or esterified of both terminal hydroxyl groups of these halogen substitu
- the (meth) acrylic resin may be modified by further reacting between the functional groups of the copolymer.
- the reaction includes, for example, a demethanol condensation reaction in a polymer chain between a methyl ester group of methyl acrylate and a hydroxyl group of methyl 2- (hydroxymethyl) acrylate, and a carboxyl group of acrylate and 2- (hydroxymethyl) acrylic. Examples thereof include a dehydration condensation reaction in a polymer chain with a hydroxyl group of methyl acid.
- the glass transition temperature of the (meth) acrylic resin is preferably 80 to 160 ° C.
- the glass transition temperature is the polymerization ratio of the methacrylic acid ester-based monomer and the acrylic acid ester-based monomer, the carbon chain length of each ester group, the types of functional groups having them, and the polyfunctional monomer for the entire monomer. It can be controlled by adjusting the polymerization ratio of the monomer. It is also effective to introduce a ring structure into the main chain of the polymer as a means for increasing the glass transition temperature of the (meth) acrylic resin.
- the ring structure is preferably a heterocyclic structure such as a cyclic acid anhydride structure, a cyclic imide structure and a lactone structure.
- the (meth) acrylic resin may contain an additive if necessary.
- the additive include a lubricant, an antiblocking agent, a heat stabilizer, an antioxidant, an antistatic agent, a light resistant agent, an impact resistance improving agent, a surfactant and the like. These additives may be contained in a protective film made of a thermoplastic resin other than the (meth) acrylic resin.
- the (meth) acrylic resin may contain acrylic rubber particles which are impact-improving agents from the viewpoint of film-forming property on the film, impact resistance of the film, and the like.
- Acrylic rubber particles are particles containing an elastic polymer mainly composed of an acrylic acid ester as an essential component, and have a single-layer structure substantially composed of only this elastic polymer, or one elastic polymer. Examples thereof include a multi-layer structure having layers.
- the first protective film 10 and / or the second protective film 20 may contain an ultraviolet absorber.
- an ultraviolet absorber When the polarizing plate is applied to an image display device such as a liquid crystal display device, the image display element is deteriorated by ultraviolet rays by arranging a protective film containing an ultraviolet absorber on the visible side of the image display element (for example, a liquid crystal cell). Can be suppressed.
- the ultraviolet absorber include salicylic acid ester compounds, benzophenone compounds, benzotriazole compounds, cyanoacrylate compounds, nickel complex salt compounds and the like.
- the first protective film 10 and the second protective film 20 may be films made of the same resin or may be made of different resins. Further, the first protective film 10 and the second protective film 20 may be the same or different in terms of thickness, presence / absence of additives, their types, retardation characteristics, and the like.
- the first protective film 10 and / or the second protective film 20 has a hard coat layer, an antiglare layer, an antireflection layer, a light diffusion layer, an antistatic layer, and an antistatic layer on the outer surface thereof (the surface opposite to the polarizing film 30). It may have a surface treatment layer (coating layer) such as a dirty layer and a conductive layer.
- the thicknesses of the first protective film 10 and the second protective film 20 are usually 5 to 200 ⁇ m, preferably 10 to 120 ⁇ m, and more preferably 10 to 85 ⁇ m, respectively. Reducing the thickness of the first protective film 10 and the second protective film 20 is advantageous for reducing the thickness of the polarizing plate and the image display device. The thinner the protective film, the easier it is for the curl resistance to decrease. However, according to the present invention, the curl resistance of the polarizing plate can be effectively improved even if the thickness of the first protective film 10 and the second protective film 20 is thin. Can be done.
- the first adhesive layer 15 is a cured product layer of the first cationic polymerization type adhesive containing one or more kinds of cationic polymerization initiators
- the second adhesive layer 25 is one or more kinds. It is a cured product layer of the second cationic polymerization type adhesive containing a cationic polymerization initiator.
- the first and second cationically polymerizable adhesives usually contain a cationically polymerizable compound and a cationically polymerizable initiator, respectively.
- the cationic polymerization initiator generates a cationic species or Lewis acid by irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, or electron beams, and initiates a polymerization reaction of a cationically curable compound.
- the above-mentioned one or more cationic polymerization initiators contained in the first cationic polymerization type adhesive include the first cationic polymerization initiator.
- the first cationic polymerization initiator includes a cationic component and the following formula (i): (In the formula, Y indicates an aryl group having 6 to 30 carbon atoms or a heterocyclic group having 4 to 30 carbon atoms, or a halogen atom, which may have a substituent (excluding a group containing a halogen atom).
- Phf represents a phenyl group in which at least one of the hydrogen atoms is substituted with at least one selected from a perfluoroalkyl group, a perfluoroalkoxy group, and a halogen atom.
- K is an integer of 0 to 4.
- the plurality of Ys may be the same or different.
- the plurality of Rhfs may be the same or different.
- It is a borate salt composed of an anion component represented by.
- the above-mentioned one or more kinds of cationic polymerization initiators contained in the first cationic polymerization initiator and the second cationic polymerization type adhesive are the above-mentioned one kind in which the molecular weight of the first cationic polymerization initiator is contained in the second cationic polymerization type adhesive. It is selected so as to be larger than the molecular weight of the above cationic polymerization initiator.
- the molecular weight of the first cationic polymerization initiator is larger than the molecular weight of the above-mentioned one or more kinds of cationic polymerization initiators contained in the second cationic polymerization type adhesive, that is, the molecular weight of the first cationic polymerization initiator is the second cationic polymerization. It means that it is larger than the molecular weight of any of the cationic polymerization initiators contained in the mold adhesive.
- the first cationic polymerization type adhesive can contain two or more kinds of first cationic polymerization initiators.
- the molecular weight of at least one first cationic polymerization initiator is any of the cationic polymerization initiators contained in the second cationic polymerization type adhesive.
- the molecular weight of all the first cationic polymerization initiators is the second cationic polymerization type from the viewpoint of providing a polarizing plate having good curl resistance even when placed in a high humidity environment. It is preferably larger than the molecular weight of any of the cationic polymerization initiators contained in the adhesive.
- the present invention it is possible to provide a polarizing plate having good curl resistance even when placed in a high humidity environment.
- the first protective film 10 side is concave and the second protective film 20 side is convex. It is possible to effectively suppress the curl. It is considered that such an action effect is caused by using the above-mentioned predetermined borate salt as the first cationic polymerization initiator and satisfying the above-mentioned predetermined relationship with respect to the molecular weight of the cationic polymerization initiator.
- the first cationic polymerization type adhesive forming the first adhesive layer 15 contains one or more kinds of cationic polymerization initiators, and the one or more kinds of cationic polymerization initiators are the first.
- the first cationic polymerization initiator is a borate salt composed of a cationic component and an anionic component represented by the above formula (i).
- the first cationic polymerization initiator may contain one or more types of cationic components, and may contain one or more types of anionic components represented by the formula (i).
- Examples of the perfluoroalkyl group in the formula (i) include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl group, a perfluoropentyl group, a perfluorooctyl group, and the like having one carbon number.
- Examples thereof include a perfluorocycloalkyl group having 3 to 8 carbon atoms, preferably 3 to 4 carbon atoms such as a perfluorocyclopropyl group and a perfluorocyclobutyl group.
- Examples of the perfluoroalkoxy group in the formula (i) include a trifluoromethoxy group, a pentafluoroethoxy group, a heptafluoropropoxy group, a nonafluorobutoxy group, a perfluoropentyloxy group, a perfluorooctyloxy group and the like.
- halogen atom in the formula (i) examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- Rhf examples include pentafluorophenyl group (C 6 F 5 ), trifluorophenyl group (C 6 H 2 F 3 ), tetrafluorophenyl group (C 6 HF 4 ), and trifluoromethyl phenyl group (CF 3 C).
- Rhf is preferably a phenyl group in which at least one hydrogen atom is substituted with a halogen atom, and more preferably a phenyl group in which at least one hydrogen atom is substituted with a fluorine atom.
- Examples of the aryl group having 6 to 30 carbon atoms in Y in the formula (i) include a phenyl group, a biphenyl group, a naphthyl group, an anthrasenyl group, a phenanthrenyl group and the like.
- the heterocyclic group having 4 to 30 carbon atoms in Y in the formula (i) is a group obtained by removing one hydrogen atom from the heterocyclic ring having 4 to 30 carbon atoms.
- heterocycles examples include a heterocycle containing an oxygen atom such as an oxetane ring, a tetrahydrofuran ring and a morpholin ring; a heterocycle containing a sulfur atom such as a thiophene ring and a thiazole ring; and a nitrogen atom such as a pyrrole ring, an imidazoline ring and an indole ring.
- oxygen atom such as an oxetane ring, a tetrahydrofuran ring and a morpholin ring
- sulfur atom such as a thiophene ring and a thiazole ring
- nitrogen atom such as a pyrrole ring, an imidazoline ring and an indole ring.
- heterocycles including.
- the substituent that Y may have is a group other than the group containing a halogen atom, for example, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and a group having 1 to 6 carbon atoms. Examples thereof include an alkoxy group, an alkylthio group having 1 to 6 carbon atoms, an arylthio group having 6 to 12 carbon atoms, and an alkylcarbonyl group having 2 to 7 carbon atoms.
- each of these substituents may be the same or different.
- k is preferably an integer of 0 to 2, more preferably an integer of 0 or 1. It is more preferably 0.
- the plurality of Rhfs are preferably the same group, and all Rhfs are phenyl groups in which at least one hydrogen atom is substituted with a fluorine atom. Is more preferable.
- the anion component represented by the formula (i) is an anion in which k is 0 and Rhf is a phenyl group in which at least one hydrogen atom is substituted with a halogen atom. It is preferably a component, and more preferably an anionic component in which k is 0 and Rhf is a pentafluorophenyl group (C 6 F 5 ).
- the anion component of the first cationic polymerization initiator is preferably tetrakis (pentafluorophenyl) borate anion B (C 6 F 5 ) 4- or the like.
- Examples of the cationic component of the first cationic polymerization initiator include aryl sulfonium ions, aryl iodonium ions, aryl diazonium ions and the like.
- Examples of the aryl sulfonium ion include a triphenyl sulfonium cation, a 4,4'-bis (diphenyl sulfonio) diphenyl sulfide cation and the like.
- Examples of the aryl iodonium ion include a diphenyl iodonium cation.
- Examples of the aryl diazonium ion include a benzenediazonium cation.
- aryl sulfonium ions are preferable from the viewpoint of curl resistance of the polarizing plate.
- the cationic component of the first cationic polymerization initiator more preferably contains 4,4'-bis (diphenylsulfonate) diphenylsulfide cation.
- the first cationic polymerization type adhesive contains only the first cationic polymerization initiator as the cationic polymerization initiator.
- the molecular weight of the first cationic polymerization type initiator may be 900 or more, 1000 or more, 1500 or more, 1900 or more, or 3000 or less. Well, it may be 2500 or less.
- the second cationically polymerizable adhesive forming the second adhesive layer 25 contains one or more cationic polymerization initiators.
- the cationic polymerization initiator contained in the second cationic polymerization type adhesive is the above-mentioned one or more kinds of cationic polymerization initiators in which the molecular weight of the first cationic polymerization initiator is contained in the second cationic polymerization type adhesive. It is selected to be larger than the molecular weight.
- one or more types of cationic polymerization initiators contained in the second cationic polymerization type adhesive are also collectively referred to as “second cationic polymerization initiator”.
- the second cationic polymerization initiator may contain one or more types of cationic components, and may contain one or more types of anionic components.
- examples of the second cationic polymerization initiator include aryl sulfonium salts, aryl iodonium salts, aryl diazonium salts, iron-allene complexes and the like.
- examples of the cation component constituting the aryl sulfonium salt include aryl sulfonium ions such as triphenyl sulfonium cation and 4,4'-bis (diphenyl sulfonate) diphenyl sulfide cation.
- Examples of the cation component constituting the aryliodonium salt include aryliodonium ions such as diphenyliodonium cations.
- aryldiazonium salt examples include aryldiazonium ions such as benzenediazonium cations.
- the iron-arene complex is, for example, cyclopentadienyl iron (II) arene cationic complex salt.
- the cationic component of the first cationic polymerization initiator and the cationic component of the second cationic polymerization initiator are both from the viewpoint of curl resistance of the polarizing plate and adhesion between the polarizing film and the protective film. It is an aryl sulfonium ion.
- the cationic component of the first cationic polymerization initiator and the cationic component of the second cationic polymerization initiator are both triphenylsulfonium cations and / or 4,4'-bis (diphenylsulfonate) diphenylsulfides. It is a cation.
- the anion component constituting the second cationic polymerization initiator includes a special phosphorus anion [(Rf) n PF 6-n ] - (n represents an integer of 1 to 6 and Rf represents an alkyl halide group).
- Hexafluorophosphate anion PF 6- hexafluoroantimonate anion SbF 6- , pentafluorohydroxyantimonate anion SbF 5 (OH) - , hexafluoroarsenate anion AsF 6- , tetrafluoroborate anion BF 4- , tetrakis (penta).
- a preferred example is the hexafluorophosphate anion PF 6 ⁇ .
- the anion component of the first cationic polymerization initiator is the anion represented by the above formula (i), and the anion of the second cationic polymerization initiator.
- the component is PF 6- .
- the anionic component of the first cationic polymerization initiator is B ( C6 F 5 ) 4- , and the anionic component of the second cationic polymerization initiator. Is PF 6- .
- the cationic polymerization initiator contained in the second cationic polymerization type adhesive preferably does not have an anion component represented by the above formula (i), and is not a borate anion. Is more preferable.
- the molecular weight of the second cationic polymerization initiator is not particularly limited as long as it is smaller than the molecular weight of the first cationic polymerization initiator, but it may be 1000 or less, 800 or less, or 600 or less. , 200 or more.
- the content of the cationic polymerization initiator contained in the first cationically polymerizable adhesive (the total content of two or more kinds of cationic polymerization initiators if they are contained) and the cation contained in the second cationically polymerizable adhesive.
- the content of the polymerization initiator (when two or more kinds of cationic polymerization initiators are contained, the total content thereof) is usually 0.5 parts by mass or more and 10 parts by mass with respect to 100 parts by mass of the cationically polymerizable compound. It is 5 parts by mass or less, preferably 0.5 parts by mass or more and 5 parts by mass or less, and more preferably 1.0 part by mass or more and 5 parts by mass or less.
- the content is more preferably 1.3 parts by mass or more. If the amount of the cationic polymerization initiator is excessively large, the amount of ionic substances in the adhesive layer increases, so that the hygroscopicity of the adhesive layer increases, and the durability of the polarizing plate may decrease.
- the cationically polymerizable compound contained in the first cationically polymerizable adhesive and the second cationically polymerizable adhesive is irradiated with active energy rays such as ultraviolet rays, visible light, electron beams, and X-rays.
- active energy rays such as ultraviolet rays, visible light, electron beams, and X-rays.
- the preferable cationically polymerizable compound is an epoxy compound.
- the epoxy compound is a compound having one or more, preferably two or more epoxy groups in the molecule.
- the epoxy compound includes an alicyclic epoxy compound, an aromatic epoxy compound, a hydrogenated epoxy compound, and an aliphatic epoxy compound.
- the epoxy compound preferably contains an alicyclic epoxy compound or an aliphatic epoxy compound, and more preferably contains an alicyclic epoxy compound.
- the first cationically polymerizable adhesive and the second cationically polymerizable adhesive may contain one or more cationically polymerizable compounds.
- the alicyclic epoxy compound is a compound having one or more epoxy groups bonded to the alicyclic ring in the molecule.
- the "epoxide group bonded to the alicyclic ring” means a bridging oxygen atom-O- in the structure represented by the following formula (I).
- m is an integer of 2 to 5.
- a compound in which one or more hydrogen atoms in the (CH 2 ) m in the above formula (I) are removed and a group bonded to another chemical structure can be an alicyclic epoxy compound.
- One or more hydrogen atoms in (CH 2 ) m may be appropriately substituted with a linear alkyl group such as a methyl group or an ethyl group.
- the transition temperature is high, which is advantageous in increasing the glass transition temperature of the adhesive layer, and is also advantageous in terms of the adhesiveness between the polarizing film and the protective film.
- Specific examples of the alicyclic epoxy compound are given below.
- the compound names are first listed, and then the chemical formulas corresponding to the respective compounds are shown, and the compound names and the corresponding chemical formulas are given the same reference numerals.
- An aromatic epoxy compound is a compound having an aromatic ring and an epoxy group in the molecule.
- Specific examples thereof include bisphenol type epoxy compounds such as bisphenol A diglycidyl ether, bisfer F diglycidyl ether, and bisphenol S diglycidyl ether or oligomers thereof; phenol novolac epoxy resin, cresol novolac epoxy resin, hydroxybenzaldehyde phenol novolac.
- Novolak type epoxy resin such as epoxy resin; polyfunctional epoxy such as 2,2', 4,4'-tetrahydroxydiphenylmethane glycidyl ether, 2,2', 4,4'-tetrahydroxybenzophenone glycidyl ether Compounds; Containing polyfunctional epoxy resins such as epoxidized polyvinylphenol.
- the hydrogenated epoxy compound is a glycidyl ether of a polyol having an alicyclic ring, and is a nuclear hydrogenated poly obtained by selectively hydrogenating an aromatic polyol in the aromatic ring under pressure in the presence of a catalyst.
- the hydroxy compound can be glycidyl etherified.
- Specific examples of the aromatic polyol include bisphenol type compounds such as bisphenol A, bisfer F and bisphenol S; novolak type resins such as phenol novolac resin, cresol novolak resin and hydroxybenzaldehyde phenol novolac resin; tetrahydroxydiphenylmethane and tetrahydroxy. Contains polyfunctional compounds such as benzophenone and polyvinylphenol.
- a glycidyl ether can be obtained by reacting an alicyclic polyol obtained by hydrogenating the aromatic ring of an aromatic polyol with epichlorohydrin.
- the hydrogenated epoxy compounds the diglycidyl ether of hydrogenated bisphenol A can be mentioned.
- the aliphatic epoxy compound is a compound having at least one oxylan ring (3-membered cyclic ether) bonded to an aliphatic carbon atom in the molecule.
- monofunctional epoxy compounds such as butyl glycidyl ether and 2-ethylhexyl glycidyl ether; 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4- Bifunctional epoxy compounds such as cyclohexanedimethanol diglycidyl ether; trifunctional or higher functional epoxy compounds such as trimethylolpropane triglycidyl ether and pentaerythritol tetraglycidyl ether; alicyclic such as 4-vinylcyclohexenedioxide and limonendioxide.
- epoxy compounds having one epoxy group directly bonded to the formula ring and an oxylan ring bonded to an aliphatic carbon atom.
- a bifunctional epoxy compound also referred to as an aliphatic diepoxy compound
- Such a suitable aliphatic diepoxy compound can be represented by, for example, the following formula (II).
- Y in the above formula (II) is an alkylene group having 2 to 9 carbon atoms, an alkylene group having 4 to 9 total carbon atoms intervening with an ether bond, or a divalent group having 6 to 18 carbon atoms having an alicyclic structure. It is a hydrocarbon group of.
- the aliphatic diepoxy compound represented by the above formula (II) is a diglycidyl ether of an alkane diol, a diglycidyl ether of an oligoalkylene glycol up to about 4 repetitions, or a diglycidyl ether of an alicyclic diol. Is.
- Alcandiols include ethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, and 1,4-butanediol.
- Neopentyl glycol 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentane Diol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1,8-octanediol, 2-methyl-1,8 -There are octanediol, 1,9-nonanediol and the like.
- Examples of the oligoalkylene glycol include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol and the like.
- Examples of the alicyclic diol include cyclohexanediol such as 1,2-cyclohexanediol, 1,3-cyclohexanediol, and 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 1, There are cyclohexanedimethanol and the like such as 4-cyclohexanedimethanol.
- An oxetane compound which is one of the cationically polymerizable compounds, is a compound containing one or more oxetane rings (oxetaneyl groups) in the molecule, and specific examples thereof are 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol).
- 2-ethylhexyloxetane, 1,4-bis [ ⁇ (3-ethyloxetane-3-yl) methoxy ⁇ methyl] benzene also called xylylenebis oxetane
- 3-ethyl-3 [ ⁇ ( 3-Ethyloxetane-3-yl) methoxy ⁇ methyl] oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3- (cyclohexyloxy) methyl-3-ethyloxetane.
- the oxetane compound may be used as the main component of the cationically polymerizable compound, or may be used in combination with the epoxy compound. By using an oxetane compound in combination, the curing speed and adhesiveness may be improved.
- Examples of the vinyl compound that can be a cationically polymerizable compound include an aliphatic or alicyclic vinyl ether compound, and specific examples thereof include n-amyl vinyl ether, i-amyl vinyl ether, n-hexyl vinyl ether, and n-octyl vinyl ether. , 2-Ethylhexyl vinyl ether, n-dodecyl vinyl ether, stearyl vinyl ether, oleyl vinyl ether and other alkyl or alkenyl alcohol vinyl ethers having 5 to 20 carbon atoms; 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether and the like.
- Monoalcohol vinyl ether having an aliphatic ring or aromatic ring such as cyclohexyl vinyl ether, 2-methylcyclohexylvinyl ether, cyclohexylmethylvinyl ether, benzylvinyl ether; glycerol monovinyl ether, 1,4-butanediol monovinyl ether, 1, 4-Butanediol divinyl ether, 1,6-hexanediol divinyl ether, neopentyl glycol divinyl ether, pentaerythritol divinyl ether, pentaerythritol tetravinyl ether, trimethylolpropane divinyl ether, trimethylolpropanetrivinyl ether, 1,4-dihydroxycyclohexane Mono-polyvinyl ethers of polyvalent alcohols such as monovinyl ether, 1,4-dihydroxycyclohexan
- the vinyl compound may be used as a main component of the cationically polymerizable compound, or may be used in combination with an epoxy compound, or an epoxy compound and an oxetane compound. By using a vinyl compound in combination, it may be possible to improve the curing speed and the low viscosity of the adhesive.
- the cationically polymerizable adhesive can further contain other cationically polymerizable compounds other than the above, such as a cyclic lactone compound, a cyclic acetal compound, a cyclic thioether compound, and a spiro ortho ester compound.
- the cationic polymerization is carried out.
- the content of the sex compound (the content of all the cationically polymerizable compounds contained in the cationically polymerizable adhesive, and the total content of two or more kinds of cationically polymerizable compounds when they are contained) is 50 mass by mass. % Or more, more preferably 60% by mass or more, further preferably 80% by mass or more, still more preferably 90% by mass or more, and particularly preferably 100% by mass. preferable.
- the cationically polymerizable compound contained in the first cationically polymerizable adhesive and the cationically polymerizable compound contained in the second cationically polymerizable adhesive may be of the same type or different from each other.
- the first and / or second cationically polymerized adhesives may contain other additives, if necessary.
- the additive include an ion trapping agent, an antioxidant, a chain transfer agent, a polymerization accelerator (polyol, etc.), a sensitizer, a sensitizing aid, a light stabilizer, a tackifier, a thermoplastic resin, and a filler.
- Flow conditioner plasticizer, defoaming agent, leveling agent, silane coupling agent, dye, antistatic agent, ultraviolet absorber.
- the first protective film 10 is laminated and adhered to one surface of the polarizing film 30 via the first adhesive layer 15, and the polarizing film 30 is laminated.
- the polarizing plate according to the present invention can be obtained by laminating and adhering the second protective film 20 to the other surface of the film via the second adhesive layer 25.
- the first protective film 10 and the second protective film 20 (collectively referred to as simply "protective film") may be laminated and adhered one side at a time, or the protective films on both sides may be laminated in one step. It may be glued.
- an adhesive is applied to the bonding surface of the polarizing film 30 and / or the bonding surface of the protective film, and both are coated via the coating layer of the adhesive. This can be done by stacking the films of the above, pressing them from above and below using, for example, a bonding roll or the like, bonding them, and then irradiating them with active energy rays to cure them.
- the heat treatment may be performed at the same time as the irradiation with the active energy ray or after the irradiation with the active energy ray.
- one or both of the bonding surfaces of the polarizing film 30 and the protective film are subjected to saponification treatment, corona discharge treatment, plasma treatment, flame treatment, primer treatment, and anchor coating treatment.
- the easy-adhesion treatment such as the above may be applied.
- the coating layer of the adhesive for example, various coating methods such as a doctor blade, a wire bar, a die coater, a comma coater, and a gravure coater can be used. Further, it is also possible to adopt a method in which the polarizing film 30 and the protective film are continuously supplied so that the bonding surface of both is on the inside, and the adhesive is spread between them.
- the adhesive forming the first adhesive layer 15 and the second adhesive layer 25 has a low viscosity.
- the viscosity at 25 ° C. is preferably 1000 mPa ⁇ s or less, more preferably 500 mPa ⁇ s or less, still more preferably 100 mPa ⁇ s or less.
- the adhesive may be solvent-free, but may contain an organic solvent in order to adjust the viscosity to be suitable for the coating method to be adopted.
- the light source of the active energy ray may be, for example, one that generates ultraviolet rays, electron beams, X-rays, or the like.
- the active energy ray is preferably ultraviolet light.
- a light source having a light emission distribution having a wavelength of 400 nm or less is preferable, and examples thereof include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, a black light lamp, a microwave excited mercury lamp, and a metal halide lamp. be able to.
- the intensity of irradiating the adhesive layer with active energy rays is determined for each adhesive composition, but the intensity of irradiating light in the wavelength region effective for activating the photopolymerization initiator is 0.1 to 1000 mW / cm 2 . It is preferable to do so. If the light irradiation intensity is too low, the reaction time will be too long, while if the light irradiation intensity is too high, the heat radiated from the lamp and the heat generated during the polymerization of the adhesive will cause yellowing and polarization of the adhesive layer. There is a possibility that the film 30 may be deteriorated or the protective film may be poorly skinned.
- the light irradiation time to the adhesive is also controlled for each adhesive composition, but the integrated light amount expressed as the product of the light irradiation intensity and the light irradiation time is set to be 10 to 5000 mJ / cm 2 . Is preferable. If the integrated light intensity is too small, the active species derived from the photopolymerization initiator may not be sufficiently generated, and the resulting adhesive layer may be insufficiently cured. On the other hand, if the integrated light intensity is too large, the light intensity may be insufficient. The irradiation time becomes very long, which tends to be disadvantageous for improving productivity.
- the timing of laminating the protective film on the polarizing film 30 via the coating layer of the adhesive and the timing of curing the coating layer are not particularly limited.
- the coating layer can be continuously cured, and then the other protective film can be laminated to cure the coating layer.
- the coating layers on both sides may be cured at the same time.
- the irradiation of the active energy rays may be performed from either protective film side.
- one protective film contains an ultraviolet absorber and the other protective film does not contain an ultraviolet absorber, it is preferable to irradiate active energy rays from the protective film side that does not contain the ultraviolet absorber. By irradiating in this way, the irradiated active energy rays can be effectively used and the curing rate can be increased.
- the thickness of the first and second adhesive layers 15 and 25 after curing is usually 20 ⁇ m or less, preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, still more preferably less than 5 ⁇ m, and particularly preferably 3 ⁇ m or less. If the thicknesses of the first and second adhesive layers 15 and 25 are excessively large, the reaction rate of the adhesive tends to decrease, and the wet and heat durability of the polarizing plate tends to deteriorate.
- the thicknesses of the first and second adhesive layers 15 and 25 are usually 0.01 ⁇ m or more, preferably 0.1 ⁇ m or more, and more preferably 0.5 ⁇ m or more.
- the first adhesive layer and the second adhesive may have fine defects (fine dust, fine dust, etc.) on the polarizing film 30.
- Other layers first protective film 10, second protective film 20, etc. laminated via the layer may also be affected by fine defects.
- the first adhesive layer 15 and the second adhesive layer 25 may have the same thickness or different thicknesses.
- the polarizing plate preferably has the following configuration, for example.
- the first protective film 10 and the second protective film 20 are films made of different resins.
- the first protective film 10 is a (meth) acrylic resin film or a cellulose ester resin film.
- the second protective film 20 is a cyclic polyolefin resin film.
- the first cationic polymerization initiator is a borate salt composed of a cationic component which is an arylsulfonium ion and an anion component represented by the above formula (i).
- the second cationic polymerization initiator contains a cationic polymerization initiator containing PF 6 ⁇ as an anionic component.
- the first cationic polymerization initiator is a borate salt composed of a cationic component which is an aryl sulfonium ion and an anion component which is B (C 6 F 5 ) 4- .
- the second cationic polymerization initiator contains a cationic polymerization initiator composed of a cationic component which is an aryl sulfonium ion and an anionic component which is PF 6 ⁇ .
- the first cationic polymerization type adhesive contains only the first cationic polymerization initiator
- the second cationic polymerization type adhesive contains a cationic component which is an aryl sulfonium ion. It contains only a cationic polymerization initiator composed of an anionic component of PF 6 ⁇ .
- the cationic component of the first cationic polymerization initiator is a triphenylsulfonium cation and / or a 4,4'-bis (diphenylsulfonio) diphenylsulfide cation, and the second cationic polymerization type adhesive.
- the cationic component of the cationic polymerization initiator contained in the above is a triphenylsulfonium cation and / or a 4,4'-bis (diphenylsulfonio) diphenylsulfide cation.
- the polarizing plate When the polarizing plate is incorporated in the image display device, the polarizing plate is typically arranged so that the first protective film 10 side is the visual recognition side and the second protective film 20 side is the image display element side.
- the polarizing plate can be provided with an optical functional film other than the polarizing film 30 for imparting a desired optical function.
- a suitable example thereof is a retardation film.
- the first protective film 10 and / or the second protective film 20 can also serve as the retardation film, but the retardation film can also be laminated separately from the protective film. In the latter case, the retardation film can be laminated on the outer surface of the first protective film 10 and / or the second protective film 20 via the pressure-sensitive adhesive layer and the adhesive layer.
- the retardation film include a birefringent film composed of a stretched film of a translucent thermoplastic resin, a film in which a discotic liquid crystal or a nematic liquid crystal is oriented and fixed, and the above liquid crystal layer on a base film. Includes those formed.
- the base film is usually a thermoplastic resin film, and a cellulose ester resin such as triacetyl cellulose is preferably used as the thermoplastic resin.
- optically functional films examples include a condenser plate, a brightness improving film, a reflective layer (reflective film), a semi-transmissive reflective layer (semi-transmissive reflective film), and a light diffusing layer (light). Diffusing film) etc. These are generally provided when the polarizing plate is a polarizing plate arranged on the back surface side (backlight side) of the liquid crystal cell.
- the polarizing plate according to the present invention may include an adhesive layer for attaching the polarizing plate to an image display element such as a liquid crystal cell or another optical member.
- the pressure-sensitive adhesive layer can be laminated on the outer surface of the protective film.
- the pressure-sensitive adhesive layer may be laminated on the outer surface of the first protective film, or may be laminated on the outer surface of the second protective film.
- the polarizing plate has a pressure-sensitive adhesive layer
- This pressure-sensitive adhesive layer is typically a pressure-sensitive adhesive layer for adhering a polarizing plate to an image display element.
- a (meth) acrylic resin, a silicone-based resin, a polyester-based resin, a polyurethane-based resin, a polyether-based resin, or the like as a base polymer can be used.
- a (meth) acrylic pressure-sensitive adhesive is preferably used from the viewpoints of transparency, adhesive strength, reliability, weather resistance, heat resistance, reworkability and the like.
- the (meth) acrylic pressure-sensitive adhesive includes (meth) acrylic acid alkyl esters having an alkyl group having 20 or less carbon atoms such as a methyl group, an ethyl group and a butyl group, and (meth) acrylic acid and (meth) acrylic acid.
- a functional group-containing (meth) acrylic monomer such as hydroxyethyl is blended so that the glass transition temperature is preferably 25 ° C. or lower, more preferably 0 ° C. or lower, and the weight average molecular weight is 100,000 or more (meth).
- Acrylic resins are useful as base polymers.
- the pressure-sensitive adhesive composition is dissolved or dispersed in an organic solvent such as toluene or ethyl acetate to prepare a solution of 10 to 40% by mass, and this is used as the target surface of the polarizing plate.
- an organic solvent such as toluene or ethyl acetate
- the thickness of the pressure-sensitive adhesive layer is determined according to the adhesive strength and the like, but is appropriately in the range of about 1 to 50 ⁇ m, preferably 2 to 40 ⁇ m.
- the polarizing plate may include the above-mentioned separate film.
- the separate film can be a film made of a polyethylene resin such as polyethylene, a polypropylene resin such as polypropylene, a polyester resin such as polyethylene terephthalate, or the like. Of these, a stretched film of polyethylene terephthalate is preferable.
- the pressure-sensitive adhesive layer contains, if necessary, a filler made of glass fiber, glass beads, resin beads, metal powder or other inorganic powder, a pigment, a colorant, an antioxidant, an ultraviolet absorber, an antioxidant, and the like. It may have been done.
- the polarizing plate according to the present invention may include a protective film for temporarily adhering and protecting the surface (protective film surface) thereof. After the polarizing plate is attached to, for example, an image display element or another optical member, the protective film is peeled off and removed together with the pressure-sensitive adhesive layer contained therein.
- the polarizing plate of the present invention can be attached to an image display element such as a liquid crystal cell via an adhesive layer.
- an image display element such as a liquid crystal cell
- the liquid crystal cell include an IPS type and a VA type.
- the polarizing plate of the present invention can be bonded to an organic EL panel as an antireflection polarizing plate via an adhesive layer.
- Cationic polymerizable compound A-1 3', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, trade name "CEL2021P")
- Cationic Polymerizable Compound A-2 Neopentyl Glycol Diglycidyl Ether (manufactured by Nagase ChemteX Corporation, trade name "EX-211L”)
- Cationic polymerizable compound A-3 4-hydroxybutyl vinyl ether (manufactured by Nippon Carbide, trade name "HBVE")
- Cationic Polymerizable Compound A-4 Methyl Methacrylate-Glyzyl Methacrylic Acid Ether Copolymer (Cationic Polymerizable Polymer) (manufactured by NOF CORPORATION, trade name "Marproof G-01100”)
- Cationic Polymerization Initiator B-1 3', 4'-epoxycycl
- Cationic polymerization initiator B-2 A cationic polymerization initiator composed of the following cationic and anionic components.
- Molecular weight 517 manufactured by Sun Appro Co., Ltd., trade name "CPI-100P"
- one side of the second protective film shown in Table 2 is subjected to corona discharge treatment, and the thickness of the second cationically polymerizable adhesive shown in Table 2 after curing is applied to the corona discharge treated surface using a bar coater.
- the polarizing film with the first protective film produced above was laminated on the coated surface on the polarizing film side, and pressed and bonded using a bonding roll to obtain a laminated body.
- the integrated light intensity is 200 mJ / cm 2 (UVB) using an ultraviolet irradiation device with a belt conveyor [the lamp uses a "D valve" manufactured by Fusion UV Systems).
- a polarizing plate was produced by irradiating ultraviolet rays so as to obtain the above, and curing the adhesive layers on both sides.
- the polarizing plate When the obtained polarizing plate is incorporated in an image display device, the polarizing plate is arranged so that the second protective film (phase difference film) side is the image display element side and the first protective film side is the visual recognition side.
- the second protective film (phase difference film) side is the image display element side
- the first protective film side is the visual recognition side.
- Protective film a A (meth) acrylic resin film having a thickness of 60 ⁇ m containing an ultraviolet absorber.
- the (meth) acrylic resin constituting the film is a copolymer obtained by copolymerizing methyl methacrylate and methyl acrylate at a mass ratio of 96: 4.
- Protective film b Cellulose ester-based resin film with a thickness of 60 ⁇ m (manufactured by Fuji Photo Film Co., Ltd., trade name “TG”)
- Protective film c A retardation film having a thickness of 50 ⁇ m made of a cyclic polyolefin resin (norbornene resin) (manufactured by Nippon Zeon Corporation, trade name “ZEONOR”).
- Protective film d A retardation film having a thickness of 40 ⁇ m made of (meth) acrylic resin (manufactured by LG Chem Co., Ltd., trade name “GA-01”).
- the amount of curl was obtained by placing a curved sheet of leaf on a horizontal table so that it was convex downward, and measuring the height from the table to the four corners of the sheet with a ruler. It was calculated as the average value of the points. Based on the obtained curl amount, the curl resistance was evaluated according to the following criteria. The evaluation results are shown in Table 2.
- the obtained optical laminate was measured for MD transmittance and TD transmittance in the wavelength range of 380 to 780 nm using a spectrophotometer with an integrating sphere (manufactured by Nippon Spectroscopy Co., Ltd., product name "V7100").
- the single transmittance at the wavelength was calculated.
- the calculated single transmittance is corrected for luminosity factor by the double field (C light source) of JIS Z 8701 : 1999 "Color display method - XYZ color system and X10 Y10 Z10 color system", and the humidity and heat endurance.
- the luminous efficiency correction single transmittance (Ty) before the test was determined.
- the optical laminate was set in a spectrophotometer with an integrating sphere so that the first protective film surface side of the polarizing plate was the detector side and the light entered from the glass substrate side.
- Tp ( ⁇ ) is the transmittance (%) of the measurement sample measured in relation to the linear polarization of the incident wavelength ⁇ (nm) and the parallel Nicol.
- Tc ( ⁇ ) is the transmittance (%) of the measurement sample measured in relation to the linear polarization of the incident wavelength ⁇ (nm) and the cross Nicol.
- the optical laminate was placed in a moist heat environment with a temperature of 80 ° C. and a relative humidity of 90% for 48 hours, and further subjected to a moist heat durability test in which the optical laminate was placed in an environment with a temperature of 23 ° C. and a relative humidity of 60% for 24 hours.
- the luminous efficiency correction single transmittance Ty was determined by the same method as before the moist heat endurance test.
- the amount of change in Ty was calculated from the luminous efficiency correction unit transmittance Ty after the wet heat durability test and before the test based on the following formula, and the wet heat durability was evaluated according to the following criteria.
- the evaluation results are shown in Table 2.
- Ty change amount (%)
- Ty change amount is 1.0% or less 3: Ty change amount is more than 1.0% and 2.0% or less 2: Ty change amount is more than 2.0% and 3.0% or less 1 : Ty change amount is more than 3.0%
- first protective film 15 first adhesive layer
- 20 second protective film 25 second adhesive layer
- 30 polarizing film 10 first protective film, 15 first adhesive layer, 20 second protective film, 25 second adhesive layer, 30 polarizing film.
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Abstract
Description
[1]第1保護フィルム、第1接着剤層、偏光フィルム、第2接着剤層、及び第2保護フィルムをこの順に含む偏光板であって、
前記第1接着剤層は、1種以上のカチオン重合開始剤を含む第1カチオン重合型接着剤の硬化物層であり、
前記第2接着剤層は、1種以上のカチオン重合開始剤を含む第2カチオン重合型接着剤の硬化物層であり、
前記第1カチオン重合型接着剤に含まれる前記1種以上のカチオン重合開始剤は、第1カチオン重合開始剤を含み、
前記第1カチオン重合開始剤は、カチオン成分と、下記式(i):
(式中、Yは置換基(ハロゲン原子を含む基を除く)を有していてもよい、炭素数6~30のアリール基又は炭素数4~30の複素環式基、又はハロゲン原子を示す。Phfは水素原子の少なくとも1つが、パーフルオロアルキル基、パーフルオロアルコキシ基、及びハロゲン原子から選択される少なくとも1種で置換されたフェニル基を示す。kは0~4のいずれかの整数である。)
で表されるアニオン成分とからなるボレート塩であり、
前記第1カチオン重合開始剤の分子量は、前記第2カチオン重合型接着剤に含まれる前記1種以上のカチオン重合開始剤の分子量よりも大きい、偏光板。
[2]前記カチオン成分は、アリールスルホニウムイオンである、[1]に記載の偏光板。
[3]前記第1カチオン重合型接着剤及び前記第2カチオン重合型接着剤は、カチオン重合性化合物をさらに含み、
前記第1カチオン重合型接着剤に含まれる前記1種以上のカチオン重合開始剤の含有量及び前記第2カチオン重合型接着剤に含まれる前記1種以上のカチオン重合開始剤の含有量は、前記カチオン重合性化合物100質量部に対して0.5質量部以上5質量部以下である、[1]又は[2]に記載の偏光板。
[4]前記第1保護フィルムは、(メタ)アクリル系樹脂又はセルロースエステル系樹脂から構成される、[1]~[3]のいずれかに記載の偏光板。
[5]前記第2保護フィルムにおける前記第2接着剤層側とは反対側に粘着剤層をさらに有する、[1]~[4]のいずれかに記載の偏光板。
図1に示されるように偏光板は、第1保護フィルム10、第1接着剤層15、偏光フィルム30、第2接着剤層25、及び第2保護フィルム20をこの順に含む。すなわち、第1保護フィルム10は第1接着剤層15を介して偏光フィルム30の一方の面に積層され、第2保護フィルム20は第2接着剤層25を介して偏光フィルム30の他方の面に積層される。
第1接着剤層15は、第1保護フィルム10及び偏光フィルム30と接していることが好ましい。第2接着剤層25は、偏光フィルム30及び第2保護フィルム20と接していることが好ましい。
偏光板が長尺物やその巻回ロールである場合、耐カール性とは、長尺物やその巻回ロールから裁断された枚葉体についての耐カール性をいう。偏光板が枚葉体である場合、耐カール性とは、該枚葉体又は該枚葉体から裁断されるさらに小サイズの枚葉体についての耐カール性をいう。
偏光フィルム30は、自然光からある一方向の直線偏光を選択的に透過する機能を有するフィルムである。例えば、ポリビニルアルコール系樹脂フィルムにヨウ素を吸着・配向させたヨウ素系偏光フィルム、ポリビニルアルコール系樹脂フィルムに二色性染料を吸着・配向させた染料系偏光フィルム、及びリオトロビック液晶状態の二色性染料をコーティングし、配向・固定化した塗布型偏光フィルム等が挙げられる。これらの偏光フィルムは、自然光からある一方向の直線偏光を選択的に透過し、もう一方向の直線偏光を吸収するため吸収型偏光フィルムと呼ばれている。
第1保護フィルム10及び第2保護フィルム20はそれぞれ、透光性を有する(好ましくは光学的に透明な)熱可塑性樹脂、例えば、鎖状ポリオレフィン系樹脂(ポリプロピレン系樹脂等)、環状ポリオレフィン系樹脂(ノルボルネン系樹脂等)のようなポリオレフィン系樹脂;トリアセチルセルロース、ジアセチルセルロースのようなセルロースエステル系樹脂;ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンテレフタレートのようなポリエステル系樹脂;ポリカーボネート系樹脂;(メタ)アクリル系樹脂;又はこれらの混合物、共重合物等からなる樹脂フィルムであることができる。
中でも、第1保護フィルム10及び第2保護フィルム20はそれぞれ、ポリエステル系樹脂、ポリカーボネート系樹脂、ポリオレフィン系樹脂、(メタ)アクリル系樹脂及びセルロースエステル系樹脂からなる群より選択される樹脂から構成されることが好ましい。
本明細書において、「(メタ)アクリル」とは、メタクリル及び/又はアクリルを意味し、「(メタ)アクリレート」などというときの「(メタ)」も同様の意味である。
ポリカーボネート系樹脂は、炭酸とグリコール又はビスフェノールから形成されるポリエステルである。
第1接着剤層15は、1種以上のカチオン重合開始剤を含む第1カチオン重合型接着剤の硬化物層であり、第2接着剤層25は、1種以上のカチオン重合開始剤を含む第2カチオン重合型接着剤の硬化物層である。
第1及び第2カチオン重合型接着剤はそれぞれ、通常、カチオン重合性化合物とカチオン重合開始剤とを含む。
カチオン重合開始剤は、可視光線、紫外線、X線、又は電子線のような活性エネルギー線の照射によって、カチオン種又はルイス酸を発生し、カチオン硬化性化合物の重合反応を開始させるものである。
(式中、Yは置換基(ハロゲン原子を含む基を除く)を有していてもよい、炭素数6~30のアリール基又は炭素数4~30の複素環式基、又はハロゲン原子を示す。Phfは水素原子の少なくとも1つが、パーフルオロアルキル基、パーフルオロアルコキシ基、及びハロゲン原子から選択される少なくとも1種で置換されたフェニル基を示す。kは0~4のいずれかの整数である。Yが複数ある場合、複数のYは同じであってもよいし異なっていてもよい。Phfが複数ある場合、複数のRhfは同じであってもよいし異なっていてもよい。)
で表されるアニオン成分とからなるボレート塩である。
第1接着剤層15を形成する第1カチオン重合型接着剤は1種以上のカチオン重合開始剤を含み、該1種以上のカチオン重合開始剤は、第1カチオン重合開始剤を含む。第1カチオン重合開始剤は、カチオン成分と上記式(i)で表されるアニオン成分とからなるボレート塩である。
第1カチオン重合開始剤は、1種又は2種以上のカチオン成分を含んでいてもよく、式(i)で表される1種又は2種以上のアニオン成分を含んでいてもよい。
式(i)中のYにおける炭素数4~30の複素環式基は、炭素数4~30の複素環から1個の水素原子を除いた基である。前記複素環としては、オキセタン環、テトラヒドロフラン環、モルホリン環等の酸素原子を含む複素環;チオフェン環、チアゾール環等の硫黄原子を含む複素環;ピロール環、イミダゾリン環、インドール環等の窒素原子を含む複素環等が挙げられる。
0であることがさらに好ましい。
中でも偏光板の耐カール性の観点から、好ましくはアリールスルホニウムイオンである。偏光板の耐カール性の観点から、第1カチオン重合開始剤のカチオン成分は、より好ましくは、4,4’-ビス(ジフェニルスルホニオ)ジフェニルスルフィドカチオンを含む。
第2カチオン重合開始剤は、1種又は2種以上のカチオン成分を含んでいてもよく、1種又は2種以上のアニオン成分を含んでいてもよい。
アリールスルホニウム塩を構成するカチオン成分としては、トリフェニルスルホニウムカチオン、4,4’-ビス(ジフェニルスルホニオ)ジフェニルスルフィドカチオン等のアリールスルホニウムイオンが挙げられる。アリールヨードニウム塩を構成するカチオン成分としては、ジフェニルヨードニウムカチオン等のアリールヨードニウムイオンが挙げられる。アリールジアゾニウム塩を構成するカチオン成分としては、ベンゼンジアゾニウムカチオン等のアリールジアゾニウムイオンが挙げられる。鉄-アレーン錯体は、例えばシクロペンタジエニル鉄(II)アレーンカチオン錯塩である。
偏光板の耐カール性の観点から、第2カチオン重合型接着剤に含まれるカチオン重合開始剤は、アニオン成分が上記式(i)で表されるアニオンではないことが好ましく、ボレートアニオンではないことがより好ましい。
なお、カチオン重合開始剤の量が過度に多くなると、接着剤層中のイオン性物質が増加することで接着剤層の吸湿性が高くなり、偏光板の耐久性が低下する可能性がある。
第1カチオン重合型接着剤及び第2カチオン重合型接着剤に含まれるカチオン重合性化合物は、紫外線、可視光、電子線、X線等の活性エネルギー線の照射によりカチオン重合反応が進行し、硬化する化合物又はオリゴマーをいい、エポキシ化合物、オキセタン化合物、ビニル化合物等を例示することができる。中でも、好ましいカチオン重合性化合物はエポキシ化合物である。エポキシ化合物とは、分子内に1個以上、好ましくは2個以上のエポキシ基を有する化合物である。エポキシ化合物は、1種のみを単独で使用してもよいし2種以上を併用してもよい。エポキシ化合物としては、脂環式エポキシ化合物、芳香族エポキシ化合物、水素化エポキシ化合物、脂肪族エポキシ化合物等を挙げることができる。中でも、耐候性、硬化速度及び接着性の観点から、エポキシ化合物は、脂環式エポキシ化合物や脂肪族エポキシ化合物を含むことが好ましく、脂環式エポキシ化合物を含むことがより好ましい。
第1カチオン重合型接着剤及び第2カチオン重合型接着剤は、1種又は2種以上のカチオン重合性化合物を含むことができる。
B:3,4-エポキシ-6-メチルシクロヘキシルメチル 3,4-エポキシ-6-メチルシクロヘキサンカルボキシレート、
C:エチレンビス(3,4-エポキシシクロヘキサンカルボキシレート)、
D:ビス(3,4-エポキシシクロヘキシルメチル) アジペート、
E:ビス(3,4-エポキシ-6-メチルシクロヘキシルメチル) アジペート、
F:ジエチレングリコールビス(3,4-エポキシシクロヘキシルメチルエーテル)、
G:エチレングリコールビス(3,4-エポキシシクロヘキシルメチルエーテル)、
H:2,3,14,15-ジエポキシ-7,11,18,21-テトラオキサトリスピロ[5.2.2.5.2.2]ヘンイコサン、
I:3-(3,4-エポキシシクロヘキシル)-8,9-エポキシ-1,5-ジオキサスピロ[5.5]ウンデカン、
J:4-ビニルシクロヘキセンジオキサイド、
K:リモネンジオキサイド、
L:ビス(2,3-エポキシシクロペンチル)エーテル、
M:ジシクロペンタジエンジオキサイド。
第1及び/又は第2カチオン重合型接着剤は、必要に応じて、その他の添加剤を含むことができる。添加剤としては、例えば、イオントラップ剤、酸化防止剤、連鎖移動剤、重合促進剤(ポリオール等)、増感剤、増感助剤、光安定剤、粘着付与剤、熱可塑性樹脂、充填剤、流動調整剤、可塑剤、消泡剤、レベリング剤、シランカップリング剤、色素、帯電防止剤、紫外線吸収剤が挙げられる。
偏光フィルム30の一方の面に第1接着剤層15を介して第1保護フィルム10を積層接着し、偏光フィルム30の他方の面に第2接着剤層25を介して第2保護フィルム20を積層接着することにより、本発明に係る偏光板が得られる。第1保護フィルム10及び第2保護フィルム20(これらを総称して単に「保護フィルム」ともいう。)は、段階的に片面ずつ積層接着してもよいし、両面の保護フィルムを一段階で積層接着してもよい。
高湿環境下に置かれても、耐カール性効果が効果的に得られ得ること、とりわけ、第1保護フィルム10側を凹とし、第2保護フィルム20側を凸とするカールを効果的に抑制し得ることから、偏光板は、例えば次のような構成を有することが好ましい。
〔a〕第1保護フィルム10と第2保護フィルム20とが異なる樹脂から構成されるフィルムである。
〔b〕上記〔a〕において、第1保護フィルム10が(メタ)アクリル系樹脂フィルム又はセルロースエステル系樹脂フィルムである。
〔c〕上記〔b〕において、第2保護フィルム20が環状ポリオレフィン系樹脂フィルムである。
〔d〕上記〔a〕~〔c〕のいずれかにおいて、第1カチオン重合開始剤がアリールスルホニウムイオンであるカチオン成分と上記式(i)で表されるアニオン成分とからなるボレート塩であり、第2カチオン重合開始剤がPF6 -をアニオン成分とするカチオン重合開始剤を含む。
〔e〕上記〔d〕において、第1カチオン重合開始剤がアリールスルホニウムイオンであるカチオン成分とB(C6F5)4 -であるアニオン成分とからなるボレート塩である。
〔f〕上記〔d〕又は〔e〕において、第2カチオン重合開始剤がアリールスルホニウムイオンであるカチオン成分とPF6 -であるアニオン成分とからなるカチオン重合開始剤を含む。
〔g〕上記〔a〕~〔f〕のいずれかにおいて、第1カチオン重合型接着剤は第1カチオン重合開始剤のみを含み、第2カチオン重合型接着剤はアリールスルホニウムイオンであるカチオン成分とPF6 -であるアニオン成分とからなるカチオン重合開始剤のみを含む。
〔h〕上記〔g〕において、第1カチオン重合開始剤のカチオン成分がトリフェニルスルホニウムカチオン及び/又は4,4’-ビス(ジフェニルスルホニオ)ジフェニルスルフィドカチオンであり、第2カチオン重合型接着剤に含まれるカチオン重合開始剤のカチオン成分がトリフェニルスルホニウムカチオン及び/又は4,4’-ビス(ジフェニルスルホニオ)ジフェニルスルフィドカチオンである。
(6-1)光学機能性フィルム
偏光板は、所望の光学機能を付与するための、偏光フィルム30以外の他の光学機能性フィルムを備えることができ、その好適な一例は位相差フィルムである。上述のように、第1保護フィルム10及び/又は第2保護フィルム20が位相差フィルムを兼ねることもできるが、保護フィルムとは別途に位相差フィルムを積層することもできる。後者の場合、位相差フィルムは、粘着剤層や接着剤層を介して第1保護フィルム10及び/又は第2保護フィルム20の外面に積層することができる。
本発明に係る偏光板は、これを液晶セル等の画像表示素子、又は他の光学部材に貼合するための粘着剤層を含むことができる。粘着剤層は、保護フィルムの外面に積層することができる。粘着剤層は、第1保護フィルムの外面に積層してもよいし、第2保護フィルムの外面に積層してもよい。
本発明に係る偏光板は、その表面(保護フィルム表面)を仮着保護するためのプロテクトフィルムを含むことができる。プロテクトフィルムは、例えば画像表示素子や他の光学部材に偏光板が貼合された後、それが有する粘着剤層ごと剥離除去される。
〔2〕カチオン重合性化合物A-2:ネオペンチルグリコールジグリシジルエーテル(ナガセケムテックス(株)製、商品名「EX-211L」)
〔3〕カチオン重合性化合物A-3:4-ヒドロキシブチルビニルエーテル(日本カーバイド製、商品名「HBVE」)
〔4〕カチオン重合性化合物A-4:メタクリル酸メチルーメタクリル酸グリジジルエーテル共重合体(カチオン重合性ポリマー)(日油製、商品名「マープルーフG-01100」)
〔5〕カチオン重合開始剤B-1:下記カチオン成分及びアニオン成分からなるカチオン重合開始剤。分子量1050の化合物と分子量1915の化合物の混合物((株)エストケム製、商品名「PAG-20008」)
表1に記載のカチオン重合性化合物及びカチオン重合開始剤を表1に記載の配合割合で混合し、脱泡して、液状のカチオン重合型接着剤A~Nをそれぞれ調製した。表1の数値は質量部を示す。カチオン重合開始剤B-1及びB-2は、50質量%プロピレンカーボネート溶液として配合したが、表1に示される数値は、それに含まれる固形分としての量である。
(1)偏光板の作製
表2に示される第1保護フィルムの片面にコロナ放電処理を施し、そのコロナ放電処理面に、表2に示される第1カチオン重合型接着剤をバーコーターを用いて硬化後の厚みが約5μmとなるように塗工した。次いで、その塗工面に厚み25μmのポリビニルアルコール(PVA)-ヨウ素系偏光フィルムを貼合した。次に、表2に示される第2保護フィルムの片面にコロナ放電処理を施し、そのコロナ放電処理面に、表2に示される第2カチオン重合型接着剤をバーコーターを用いて硬化後の厚みが約5μmとなるように塗工した。その塗工面に、上で作製した第1保護フィルム付の偏光フィルムを偏光フィルム側で重ね、貼合ロールを用いて押圧、貼合して積層体を得た。この積層体に対して、その第2保護フィルム側から、ベルトコンベア付の紫外線照射装置〔ランプはフュージョンUVシステムズ社製の「Dバルブ」使用〕を用いて積算光量が200mJ/cm2(UVB)となるように紫外線を照射し、両面の接着剤層を硬化させて偏光板を作製した。
〔1〕保護フィルムa:紫外線吸収剤を含有する厚み60μmの(メタ)アクリル系樹脂フィルム。該フィルムを構成する(メタ)アクリル系樹脂は、メタクリル酸メチルとアクリル酸メチルとを96:4の質量比で共重合させた共重合体である。
〔2〕保護フィルムb:厚み60μmのセルロースエステル系樹脂フィルム(富士写真フイルム(株)製、商品名「TG」)
〔3〕保護フィルムc:環状ポリオレフィン系樹脂(ノルボルネン系樹脂)からなる厚み50μmの位相差フィルム(日本ゼオン(株)製、商品名「ZEONOR」)
〔4〕保護フィルムd:(メタ)アクリル系樹脂からなる厚み40μmの位相差フィルム(LGケミカル(株)製、商品名「GA-01」)
上記(1)で作製した偏光板から、温度25℃相対湿度55%の環境下で、8cm×8cmサイズの枚葉体を切り出した。この枚葉体において、1組の対向する2辺は偏光フィルムの吸収軸方向と平行である。この時、枚葉体はカールしていなかった(カール量0mm)。この枚葉体を温度25℃相対湿度90%の環境下に2時間放置した後、枚葉体のカール量を計測した。カール量は、水平な台の上に湾曲した枚葉体を下に凸になるように置き、台から枚葉体の4つの角部までの高さを定規でそれぞれ計測し、得られた4点の値の平均値として求めた。得られたカール量に基づき、下記の基準で耐カール性を評価した。評価結果を表2に示す。
4:カール量が1mm超2mm以下である
3:カール量が2mm超5mm以下である
2:カール量が5mm超20mm以下である
1:カールが強すぎて偏光板が丸まった状態になっている
(メタ)アクリル系粘着剤の有機溶剤溶液を、離型処理が施されたポリエチレンテレフタレートからなる厚み38μmのセパレートフィルムの離型処理面に、ダイコーターにて乾燥後の厚みが20μmとなるように塗工し、セパレートフィルム付シート状粘着剤を作製した。次いで、上記(1)で作製した偏光板の第2保護フィルム面にコロナ放電処理を施し、そのコロナ放電処理面に、上で得たシート状粘着剤のセパレートフィルムと反対側の面(粘着剤面)をラミネーターにより貼合した後、温度23℃相対湿度65%の条件で7日間養生して、粘着剤層を有する偏光板を得た。
上記(3)で作製した粘着剤層を有する偏光板から、3cm×3cmサイズの枚葉体を切り出した。この枚葉体において、1組の対向する2辺は偏光フィルムの吸収軸方向と平行である。この枚葉体からセパレートフィルムを剥離し、露出した粘着剤層面をガラス基板に貼合した。ガラス基板には、コーニング社製の無アルカリガラス 商品名「Eagle XG」を使用した。得られた光学積層体について、積分球付き分光光度計(日本分光(株)製、製品名「V7100」)を用いて波長380~780nmの範囲におけるMD透過率とTD透過率を測定し、各波長における単体透過率を算出した。算出した単体透過率について、JIS Z 8701:1999「色の表示方法-XYZ表色系及びX10Y10Z10表色系」の2度視野(C光源)により視感度補正を行い、湿熱耐久試験前の視感度補正単体透過率(Ty)を求めた。なお、光学積層体は、偏光板の第1保護フィルム面側をディテクター側とし、ガラス基板側から光が入光するように積分球付き分光光度計にセットした。
単体透過率(λ)=(Tp(λ)+Tc(λ))/2で定義される。
Tp(λ)は、入射する波長λ(nm)の直線偏光とパラレルニコルの関係で測定した測定サンプルの透過率(%)である。
Tc(λ)は、入射する波長λ(nm)の直線偏光とクロスニコルの関係で測定した測定サンプルの透過率(%)である。
湿熱耐久試験後及び試験前の視感度補正単体透過率Tyから、下記式に基づきTy変化量を算出し、下記の基準で湿熱耐久性を評価した。評価結果を表2に示す。
Ty変化量(%)=|Ty(湿熱耐久試験後)-Ty(湿熱耐久試験前)|
3:Ty変化量が1.0%超2.0%以下である
2:Ty変化量が2.0%超3.0%以下である
1:Ty変化量が3.0%超である
Claims (5)
- 第1保護フィルム、第1接着剤層、偏光フィルム、第2接着剤層、及び第2保護フィルムをこの順に含む偏光板であって、
前記第1接着剤層は、1種以上のカチオン重合開始剤を含む第1カチオン重合型接着剤の硬化物層であり、
前記第2接着剤層は、1種以上のカチオン重合開始剤を含む第2カチオン重合型接着剤の硬化物層であり、
前記第1カチオン重合型接着剤に含まれる前記1種以上のカチオン重合開始剤は、第1カチオン重合開始剤を含み、
前記第1カチオン重合開始剤は、カチオン成分と、下記式(i):
(式中、Yは置換基(ハロゲン原子を含む基を除く)を有していてもよい、炭素数6~30のアリール基又は炭素数4~30の複素環式基、又はハロゲン原子を示す。Phfは水素原子の少なくとも1つが、パーフルオロアルキル基、パーフルオロアルコキシ基、及びハロゲン原子から選択される少なくとも1種で置換されたフェニル基を示す。kは0~4のいずれかの整数である。)
で表されるアニオン成分とからなるボレート塩であり、
前記第1カチオン重合開始剤の分子量は、前記第2カチオン重合型接着剤に含まれる前記1種以上のカチオン重合開始剤の分子量よりも大きい、偏光板。 - 前記カチオン成分は、アリールスルホニウムイオンである、請求項1に記載の偏光板。
- 前記第1カチオン重合型接着剤及び前記第2カチオン重合型接着剤は、カチオン重合性化合物をさらに含み、
前記第1カチオン重合型接着剤に含まれる前記1種以上のカチオン重合開始剤の含有量及び前記第2カチオン重合型接着剤に含まれる前記1種以上のカチオン重合開始剤の含有量は、前記カチオン重合性化合物100質量部に対して0.5質量部以上5質量部以下である、請求項1又は2に記載の偏光板。 - 前記第1保護フィルムは、(メタ)アクリル系樹脂又はセルロースエステル系樹脂から構成される、請求項1~3のいずれか1項に記載の偏光板。
- 前記第2保護フィルムにおける前記第2接着剤層側とは反対側に粘着剤層をさらに有する、請求項1~4のいずれか1項に記載の偏光板。
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