WO2019116969A1 - 硬化性組成物、光学積層体及び画像表示装置 - Google Patents
硬化性組成物、光学積層体及び画像表示装置 Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
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- 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
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- C08F26/00—Homopolymers and 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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F26/06—Homopolymers and 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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/025—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
- C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
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- 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
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J139/00—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Adhesives based on derivatives of such polymers
- C09J139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
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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
- C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
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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
- C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C09J201/025—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing nitrogen atoms
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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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
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
Definitions
- the present invention relates to a curable composition.
- the present invention also relates to an optical laminate comprising a cured product layer composed of a cured product of the curable composition, and an image display device comprising the optical laminate.
- the durability is also required in the same way for optical members constituting liquid crystal displays and the like, for example, optical laminates. That is, although the optical member incorporated in a liquid crystal display or the like may be placed under a high temperature or high temperature / high humidity environment, or under an environment in which high temperature and low temperature are repeated, the optical member It is required that the optical characteristics do not deteriorate even under these circumstances.
- the optical laminated body containing the hardened
- An example of such an optical laminate is a polarizing plate.
- JP-A 2009-008860 Patent Document 1 discloses a polarizing plate in which a transparent protective film is laminated on a polarizer via a cured product layer (adhesive layer).
- An object of the present invention is a curable composition comprising a cured product layer composed of a cured product of a curable composition and capable of providing an optical laminate having good wet heat durability (durable in a high temperature and high humidity environment). It is in providing a composition.
- Another object of the present invention is to provide an optical laminate including a cured product layer composed of a cured product of a curable composition and having good wet heat durability, and an image display apparatus including the same.
- the present invention provides a curable composition, an optical laminate, an image display device, and an adhesive composition for a polarizing plate described below.
- An image display device comprising the optical laminate according to any one of [4] to [7] and an image display element.
- An adhesive composition for a polarizing plate comprising an oxazoline group-containing polymer (A) and an iodine compound (B).
- curable composition capable of providing an optical laminate having good wet heat durability, which comprises a cured product layer composed of a cured product of the curable composition.
- the curable composition concerning this invention contains an oxazoline group containing polymer (A) and an iodine compound (B).
- curable composition (S) The cured product layer composed of the cured product of the curable composition (S) is also referred to as "first cured product layer”.
- an optical laminate having good wet heat durability can be provided.
- the oxazoline group-containing polymer (A) is preferably a polymer having an oxazoline group in the molecule, and preferably a polymer having an oxazoline group in the side chain.
- the skeleton structure of the oxazoline group-containing polymer (A) is not particularly limited, but may be, for example, one or more skeletons selected from (meth) acrylic skeleton, styrene skeleton, olefin skeleton, ester skeleton, carbonate skeleton and the like it can.
- (meth) acrylic represents at least one selected from the group consisting of acrylic and methacrylic. The same applies to the notation of “(meth) acryloyl” and “(meth) acrylate”.
- the oxazoline group-containing polymer (A) can have an oxazoline group on the side chain of the above-mentioned skeleton structure.
- the oxazoline group-containing polymer (A) may contain a constitutional unit having a oxazoline group in the side chain (a constitutional unit derived from an oxazoline group-containing monomer) and a constitutional unit not having an oxazoline group.
- a preferred example of the oxazoline group-containing polymer (A) comprises a structural unit having a (meth) acrylic skeleton as a main component of the structural unit, and a structural unit having an oxazoline group in a side chain as a copolymer component And (x) an oxazoline group-containing (meth) acrylic polymer introduced with a structural unit of
- the oxazoline group-containing polymer (A) may be one obtained by copolymerizing an oxazoline group-containing monomer, or one containing an oxazoline group by modifying the side chain functional group of the polymer.
- oxazoline group examples include 2-oxazoline group, 3-oxazoline group, 4-oxazoline group and the like.
- the oxazoline group is preferably a 2-oxazoline group or the like.
- oxazoline group-containing monomer examples include 2-isopropenyl-2-oxazoline, vinyl-2-oxazoline and the like.
- the weight average molecular weight of the oxazoline group-containing polymer (A) is preferably 5,000 or more, and more preferably 10,000 or more.
- the weight average molecular weight is in the above range, the wet heat durability of the optical laminate is improved, the adhesion between the optical film and the first cured product layer in the optical laminate, the first cured product layer and the first thermoplastic resin It may be advantageous from the viewpoint of adhesion to the resin film.
- the weight average molecular weight of the oxazoline group-containing polymer (A) is usually 1,000,000 or less.
- the weight average molecular weight of the oxazoline group-containing polymer (A) can be measured as a standard polystyrene conversion value by gel permeation chromatography (GPC).
- the amount of oxazoline groups of the oxazoline group-containing polymer (A) is preferably 0.4 mmol / g ⁇ solid or more. If the amount of oxazoline group is smaller than the above range, the wet heat durability of the optical laminate may be disadvantageous. From this point of view, the oxazoline group content of the oxazoline group-containing polymer is more preferably 3 mmol / g solid or more, still more preferably 5 mmol / g solid or more and 9 mmol / g solid or less.
- the upper limit of the amount of oxazoline group is not particularly limited, but is usually 50 mmol / g ⁇ solid or less.
- the oxazoline group-containing polymer (A) is preferably an aqueous system, that is, a water-soluble polymer, or a water-dispersible polymer. From the viewpoint of the optical properties of the first cured product layer, the oxazoline group-containing polymer (A) is preferably a water-soluble polymer.
- a commercial item may be used as the oxazoline group-containing polymer (A).
- oxazoline group-containing acrylic polymers such as Epocross WS-300, Epocross WS-500, Epocross WS-700 (all trade names) manufactured by Nippon Shokubai Co., Ltd .; Epocross K-1000 series made by Nippon Shokubai Co., Ltd.
- Epocross Examples include oxazoline group-containing acrylic / styrene polymers such as K-2000 series and Epocross RPS series (all trade names).
- the oxazoline group-containing polymer (A) can be used in combination of two or more. Wet heat durability and optical properties of the optical laminate, adhesion between the optical film and the first cured product layer in the optical laminate, adhesion between the first cured product layer and the first thermoplastic resin film, and From the viewpoint of water resistance of the first cured product layer, the oxazoline group-containing polymer (A) is preferably an oxazoline group-containing acrylic polymer such as Epocross WS-300, Epocross WS-500, or Epocross WS-700.
- the content of the oxazoline group-containing polymer (A) is preferably 5% by mass to 95% by mass, more preferably 10% by mass or more, when the solid content concentration of the curable composition (S) is 100% by mass. It is 90 mass% or less, more preferably 20 mass% or more and 85 mass% or less.
- the content of the oxazoline group-containing polymer (A) is within the above range, the wet heat durability of the optical laminate is improved, the adhesion between the optical film and the first cured product layer in the optical laminate, It is preferable from the viewpoint of the adhesiveness between the first cured product layer and the first thermoplastic resin film.
- the solid content concentration refers to the total concentration of components other than the solvent contained in the curable composition (S).
- the iodine compound (B) is a compound containing an iodine element.
- the curable composition (S) may contain one type of iodine compound (B), or may contain two or more types of iodine compound (B).
- Inorganic iodide salt Alkali metal salt of iodide such as lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide and the like; Iodide alkaline earth metal salts such as beryllium iodide, magnesium iodide, calcium iodide, barium iodide, strontium iodide; Light metal salts or heavy metal salts of iodides such as boron iodide, aluminum iodide, zinc iodide, titanium iodide, copper iodide, vanadium iodide, chromium iodide, manganese iodide, nickel iodide and the like; Ammonium iodide b) Other inorganic iodine compounds iodide, aluminum iodide, zinc iodide, titanium io
- the iodine compound (B) is preferably an iodide salt from the viewpoint of solubility or dispersibility in the composition, and is preferably an inorganic iodide salt. It is more preferable that For the same reason, the iodine compound (B) is preferably water soluble.
- the content of the iodine compound (B) in the curable composition (S) is usually 1 part by mass or more with respect to 100 parts by mass of the oxazoline group-containing polymer (A) from the viewpoint of enhancing the wet heat durability of the optical laminate.
- 300 parts by mass or less preferably 2 parts by mass or more and 250 parts by mass or less, more preferably 5 parts by mass or more and 200 parts by mass or less, further preferably 10 parts by mass or more and 180 parts by mass or less
- it is 10 parts by mass or more and 150 parts by mass or less.
- the content of the iodine compound (B) is 10 parts by mass or more and 160 parts by mass or less, 10 parts by mass or more and 150 parts by mass or less, per 100 parts by mass of the oxazoline group-containing polymer (A). It is the mass part or more and 140 parts by mass or less, or 10 parts by mass or more and 120 parts by mass or less.
- the content of the iodine compound (B) is excessively small, it is difficult to obtain the effect of containing the iodine compound (B) to improve the wet heat durability of the optical laminate.
- the content of the iodine compound (B) is excessively large, adhesion between the optical film and the first cured product layer in the optical laminate, and between the first cured product layer and the first thermoplastic resin film At least one of the adhesion between them tends to decrease.
- the curable composition (S) is selected from a compound (C) having a carboxyl group and an acid anhydride of the compound (C) Can further include at least one.
- the compound (C) which has a carboxyl group is also called “compound (C).”
- the compound (C) is a compound having a carboxyl group capable of reacting with the oxazoline group of the oxazoline group-containing polymer (A). Although the derivative of a carboxyl group is also contained in a carboxyl group said here, the acid anhydride of a compound (C) is not contained.
- carboxyl groups include carboxylate anion groups.
- the cation to be a counter ion of a carboxylate anion group include metal ions such as lithium ion, sodium ion and potassium ion; and organic cations such as ammonium ion, sulfonium ion and phosphonium ion.
- the curable composition (S) may contain one type of compound (C) or may contain two or more types of compound (C).
- the curable composition (S) may contain an acid anhydride of one type of compound (C) or may contain an acid anhydride of two or more types of compound (C).
- the curable composition (S) may contain one or more compounds (C) and an acid anhydride of one or more compounds (C).
- the compound (C) has a wet heat durability of the optical laminate, an adhesion between the optical film and the first cured product layer in the optical laminate, and a distance between the first cured product layer and the first thermoplastic resin film. It is preferable that it is a compound (polyfunctional carboxylic acid compound) which has a carboxyl group (or its derivative (s)) in a molecule
- An example of a polyfunctional carboxylic acid compound is a dicarboxylic acid compound.
- dicarboxylic acid compounds include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, tartaric acid, glutamic acid, malic acid and maleic acid Acid, fumaric acid, itaconic acid, muconic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid
- the acid include 2,5-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, diphenylsulfonedicarboxylic acid, dipheny
- polyfunctional carboxylic acid compound is a tricarboxylic acid compound.
- tricarboxylic acid compounds include citric acid, aconitic acid, propane-1,2,3-tricarboxylic acid, trimellitic acid, trimesic acid, hemimellitic acid, biphenyl-3,4 ', 5-tricarboxylic acid, 1,3, 5-cyclohexane tricarboxylic acid and the like.
- Still another example of the polyfunctional carboxylic acid compound is a tetracarboxylic acid compound.
- a tetracarboxylic acid compound pyromellitic acid, diphenyl sulfone tetracarboxylic acid, biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid, naphthalene tetracarboxylic acid, thiophene tetracarboxylic acid, butane tetracarboxylic acid, 1,2,4,5- Examples include tetrakis (4-carboxyphenyl) benzene and the like.
- At least one carboxyl group may be a derivative thereof.
- the compound (C) may have another functional group other than a carboxyl group.
- Another functional group is a hydroxy group.
- the number of carboxyl groups contained in the compound (C) is preferably 2 or 3.
- the polyfunctional carboxylic acid compound may be a polymer having two or more carboxyl groups (or derivatives thereof) in the molecule.
- An example of the polymer is a carboxyl group-modified polymer.
- One example of the carboxyl group-modified polymer is a carboxyl group-modified polyvinyl alcohol polymer.
- the carboxyl group-modified polyvinyl alcohol polymer is a polyvinyl alcohol polymer modified by introducing a carboxyl group or a derivative thereof into a side chain.
- carboxyl groups include carboxylate anion groups.
- the example of the cation used as the counter ion of carboxylate anion group is as above-mentioned.
- An example of a preferred cation is sodium ion.
- a polyvinyl alcohol polymer constituting the main chain of a carboxyl group-modified polyvinyl alcohol polymer is a vinyl alcohol homopolymer (completely saponified polyvinyl alcohol) obtained by saponifying polyvinyl acetate which is a homopolymer of vinyl acetate Or a partially saponified polyvinyl alcohol), or a polyvinyl alcohol copolymer obtained by saponifying a copolymer of vinyl acetate and another monomer copolymerizable therewith. It is also good.
- Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and (meth) acrylamides having an ammonium group.
- the degree of saponification of the carboxyl group-modified polyvinyl alcohol polymer is usually 80% by mole or more and 100% by mole or less, and preferably 85% by mole or more (eg, 88% by mole or more).
- the degree of saponification of the carboxyl group-modified polyvinyl alcohol polymer can be measured according to JIS K 6726: 1994.
- the modification degree of the carboxyl group-modified polyvinyl alcohol polymer is determined by the wet heat durability of the optical laminate, the adhesion between the optical film and the first cured product layer in the optical laminate, the first cured product layer and the first thermoplastic resin From the viewpoint of enhancing the adhesion with the resin film and the water resistance of the first cured product layer, it is preferably 0.5 mol% or more and 40 mol% or less, more preferably 1 mol% or more and 20 mol% or less is there.
- the degree of modification can be measured, for example, by 1 H-NMR.
- the average degree of polymerization of the carboxyl group-modified polyvinyl alcohol polymer is usually 100 or more and 3,000 or less.
- the average degree of polymerization of the carboxyl group-modified polyvinyl alcohol polymer can be measured according to JIS K 6726: 1994.
- the compound (C) has a molecular weight of 1000 or less. This molecular weight is a molecular weight calculated from a chemical structural formula, but when compound (C) is a polymer, it is a number average molecular weight measured as a standard polystyrene equivalent value by gel permeation chromatography (GPC). May be
- the use of the compound (C) having a molecular weight of 1000 or less may be advantageous in enhancing the wet heat durability of the optical laminate.
- the molecular weight of the compound (C) is preferably 800 or less, and more preferably 500 or less.
- the molecular weight of the compound (C) is determined by the wet heat durability of the optical laminate, the adhesion between the optical film and the first cured product layer in the optical laminate, and the first cured product layer and the first thermoplastic resin film Preferably it is 90 or more, More preferably, it is 100 or more from an adhesive viewpoint between these.
- Preferred examples of the compound (C) are citric acid, malic acid, maleic acid and tartaric acid.
- carboxylic acid anhydride is mentioned.
- carboxylic acid anhydride include acetic anhydride, propionic acid anhydride, oxalic acid anhydride, succinic acid anhydride, maleic acid anhydride, phthalic acid anhydride, benzoic acid anhydride and the like.
- the content of at least one selected from the compound (C) and the acid anhydride of the compound (C) is from 100 parts by mass of the oxazoline group-containing polymer (A) from the viewpoint of enhancing the wet heat durability of the optical laminate.
- the amount is preferably 0.2 parts by mass or more and 15 parts by mass or less, and particularly preferably 0.3 parts by mass or more and 15 parts by mass or less.
- the content of at least one selected from the compound (C) and the acid anhydride of the compound (C) is 0.3 parts by mass with respect to 100 parts by mass of the oxazoline group-containing polymer (A) More than 10 mass parts or less, 0.5 mass parts or more and 10 mass parts or less 0.5 mass parts or more and 8 mass parts or less or 1 mass parts or more and 8 mass parts or less.
- Compound (D) for promoting the reaction of the oxazoline group of the oxazoline group-containing polymer (A) with the carboxyl group of the compound (C) having a carboxyl group can further contain a compound (D) that promotes the reaction of the oxazoline group of the oxazoline group-containing polymer (A) with the carboxyl group of the compound (C) having a carboxyl group.
- this compound is also referred to as “compound (D)”.
- the promotion referred to here includes the case of initiating the reaction.
- compound (D) is a carboxyl group in a carboxylic acid which is produced by hydrolysis of at least a part of the acid anhydride of compound (C) Initiate or accelerate the reaction with the group.
- Preferred examples of the compound (D) include acid compounds.
- the acid compound is a catalyst for the reaction of the oxazoline group of the oxazoline group-containing polymer (A) with the carboxyl group of the compound (C) and / or the carboxyl group produced by hydrolysis of the acid anhydride of the compound (C). It may be a compound that functions as
- the acid compounds include inorganic acids such as sulfuric acid, hydrogen chloride, nitric acid, phosphoric acid, phosphorous acid and boric acid; p-toluenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, methanesulfonic acid, benzenesulfonic acid, Organic acids such as phenyl phosphoric acid, sulfanilic acid, phenyl phosphonic acid, acetic acid, propionic acid and the like can be mentioned.
- inorganic acids such as sulfuric acid, hydrogen chloride, nitric acid, phosphoric acid, phosphorous acid and boric acid
- p-toluenesulfonic acid dodecylbenzenesulfonic acid, naphthalenesulfonic acid, methanesulfonic acid, benzenesulfonic acid
- Organic acids such as phenyl phosphoric acid, s
- the curable composition (S) may contain one type of compound (D) or may contain two or more types of compound (D).
- the compound (D) may be blended in the curable composition (S) as a solution (for example, an aqueous solution) containing the compound (D).
- the compound (D) has a wet heat durability of the optical laminate, an adhesion between the optical film and the first cured product layer in the optical laminate, and a distance between the first cured product layer and the first thermoplastic resin film.
- relatively strong acids are preferable, and examples of such acid compounds include sulfuric acid, hydrogen chloride (hydrochloric acid), nitric acid, p-toluenesulfonic acid and the like.
- the content of the compound (D) in the curable composition (S) is usually 1 part by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the oxazoline group-containing polymer (A).
- the adhesion between the optical film and the first cured product layer in the optical laminate, and the adhesion between the first cured product layer and the first thermoplastic resin film preferably 3 parts by mass or more It is 100 parts by mass or less, more preferably 5 parts by mass or more and 100 parts by mass or less, still more preferably 10 parts by mass or more and 100 parts by mass or less.
- the content of the compound (D) is 10 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the oxazoline group-containing polymer (A) from the viewpoint of enhancing the wet heat durability of the optical laminate. Or 10 parts by mass or more and 50 parts by mass or less.
- the curable composition (S) is a polymer other than the oxazoline group-containing polymer (A), the iodine compound (B), the compound (C) and the acid anhydride of the compound (C) and the compound (D) Other ingredients can be included.
- curing components and crosslinking agents such as polyvalent aldehydes, melamine compounds, zirconia compounds, zinc compounds, aziridine compounds, glyoxals, glyoxal derivatives, water-soluble epoxy resins and the like; other than carboxyl group-modified polyvinyl alcohol polymers And modified additives such as coupling agents, tackifiers, antioxidants, ultraviolet absorbers, heat stabilizers, and hydrolysis inhibitors.
- the curable composition (S) can contain one or more other components.
- the curable composition (S) preferably contains a solvent.
- the solvent includes water, an organic solvent, or a mixture thereof.
- the solvent preferably contains water, but water and a water-soluble organic solvent may be used in combination.
- the organic solvent include alcohol solvents such as ethanol and 1-methoxy-2-propanol.
- the main component of the solvent is preferably water.
- the main component means that it occupies 50% by mass or more of the total solvent.
- the solid content concentration of the curable composition (S) is usually 0.5% by mass or more and 20% by mass or less, preferably 1% by mass or more and 15% by mass or less.
- the curable composition (S) can be used as a coating liquid for forming a coating film (coating layer) on a substrate.
- a curable composition (S) can be coated on a base material, and a coating film can be formed by hardening a coating layer.
- the substrate is preferably an optical film.
- the optical film will be described later.
- the optical laminate includes an optical film and a first cured product layer composed of a cured product of the curable composition (S).
- the curable composition (S) can also be used as an adhesive composition.
- the curable composition (S) is an adhesive composition for laminating an optical film and a first thermoplastic resin film.
- the optical laminate includes an optical film, a first cured product layer (adhesive layer) composed of a cured product of the curable composition (S), and a first thermoplastic resin film in this order.
- the curable composition (S) is applied to the bonding surface of at least one of the optical film and the first thermoplastic resin film, and the optical film and the first thermoplastic resin are coated via the coating layer. After laminating a resin film to obtain a laminate, it can be produced by curing the coating layer.
- the optical laminate is preferably a polarizing plate in which the optical film is a polarizer.
- the polarizing plate is an optical laminate including a polarizer and a first cured product layer (cured product layer composed of a cured product of a curable composition (S)) laminated on at least one surface of the polarizer. .
- the curable composition (S) which is an adhesive composition is preferably an adhesive composition for a polarizing plate, that is, an adhesive composition used to produce a polarizing plate.
- the curable composition (S) is used, for example, to bond the polarizer and the first thermoplastic resin film.
- the curable composition (S) is preferably an aqueous composition. That is, the curable composition (S) is preferably a solution in which the compounding component is dissolved in a solvent containing water, or a dispersion (for example, an emulsion) in which the compounding component is dispersed in a solvent containing water.
- the viscosity of the curable composition (S) at 25 ° C. is preferably 50 mPa ⁇ sec or less, more preferably 1 mPa ⁇ sec or more and 30 mPa ⁇ sec or less, and 2 mPa ⁇ sec or more and 20 mPa ⁇ sec or less Is more preferred.
- the viscosity at 25 ° C. exceeds 50 mPa ⁇ s, it is difficult to apply uniformly, which may cause uneven coating, and may cause problems such as clogging of piping.
- the viscosity at 25 ° C. of the curable composition (S) can be measured by an E-type viscometer.
- the optical laminate according to the present invention includes an optical film and a first cured product layer (cured product layer composed of a cured product of a curable composition (S)) laminated on at least one surface of the optical film.
- the cured product layer contained in the optical laminate is composed of the cured product of the curable composition (S)
- the wet heat durability of the optical laminate can be made favorable.
- the optical laminate shown in FIG. 1 includes an optical film 30 and a first cured product layer 15 laminated on one surface thereof.
- the first cured product layer 15 can function as an overcoat layer that covers and protects the surface of the optical film 30, an optical functional layer that additionally provides an optical function to the optical film 30, and the like.
- the optical laminate shown in FIG. 2 includes an optical film 30 and a first thermoplastic resin film 10 laminated and bonded to one side of the optical film 30 via the first cured product layer 15.
- the first cured product layer 15 can function as an adhesive layer for bonding the optical film 30 and the first thermoplastic resin film 10.
- first cured product layer 15 and the first thermoplastic resin film 10 be in direct contact with each other.
- the optical laminate shown in FIG. 3 includes an optical film 30, a first thermoplastic resin film 10 laminated and bonded to one side of the optical film 30 via the first cured product layer 15, and the other side of the optical film 30. And a second thermoplastic resin film 20 laminated and bonded via the second cured product layer 25. That is, the optical laminate according to the present invention includes the second thermoplastic resin film 20, the second cured product layer 25, the optical film 30, the first cured product layer 15, and the first thermoplastic resin film 10 in this order. It may be The first cured product layer 15 and the second cured product layer 25 respectively bond an adhesive layer for bonding the optical film 30 and the first thermoplastic resin film 10, and bond the optical film 30 and the second thermoplastic resin film 20. It can function as an adhesive layer.
- first cured product layer 15 and the first thermoplastic resin film 10 be in direct contact with each other.
- optical film 30 and the first cured product layer 15 be in direct contact with each other. It is preferable that the second cured product layer 25 and the second thermoplastic resin film 20 be in direct contact with each other.
- the optical laminated body shown in FIG. 4 is formed by laminating an optical film 30, a first cured product layer 15 laminated on one surface thereof, and a second cured product layer 25 on the other surface of the optical film 30. And a second thermoplastic resin film 20 to be combined.
- the first cured product layer 15 can function as an overcoat layer that covers and protects the surface of the optical film 30, an optical functional layer that additionally provides an optical function to the optical film 30, and the like.
- the second cured product layer 25 can function as an adhesive layer for bonding the optical film 30 and the second thermoplastic resin film 20.
- optical film 30 and the first cured product layer 15 be in direct contact with each other. It is preferable that the second cured product layer 25 and the second thermoplastic resin film 20 be in direct contact with each other.
- the optical laminate shown in FIG. 5 comprises an optical film 30, a first cured product layer 15 deposited on one surface thereof, and a second cured product layer 25 deposited on the other surface of the optical film 30.
- the first cured product layer 15 and the second cured product layer 25 function as an overcoat layer that covers and protects the surface of the optical film 30, an optical functional layer that additionally provides an optical function to the optical film 30, and the like. Can.
- optical film 30 and the first cured product layer 15 be in direct contact with each other. It is preferable that the optical film 30 and the second cured product layer 25 be in direct contact with each other.
- the optical film 30 may be various optical films (films having optical characteristics) that can be incorporated into an image display device such as a liquid crystal display device.
- Examples of the optical film 30 include a polarizer, a retardation film, a brightness enhancement film, an antiglare film, an antireflective film, a diffusion film, a light collection film and the like.
- the optical laminate can include other layers (or films) other than those described above.
- an adhesive laminated on the outer surface of the first thermoplastic resin film 10, the second thermoplastic resin film 20, the first cured material layer 15, the second cured material layer 25 and / or the optical film 30 Agent layer a separate film (also referred to as "release film") laminated on the outer surface of the pressure-sensitive adhesive layer; first thermoplastic resin film 10, second thermoplastic resin film 20, first cured product layer 15, second Protecting film (also referred to as “surface protective film”) laminated on the outer surface of the cured product layer 25 and / or the optical film 30; first thermoplastic resin film 10, second thermoplastic resin film 20, first cured material layer 15, and an optically functional film (or layer) laminated on the outer surface of the second cured product layer 25 and / or the optical film 30 via an adhesive layer or a pressure-sensitive adhesive layer.
- Polarizer A polarizer is a layer or film having a function of selectively transmitting linearly polarized light in one direction from natural light.
- suck and orientate dichroic dye is mentioned, for example.
- a dichroic dye iodine, a dichroic organic dye, etc. are mentioned.
- the polarizer may be a coating type polarizing film in which a dichroic dye in a lyotropic liquid crystal state is coated on a base film and oriented and fixed.
- the above polarizer is called an absorption-type polarizer because it selectively transmits linearly polarized light in one direction from natural light and absorbs linearly polarized light in the other direction.
- the polarizer is not limited to the absorptive polarizer, but is a reflective polarizer that selectively transmits one linearly polarized light from natural light and reflects the linearly polarized light in the other, or linearly polarized light in the other. It may be a scattering type polarizer that scatters, but an absorption type polarizer is preferable in terms of excellent visibility.
- a polyvinyl alcohol-based polarizing film composed of a polyvinyl alcohol-based resin film is more preferable, and a polyvinyl alcohol-based polarizing film having a polyvinyl alcohol-based resin film adsorbed and oriented with a dichroic dye such as iodine or a dichroic dye More preferably, a polyvinyl alcohol-based polarizing film in which iodine is adsorbed and oriented to a polyvinyl alcohol-based resin film is particularly preferable.
- polyvinyl alcohol-type resin what saponified polyvinyl acetate type resin can be used.
- polyvinyl acetate resins include polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate and other monomers copolymerizable therewith.
- examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and (meth) acrylamides having an ammonium group.
- the degree of saponification of the polyvinyl alcohol resin is usually 85% by mole or more and 100% by mole or less, preferably 98% by mole or more.
- the polyvinyl alcohol-based resin may be modified, and for example, polyvinyl formal or polyvinyl acetal modified with aldehydes can also be used.
- the average degree of polymerization of the polyvinyl alcohol resin is usually 1000 or more and 10000 or less, preferably 1500 or more and 5000 or less.
- the average degree of polymerization of the polyvinyl alcohol-based resin can be determined in accordance with JIS K 6726: 1994.
- What formed such a polyvinyl alcohol-type resin into a film is used as a raw film of the polarizing film comprised with the polyvinyl alcohol-type resin film.
- the method of forming a polyvinyl alcohol-based resin into a film is not particularly limited, and a known method is adopted.
- the thickness of the polyvinyl alcohol-based raw film is, for example, 150 ⁇ m or less, preferably 100 ⁇ m or less (eg, 50 ⁇ m or less), and 5 ⁇ m or more.
- the polarizing film comprised with the polyvinyl alcohol-type resin film can be manufactured by a well-known method. Specifically, a step of uniaxially stretching a polyvinyl alcohol-based resin film; a step of adsorbing a dichroic dye by dyeing a polyvinyl alcohol-based resin film with a dichroic dye; a polyvinyl alcohol to which a dichroic dye is adsorbed It can manufacture by the method including the process of processing (crosslinking processing) a system resin film with boric acid aqueous solution; and the process washed with water after the treatment with boric acid aqueous solution.
- the thickness of the polarizer can be 40 ⁇ m or less, preferably 30 ⁇ m or less (eg, 20 ⁇ m or less, further 15 ⁇ m or less, still further 10 ⁇ m or less or 8 ⁇ m or less).
- thin film polarizers can be manufactured more easily, and the thickness of the polarizer is, for example, 20 ⁇ m or less, and further 15 ⁇ m. In the following, it is even easier to set the thickness to 10 ⁇ m or less or 8 ⁇ m or less.
- the thickness of the polarizer is usually 2 ⁇ m or more. Reducing the thickness of the polarizer is advantageous for reducing the thickness of the optical laminate (polarizing plate) and the image display apparatus including the same.
- Retardation Film As a retardation film, a stretched film obtained by uniaxially or biaxially stretching a light-transmitting thermoplastic resin; a film in which a liquid crystalline compound such as a discotic liquid crystal or a nematic liquid crystal is oriented and fixed; A material film in which the above liquid crystal layer is formed on a material film, and the like can be mentioned. Moreover, in the present specification, a zero retardation film is also included in the retardation film.
- the base film is usually a film made of a thermoplastic resin, and one example of the thermoplastic resin is a cellulose ester-based resin such as triacetyl cellulose.
- thermoplastic resin which has translucency, resin etc. which comprise the 1st thermoplastic resin film 10 mentioned later are mentioned.
- the zero retardation film refers to a film having an in-plane retardation value Re and a thickness direction retardation value Rth of -15 to 15 nm. This retardation film is suitably used for a liquid crystal display device of IPS mode.
- the in-plane retardation value R e and the thickness direction retardation value R th are both preferably ⁇ 10 to 10 nm, and more preferably both ⁇ 5 to 5 nm.
- the in-plane retardation value R e and the thickness direction retardation value R th referred to here are values at a wavelength of 590 nm.
- a resin film made of a polyolefin resin such as a cellulose resin, a chain polyolefin resin, and a cyclic polyolefin resin, a polyethylene terephthalate resin, or a (meth) acrylic resin
- a cellulose resin, a polyolefin resin or a (meth) acrylic resin is preferably used because control of the retardation value is easy and acquisition is easy.
- First embodiment a retardation film in which a rod-like liquid crystal compound is oriented horizontally to a supporting substrate
- Second embodiment a retardation film in which a rod-like liquid crystal compound is oriented in a direction perpendicular to a supporting substrate
- Third embodiment Retardation film in which the direction of alignment of the rod-like liquid crystal compound is helically changed in the plane
- Fourth embodiment a retardation film in which a discotic liquid crystal compound is inclined and aligned
- Fifth embodiment A biaxial retardation film in which the discotic liquid crystal compound is oriented in the direction perpendicular to the support substrate can be mentioned.
- the 1st form, the 2nd form, and the 5th form are used suitably. Or these may be laminated and used.
- the retardation film When the retardation film is a layer composed of a polymer in the alignment state of the polymerizable liquid crystal compound (hereinafter sometimes referred to as "optically anisotropic layer"), the retardation film has reverse wavelength dispersion.
- Reverse wavelength dispersion is an optical characteristic in which the in-plane retardation value at the short wavelength is smaller than the in-plane retardation value at the long wavelength, and preferably the retardation film has the following formula It is to satisfy (1) and equation (2).
- R e ( ⁇ ) represents an in-plane retardation value for light at a wavelength of [lambda] nm.
- the retardation film is in the first form and has reverse wavelength dispersion, it is preferable because the coloration at the time of black display in the display device is reduced, and in the formula (1), 0.82 ⁇ R e (450) / R e It is more preferable if (550) ⁇ 0.93. Furthermore, 120 ⁇ R e (550) ⁇ 150 is preferable.
- Examples of the method for producing a retardation film from a polymer in the alignment state of the polymerizable liquid crystal compound include the method described in JP-A-2010-31223.
- the in-plane retardation value R e (550) may be adjusted in the range of 0 to 10 nm, preferably in the range of 0 to 5 nm, and the thickness direction retardation value R th is ⁇ 10.
- the wavelength may be adjusted in the range of -300 nm, preferably in the range of -20 to -200 nm.
- the retardation value R th in the thickness direction which means the refractive index anisotropy in the thickness direction, is a retardation value R 50 measured with the in-plane fast axis as the inclination axis at 50 degrees and the in-plane retardation value It can be calculated from R e . That is, the phase difference value R th in the thickness direction retardation value R e in the plane retardation value R 50 measured by inclining 50 degrees inclination axis fast axis, thickness of the retardation film d, and positions the average refractive index n 0 of the retardation film, obtains the n x, n y and n z by the following equation (4) to (6), these are substituted into equation (3) can be calculated.
- the retardation film may be a multilayer film having two or more layers. For example, the thing by which the protective film was laminated
- the first cured product layer 15 is a cured product layer composed of a cured product of the curable composition (S).
- the curable composition (S) is as described above.
- the curable composition (S) can be cured, for example, by heat.
- thermoplastic resin film 10 and the second thermoplastic resin film 20 is a translucent (preferably optically transparent) thermoplastic resin, for example, a chain-like polyolefin resin (Polypropylene-based resin etc.), Polyolefin-based resin such as cyclic polyolefin-based resin (norbornene-based resin etc.); Cellulose ester-based resin such as triacetylcellulose and diacetylcellulose; Polyester-based such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate Resin; polycarbonate resin; (meth) acrylic resin; polystyrene resin; or a mixture of these, a copolymer, or the like.
- a chain-like polyolefin resin Polypropylene-based resin etc.
- Polyolefin-based resin such as cyclic polyolefin-based resin (norbornene-based resin etc.)
- Cellulose ester-based resin such as triacety
- the first thermoplastic resin film 10 and the second thermoplastic resin film 20 may each be either an unstretched film or a uniaxially or biaxially stretched film.
- the biaxial stretching may be simultaneous biaxial stretching simultaneously stretching in two stretching directions, or sequential biaxial stretching stretching in a first direction and then stretching in a second different direction.
- the first thermoplastic resin film 10 and / or the second thermoplastic resin film 20 may be a protective film having a role of protecting the optical film 30, or may be a protective film having an optical function such as a retardation film. It can also be done.
- chain polyolefin resin examples include homopolymers of chain olefins such as polyethylene resin and polypropylene resin, and copolymers composed of two or more chain olefins.
- the cyclic polyolefin-based resin is a generic term for resins containing cyclic olefin as a polymerization unit, typified by norbornene, tetracyclododecene (alias: dimethanooctahydronaphthalene) or derivatives thereof.
- Cyclic polyolefin-based resins include ring-opened (co) polymers of cyclic olefins and their hydrogenated products, addition polymers of cyclic olefins, cyclic olefins and linear olefins such as ethylene and propylene or aromatic compounds having a vinyl group and And copolymers thereof, and modified (co) polymers obtained by modifying these with unsaturated carboxylic acids and derivatives thereof.
- a norbornene-based resin using a norbornene-based monomer such as norbornene or a polycyclic norbornene-based monomer as a cyclic olefin is preferably used.
- the cellulose ester resin is a resin in which at least a part of hydroxyl groups in cellulose is acetate-esterified, and a mixed ester in which a part is acetate-esterified and a part is esterified with another acid, It is also good.
- the cellulose ester resin is preferably an acetyl cellulose resin.
- acetyl cellulose resins include triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, and cellulose acetate butyrate.
- the polyester-based resin is a resin having an ester bond and other than the above-mentioned cellulose ester-based resin, and is generally made of a polycondensate of polyvalent carboxylic acid or derivative thereof and polyvalent alcohol.
- polyester resins include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polycyclohexanedimethyl terephthalate, polycyclohexanedimethyl naphthalate and the like.
- polyethylene terephthalate is preferably used in view of mechanical properties, solvent resistance, scratch resistance, cost and the like.
- Polyethylene terephthalate refers to a resin in which 80 mol% or more of the repeating unit is composed of ethylene terephthalate, and a structural unit derived from another copolymerization component (dicarboxylic acid component such as isophthalic acid; diol component such as propylene glycol) May be included.
- Polycarbonate resins are polyesters formed from carbonic acid and glycol or bisphenol. Among them, aromatic polycarbonates having diphenyl alkane in the molecular chain are preferably used from the viewpoints of heat resistance, weather resistance and acid resistance.
- polycarbonates examples include 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1, Polycarbonates derived from bisphenols such as 1-bis (4-hydroxyphenyl) isobutane, 1,1-bis (4-hydroxyphenyl) ethane and the like.
- the (meth) acrylic resin is a polymer containing a structural unit derived from a (meth) acrylic monomer, and examples of the (meth) acrylic monomer include methacrylic esters and acrylic esters.
- methacrylic acid esters methyl methacrylate, ethyl methacrylate, n-, i- or t-butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate Etc.
- acrylic esters examples include ethyl acrylate, n-, i- or t-butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate and the like. .
- the (meth) acrylic resin may be a polymer consisting only of structural units derived from (meth) acrylic monomers, or may contain other structural units.
- the (meth) acrylic resin contains methyl methacrylate as a copolymer component, or contains methyl methacrylate and methyl acrylate.
- the (meth) acrylic resin can be a polymer containing a methacrylic acid ester as a main monomer (containing 50% by mass or more), and the methacrylic acid ester and another copolymer component It is preferable that it is a copolymer in which is copolymerized.
- the glass transition temperature of the (meth) acrylic resin is preferably 80 ° C. or more and 160 ° C. or less.
- the glass transition temperature is a polymerization ratio of a methacrylic acid ester monomer to an acrylic acid ester monomer, a carbon chain length of each ester group and a kind of functional group having them, and a polyfunctional single monomer for the whole monomer. It can be controlled by adjusting the polymerization ratio of the mer.
- the ring structure is preferably a heterocyclic structure such as a cyclic acid anhydride structure, a cyclic imide structure and a lactone structure.
- a heterocyclic structure such as a cyclic acid anhydride structure, a cyclic imide structure and a lactone structure.
- Specific examples thereof include cyclic acid anhydride structures such as a glutaric anhydride structure and a succinic anhydride structure; cyclic imide structures such as a glutarimide structure and a succinic imide structure; and lactone ring structures such as butyrolactone and valerolactone.
- the glass transition temperature of the (meth) acrylic resin tends to be able to be increased.
- Cyclic acid anhydride structure and cyclic imide structure are introduced by copolymerizing a monomer having a cyclic structure such as maleic anhydride and maleimide; cyclic acid anhydride structure is obtained by post-polymerization dehydration / demethanol condensation reaction Method of Introduction: It can be introduced by a method of reacting an amino compound to introduce a cyclic imide structure.
- the resin (polymer) having a lactone ring structure is prepared by preparing a polymer having a hydroxyl group and an ester group in the polymer chain, and then heating the hydroxyl group and the ester group in the obtained polymer by heating. Accordingly, it can be obtained by a method of forming a lactone ring structure by cyclocondensation in the presence of a catalyst such as an organophosphorus compound.
- the (meth) acrylic resin and the thermoplastic resin film formed therefrom may optionally contain an additive.
- the additive include lubricants, antiblocking agents, heat stabilizers, antioxidants, antistatic agents, light stabilizers, impact modifiers, surfactants and the like.
- thermoplastic resins other than a (meth) acrylic-type resin as a thermoplastic resin which comprises a thermoplastic resin film.
- the (meth) acrylic resin may contain acrylic rubber particles, which are impact modifiers, from the viewpoint of film forming property to a film, impact resistance of a film, and the like.
- Acrylic rubber particles are particles containing an elastic polymer mainly composed of acrylic acid ester as an essential component, and one having a single layer structure substantially consisting only of this elastic polymer, or one elastic polymer. The thing of the multilayer structure made into a layer is mentioned.
- a crosslinked elastic copolymer containing an alkyl acrylate as a main component and copolymerized with another vinyl monomer and a crosslinkable monomer copolymerizable therewith is mentioned.
- the alkyl acrylate which is the main component of the elastic polymer includes, for example, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc., having an alkyl group having a carbon number of about 1 to 8
- the alkyl acrylate having an alkyl group having 4 or more carbon atoms is preferably used.
- Examples of other vinyl monomers copolymerizable with the above alkyl acrylate include compounds having one polymerizable carbon-carbon double bond in the molecule, and more specifically methyl methacrylate And methacrylates; aromatic vinyl compounds such as styrene; and vinyl cyano compounds such as acrylonitrile.
- crosslinkable monomer examples include crosslinkable compounds having at least two polymerizable carbon-carbon double bonds in the molecule, and more specifically ethylene glycol di (meth) acrylate, butane (Meth) acrylates of polyhydric alcohols such as diol di (meth) acrylate; alkenyl esters of (meth) acrylic acid such as allyl (meth) acrylate; divinyl benzene and the like.
- thermoplastic resin film A laminate of a film made of a (meth) acrylic resin not containing rubber particles and a film made of a (meth) acrylic resin containing rubber particles is used as a thermoplastic resin film to be bonded to the optical film 30 You can also.
- a (meth) acrylic resin layer is formed on one side or both sides of a retardation expression layer made of a resin different from the (meth) acrylic resin, and the one exhibiting the retardation is bonded to the optical film 30.
- the thermoplastic resin film can also be used.
- Each of the first thermoplastic resin film 10 and the second thermoplastic resin film 20 is at least one thermoplastic resin selected from the group consisting of a cellulose ester resin, a polyester resin, a (meth) acrylic resin and a cyclic polyolefin resin. It is preferably a film containing a resin, and more preferably a cellulose ester resin film, a polyester resin film, a (meth) acrylic resin film, or a cyclic polyolefin resin film.
- the first thermoplastic resin film 10 and / or the second thermoplastic resin film 20 is an ultraviolet light absorber, an infrared light absorber, an organic dye, a pigment, an inorganic dye, an antioxidant, an antistatic agent, a surfactant, a lubricant, It may contain a dispersant, a heat stabilizer and the like.
- a thermoplastic resin film containing an ultraviolet light absorber is disposed on the viewing side of an image display element (for example, a liquid crystal cell or an organic EL display element). It is possible to suppress deterioration due to ultraviolet light.
- UV absorbers examples include salicylic acid ester compounds, benzophenone compounds, benzotriazole compounds, cyanoacrylate compounds, and nickel complex compounds.
- the first thermoplastic resin film 10 and the second thermoplastic resin film 20 may be films composed of the same thermoplastic resin, or may be films composed of different thermoplastic resins.
- the first thermoplastic resin film 10 and the second thermoplastic resin film 20 may be the same or different in thickness, presence or absence of additives, types thereof, retardation characteristics, and the like.
- the first thermoplastic resin film 10 and / or the second thermoplastic resin film 20 has a hard coat layer, an antiglare layer, an antireflective layer, a light diffusion layer, an electrification layer on the outer surface (the surface opposite to the optical film 30). You may provide surface treatment layers (coating layer), such as a prevention layer, an antifouling layer, and a conductive layer.
- each of the first thermoplastic resin film 10 and the second thermoplastic resin film 20 is generally 5 ⁇ m to 200 ⁇ m, preferably 10 ⁇ m to 120 ⁇ m, more preferably 10 ⁇ m to 85 ⁇ m, and still more preferably 15 ⁇ m to 65 ⁇ m. It is.
- the thickness of each of the first thermoplastic resin film 10 and the second thermoplastic resin film 20 may be 50 ⁇ m or less, or 40 ⁇ m or less. Reducing the thickness of the first thermoplastic resin film 10 and the second thermoplastic resin film 20 is advantageous for thinning the optical laminate (polarizing plate) and the image display apparatus including the same.
- the surface of the first thermoplastic resin film 10 and the second thermoplastic resin film 20 to which the curable composition is applied is a surface such as saponification treatment, plasma treatment, corona treatment, or primer treatment from the viewpoint of improving adhesion.
- a modification treatment may be performed, or a surface modification treatment may not be performed from the viewpoint of process simplification.
- the surface modification treatment may be performed on the bonding surface of the optical film 30 instead of or together with the bonding surface of the thermoplastic resin film.
- the first thermoplastic resin film 10 or the second thermoplastic resin film 20 is a cellulose ester-based resin film
- a saponification process the method of immersing in the aqueous solution of an alkali like sodium hydroxide or potassium hydroxide is mentioned.
- the curable composition forming the second hardened material layer 25 may be the above-mentioned curable composition (S), or another curable composition different therefrom. It may be.
- the second cured product layer 25 is preferably a cured product layer of the curable composition (S), from the viewpoint of the wet heat durability of the optical laminate and the like.
- these curable compositions may have the same composition or different compositions. May be
- curable compositions include known aqueous compositions (including aqueous adhesives) in which a curable resin component is dissolved or dispersed in water and known active energy rays containing an active energy ray-curable compound. And curable compositions (including active energy ray curable adhesives) and the like.
- polyvinyl alcohol-type resin As a resin component contained in a water-based composition, polyvinyl alcohol-type resin, a urethane resin, etc. are mentioned.
- An aqueous composition containing a polyvinyl alcohol resin is a curable component such as a polyvalent aldehyde, a melamine compound, a zirconia compound, a zinc compound, a glyoxal, a glyoxal derivative, a water-soluble epoxy resin, etc. in order to improve adhesion and adhesiveness. And may further contain a crosslinking agent.
- aqueous composition containing a urethane resin examples include an aqueous composition containing a polyester ionomer type urethane resin and a compound having a glycidyloxy group.
- a polyester-based ionomer-type urethane resin is a urethane resin having a polyester skeleton, into which a small amount of ionic component (hydrophilic component) is introduced.
- the active energy ray-curable composition is a composition that cures upon irradiation with active energy rays such as ultraviolet light, visible light, electron beams, and X-rays.
- active energy rays such as ultraviolet light, visible light, electron beams, and X-rays.
- the second cured product layer 25 is a cured product layer of the composition.
- the active energy ray curable composition can be a composition containing, as a curable component, an epoxy compound that is cured by cationic polymerization, and preferably, an ultraviolet curable composition containing such an epoxy compound as a curable component It is a thing.
- the epoxy compound means a compound having an average of one or more, preferably two or more epoxy groups in the molecule.
- the epoxy compounds may be used alone or in combination of two or more.
- an epoxy compound a hydrogenated epoxy compound obtained by reacting epichlorohydrin with an alicyclic polyol obtained by subjecting an aromatic ring of an aromatic polyol to a hydrogenation reaction (having an alicyclic ring Aliphatic epoxy compounds such as glycidyl ethers of polyols); aliphatic polyalcohols or polyglycidyl ethers of alkylene oxide adducts thereof; epoxy compounds having at least one epoxy group bonded to an alicyclic ring in the molecule A certain alicyclic epoxy type compound etc. are mentioned.
- the active energy ray-curable composition can contain, as a curable component, a (meth) acrylic compound which is radically polymerizable instead of or together with the above-mentioned epoxy compound.
- (Meth) acrylic compounds are (meth) acrylate monomers having one or more (meth) acryloyloxy groups in the molecule; obtained by reacting two or more functional group-containing compounds, and at least two in the molecule
- (meth) acryloyloxy group-containing compounds such as (meth) acrylate oligomers having a (meth) acryloyloxy group of
- the active energy ray-curable composition contains an epoxy-based compound which is cured by cationic polymerization as a curable component, it preferably contains a photo-cationic polymerization initiator.
- the cationic photopolymerization initiator include aromatic diazonium salts; onium salts such as aromatic iodonium salts and aromatic sulfonium salts; and iron-allene complexes.
- the active energy ray-curable composition contains a radically polymerizable component such as a (meth) acrylic compound
- a photoradical polymerization initiator examples include acetophenone initiators, benzophenone initiators, benzoin ether initiators, thioxanthone initiators, xanthones, fluorenones, camphorquinones, benzaldehydes, anthraquinones and the like.
- the optical laminate may include an adhesive layer instead of the second cured product layer 25. That is, the second thermoplastic resin film 20 may be bonded to the optical film 30 via the pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive layer the description of the pressure-sensitive adhesive layer described later is cited.
- thermoplastic resin film 10 and the second thermoplastic resin film 20 these films may be laminated and bonded one by one on a stepwise basis, or both films may be simultaneously formed. It may be laminated and bonded.
- the curable composition (S) is applied to either one or both of the optical film 30 and the bonding surface of the first thermoplastic resin film 10 It coats, the other bonding side is laminated on this, for example, the method of pressing and bonding from the upper and lower sides using a bonding roll etc. is mentioned.
- various coating methods such as a doctor blade, a wire bar, a die coater, a comma coater, and a gravure coater can be used, for example.
- a doctor blade a wire bar
- a die coater a die coater
- a comma coater a gravure coater
- heat treatment is performed on the laminate including the optical film 30, the first cured product layer 15, and the first thermoplastic resin film 10.
- the temperature of the heat treatment is, for example, 40 ° C. or more and 100 ° C. or less, preferably 50 ° C. or more and 90 ° C. or less.
- the heat treatment can remove the solvent contained in the curable composition layer.
- the curing / crosslinking reaction of the curable composition can be advanced by the heat treatment.
- the above bonding method can also be applied to bonding of the optical film 30 and the second thermoplastic resin film 20.
- an active energy ray curable composition as a curable composition which comprises a 2nd cured material layer, after drying a curable composition layer as needed, an active energy ray is irradiated and a curable composition is made. Harden the product layer.
- the light source used to irradiate the active energy ray may be any one capable of generating ultraviolet light, electron beam, X-ray and the like.
- low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, chemical lamps, black light lamps, microwave excited mercury lamps, metal halide lamps and the like having a light emission distribution at a wavelength of 400 nm or less are suitably used.
- cured material layer 15 as shown in FIG. 1 applies the curable composition (S) on the surface of the optical film 30, and was obtained.
- the laminate can be manufactured, for example, by heat treatment at 80 ° C. for 300 seconds in a hot air dryer.
- a separate film is peeled and the optical laminated body shown in FIG. 1 is manufactured also by heat-processing after that. be able to.
- the thickness of the first cured product layer 15 formed of the curable composition (S) is, for example, 1 nm or more and 20 ⁇ m or less, preferably 5 nm or more and 10 ⁇ m or less, more preferably 10 nm or more and 5 ⁇ m or less, more preferably Is 20 nm or more and 1 ⁇ m or less.
- the cured product layer formed from the above-mentioned known aqueous composition can also have the same thickness.
- the thickness of the cured product layer formed of the active energy ray curable composition is, for example, 10 nm or more and 20 ⁇ m or less, preferably 100 nm or more and 10 ⁇ m or less, more preferably 500 nm or more and 5 ⁇ m or less.
- the first cured product layer 15 and the second cured product layer 25 may have the same thickness or different thicknesses.
- optical laminate is an optical functional material other than the optical film 30 (for example, a polarizer) for providing a desired optical function.
- a film can be provided, a preferred example of which is a retardation film.
- the first thermoplastic resin film 10 and / or the second thermoplastic resin film 20 can also serve as a retardation film, but a retardation film can be laminated separately from these films.
- the retardation film is formed of the first thermoplastic resin film 10, the second thermoplastic resin film 20, the first cured product layer 15, and / or the second cured product layer 25 via the pressure-sensitive adhesive layer or the adhesive layer. Can be laminated to the outer surface of The description of the above [4] is cited for the retardation film.
- optical functional films optical members
- optical laminate such as a polarizing plate
- examples of other optical functional films (optical members) that may be included in an optical laminate such as a polarizing plate include a light collector, a brightness enhancement film, a reflective layer (reflective film), a semi-transmissive reflective layer (semi-transmissive reflective film), A light diffusion layer (light diffusion film) or the like.
- the light collecting plate is used for the purpose of light path control and the like, and may be a prism array sheet, a lens array sheet, a dot-attached sheet or the like.
- the brightness enhancement film is used for the purpose of improving the brightness in an image display apparatus to which an optical laminate such as a polarizing plate is applied.
- an optical laminate such as a polarizing plate
- a reflection type polarization separation sheet designed to have anisotropy in reflectance by laminating a plurality of thin film films having mutually different anisotropy of refractive index, an alignment film of cholesteric liquid crystal polymer and its alignment
- the circularly polarized light separation sheet etc. which supported the liquid crystal layer on the base film are mentioned.
- the reflective layer, the semi-transmissive reflective layer, and the light diffusion layer are provided to make the polarizing plate an optical member of a reflective type, a semi-transmissive type, or a diffusion type.
- the reflective polarizing plate is used in a liquid crystal display device of a type in which incident light from the viewing side is reflected and displayed, and a light source such as a backlight can be omitted, so that the liquid crystal display device can be easily thinned.
- a semi-transmissive polarizing plate is used as a reflective type in a bright place and in a liquid crystal display device of a type in which light from a backlight is displayed in a dark place.
- the diffusion type polarizing plate is used for a liquid crystal display device in which light diffusibility is imparted to suppress display defects such as moiré.
- the reflective layer, the semitransparent reflective layer and the light diffusion layer can be formed by a known method.
- the optical laminate can include a pressure-sensitive adhesive layer.
- a pressure-sensitive adhesive layer As an adhesive layer, the adhesive layer for bonding an optical laminated body to image display elements, such as a liquid crystal cell and an organic electroluminescent display element, or another optical member is mentioned.
- the pressure-sensitive adhesive layer is the outer surface of the optical film 30 in the optical laminate having the configuration shown in FIGS. 1 and 2, and the first thermoplastic resin film 10 or the second thermoplastic resin in the optical laminate having the configuration shown in FIG.
- FIG. 3 The example which laminated
- the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer those having a (meth) acrylic resin, a silicone resin, a polyester resin, a polyurethane resin, a polyether resin or the like as a base polymer can be used.
- (meth) acrylic pressure-sensitive adhesives are preferable from the viewpoint of transparency, adhesive strength, reliability, weather resistance, heat resistance, reworkability and the like.
- (Meth) acrylic pressure-sensitive adhesives include (meth) acrylic acid alkyl esters having an alkyl group having a carbon number of 20 or less, such as methyl group, ethyl group, n-, i- or t-butyl group, and (meth) Weight average molecular weight blended with a functional group-containing (meth) acrylic monomer such as acrylic acid or hydroxyethyl (meth) acrylate so that the glass transition temperature is preferably 25 ° C. or less, more preferably 0 ° C. or less
- a (meth) acrylic resin having a molecular weight of 100,000 or more is useful as a base polymer.
- an adhesive composition is dissolved or dispersed in an organic solvent such as toluene or ethyl acetate to prepare an adhesive solution, which is directly applied to the target surface of the optical laminate.
- an organic solvent such as toluene or ethyl acetate
- a method of forming a pressure-sensitive adhesive layer by coating, a method of forming a pressure-sensitive adhesive layer in the form of a sheet on a separate film subjected to release treatment, and transferring it to a target surface of an optical laminate Can be done by
- the thickness of the pressure-sensitive adhesive layer is determined according to the adhesive strength and the like, but a range of 1 ⁇ m to 50 ⁇ m is appropriate, and preferably 2 ⁇ m to 40 ⁇ m.
- An optical laminated body may contain the above-mentioned separate film.
- the separate film can be a film made of a polyethylene-based resin such as polyethylene, a polypropylene-based resin such as polypropylene, or a polyester-based resin such as polyethylene terephthalate. Among them, 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 antistatic agent, etc. be able to.
- the optical laminate has a surface (typically, the first thermoplastic resin film 10, the second thermoplastic resin film 20, the first cured material layer 15 and / or the second cured material layer). 25) can be included.
- the protective film is peeled off together with the pressure-sensitive adhesive layer that the protective film has, for example, after the optical laminate is bonded to an image display element or another optical member.
- the protective film is composed of, for example, a base film and a pressure-sensitive adhesive layer laminated thereon.
- the above description is cited for the pressure-sensitive adhesive layer.
- the resin constituting the substrate film is, for example, a thermoplastic resin such as a polyethylene resin such as polyethylene, a polypropylene resin such as polypropylene, a polyester resin such as polyethylene terephthalate or polyethylene naphthalate, and a polycarbonate resin.
- a thermoplastic resin such as a polyethylene resin such as polyethylene, a polypropylene resin such as polypropylene, a polyester resin such as polyethylene terephthalate or polyethylene naphthalate, and a polycarbonate resin.
- polyester resins such as polyethylene terephthalate are used.
- the optical laminate according to the present invention can be applied to an image display device.
- the image display device includes an optical laminate and an image display element.
- an image display element a liquid crystal cell, an organic EL display element, etc. are mentioned.
- these image display elements conventionally known ones can be used.
- the optical laminate that is a polarizing plate When the optical laminate that is a polarizing plate is applied to a liquid crystal display device, the optical laminate may be disposed on the back light side (rear side) of the liquid crystal cell, or may be disposed on the viewing side. It may be placed on both of them.
- an optical laminated body which is a polarizing plate When the optical laminated body which is a polarizing plate is applied to an organic electroluminescence display, an optical laminated body is normally arrange
- Examples 1 to 6, Comparative Example 1 (1) Preparation of Curable Composition
- the components shown in Table 1 were mixed together with pure water as a solvent in the amounts shown in Table 1 to prepare a curable composition (adhesive aqueous solution).
- the unit of the compounding quantity of each component shown in Table 1 is a mass part, and the compounding quantity of each component is the quantity in conversion of solid content.
- the concentration of (A) in the curable composition obtained in Example 1 is 4.0 mass%, and the concentration of (A) in the curable composition of Example 2 is 5.0 mass%, Example The concentration of (A) in the curable composition of No.
- a saponified TAC film is laminated on one side of the polarizer so that the curable composition layer is on the polarizer side, and a corona-treated zero retardation film is laminated on the other side to achieve zero retardation.
- a laminate having a layer configuration of film / curable composition layer / polarizer / curable composition layer / TAC film was obtained.
- a polarizing plate having a layer configuration of zero retardation film / cured material layer / polarizer / cured material layer / TAC film is obtained.
- the thickness of the cured product layer in the produced polarizing plate was 20 to 60 nm per layer.
- the obtained polarizing plate is cut into a size of 30 mm ⁇ 30 mm and then attached to a glass substrate via a (meth) acrylic adhesive on the zero retardation film side.
- the measurement sample was obtained.
- the layer configuration of the measurement sample is glass substrate / (meth) acrylic pressure-sensitive adhesive layer / zero retardation film / cured product layer / polarizer / cured product layer / TAC film.
- a non-alkali glass substrate (trade name "Eagle XG" manufactured by Corning Inc.) was used.
- the MD transmittance and TD transmittance in the wavelength range of 380 to 780 nm are measured for the obtained measurement sample using a spectrophotometer with an integrating sphere (product name "V7100” manufactured by JASCO Corporation), and each wavelength
- the degree of polarization was calculated.
- the calculated degree of polarization is corrected with a visual field of 2 degrees (C light source) according to JIS Z 8701: 1999 "Color display method-XYZ color system and X 10 Y 10 Z 10 color system", and the wet heat durability test
- the previous visibility corrected polarization degree Py was determined.
- the measurement sample was set to a spectrophotometer equipped with an integrating sphere so that the TAC film side of the polarizing plate was on the detector side and light was incident 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 the relationship between the linear polarization of the incident wavelength ⁇ (nm) and the cross nicol.
- this measurement sample was placed in a high temperature and high humidity environment of 85 ° C. and relative humidity 85% RH for 500 hours and then subjected to a moist heat endurance test placed in an environment of 23 ° C. and relative humidity 50% RH for 24 hours. .
- the visibility corrected polarization degree Py was determined by the same method as before the wet heat endurance test.
- ⁇ Py change rate (%) of each example based on
- the calculated values of ⁇ Py change rate are shown in Table 1. The larger the rate of change in ⁇ Py, the better the wet heat durability.
- ⁇ Py change rate (%) of each example 100 ⁇
- ⁇ Py showed a negative value.
- Table 1 The details of each component shown in Table 1 are as follows. a1: trade name “Epocross WS-300” manufactured by Nippon Shokubai Co., Ltd. [2-solution of oxazoline group-containing acrylic polymer having 2-oxazoline group as side chain, solid content concentration: 10% by mass, oxazoline value (theoretical value) : 130 g solid / eq.
- oxazoline group (theoretical value): 7.7 mmol / g, solid, number average molecular weight: 4 ⁇ 10 4 , weight average molecular weight: 12 ⁇ 10 4 )]
- b1 Zinc iodide (ZnI 2 )
- b2 Titanium iodide (TiI 4 )
- Citric acid d1 Sulfuric acid x 1: Trade name “Gosefimer Z-200” manufactured by Japan Synthetic Chemical Industry Co., Ltd.
- the concentration of (A) in the curable composition obtained in Example 7 is 8.0% by mass, and the concentration of (A) in the curable composition compositions of Examples 8 and 10 is 5.0 mass %, And the concentration of (A) in the curable compositions of Example 9 and Example 11 was 7.0% by mass.
- a saponified TAC film is laminated on one side of the polarizer so that the curable composition layer is on the polarizer side, and a corona-treated zero retardation film is laminated on the other side to achieve zero retardation.
- a laminate having a layer configuration of film / curable composition layer / polarizer / curable composition layer / TAC film was obtained.
- a polarizing plate having a layer configuration of zero retardation film / cured material layer / polarizer / cured material layer / TAC film is obtained.
- the thickness of the cured product layer in the produced polarizing plate was 20 to 60 nm per layer.
- the obtained polarizing plate is cut into a size of 30 mm ⁇ 30 mm and then attached to a glass substrate via a (meth) acrylic adhesive on the zero retardation film side.
- the measurement sample was obtained.
- the layer configuration of the measurement sample is glass substrate / (meth) acrylic pressure-sensitive adhesive layer / zero retardation film / cured product layer / polarizer / cured product layer / TAC film.
- a non-alkali glass substrate (trade name "Eagle XG" manufactured by Corning Inc.) was used.
- the MD transmittance and TD transmittance in the wavelength range of 380 to 780 nm are measured for the obtained measurement sample using a spectrophotometer with an integrating sphere (product name "V7100” manufactured by JASCO Corporation), and each wavelength
- the degree of polarization was calculated.
- the calculated degree of polarization is corrected with a visual field of 2 degrees (C light source) according to JIS Z 8701: 1999 "Color display method-XYZ color system and X 10 Y 10 Z 10 color system", and the wet heat durability test
- the previous visibility corrected polarization degree Py was determined.
- the measurement sample was set to a spectrophotometer equipped with an integrating sphere so that the TAC film side of the polarizing plate was on the detector side and light was incident 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 the relationship between the linear polarization of the incident wavelength ⁇ (nm) and the cross nicol.
- this measurement sample was placed in a high temperature and high humidity environment of 85 ° C. and relative humidity 85% RH for 500 hours and then subjected to a moist heat endurance test placed in an environment of 23 ° C. and relative humidity 50% RH for 24 hours. .
- the visibility corrected polarization degree Py was determined by the same method as before the wet heat endurance test.
- ⁇ Py change rate (%) of each example based on
- the calculated values of ⁇ Py change rate are shown in Table 1. The larger the rate of change in ⁇ Py, the better the wet heat durability.
- ⁇ Py change rate (%) of each example 100 ⁇
- Table 2 The details of each component shown in Table 2 are as follows. a1: trade name “Epocross WS-300” manufactured by Nippon Shokubai Co., Ltd. [2-solution of oxazoline group-containing acrylic polymer having 2-oxazoline group as side chain, solid content concentration: 10% by mass, oxazoline value (theoretical value) : 130 g solid / eq.
- first thermoplastic resin film 10 first thermoplastic resin film, 15 first cured product layer, 20 second thermoplastic resin film, 25 second cured product layer, 30 optical film, 40 pressure-sensitive adhesive layer.
Abstract
Description
本発明に係る硬化性組成物は、オキサゾリン基含有重合体(A)と、ヨウ素化合物(B)とを含む。
オキサゾリン基含有重合体(A)は、分子内にオキサゾリン基を有する重合体であり、側鎖にオキサゾリン基を有する重合体であることが好ましい。
光学積層体の湿熱耐久性や光学特性、光学積層体における光学フィルムと第1硬化物層との間の密着性、第1硬化物層と第1熱可塑性樹脂フィルムとの間の密着性、並びに第1硬化物層の耐水性の観点から、オキサゾリン基含有重合体(A)は、エポクロスWS-300、エポクロスWS-500、エポクロスWS-700等のオキサゾリン基含有アクリルポリマーであることが好ましい。
〔2〕ヨウ素化合物(B)
ヨウ素化合物(B)は、ヨウ素元素を含む化合物である。硬化性組成物(S)は、1種のヨウ素化合物(B)を含んでいてもよいし、2種以上のヨウ素化合物(B)を含んでいてもよい。
a)無機ヨウ化物塩
ヨウ化リチウム、ヨウ化ナトリウム、ヨウ化カリウム、ヨウ化ルビジウム、ヨウ化セシウム等のヨウ化物アルカリ金属塩;
ヨウ化ベリリウム、ヨウ化マグネシウム、ヨウ化カルシウム、ヨウ化バリウム、ヨウ化ストロンチウム等のヨウ化物アルカリ土類金属塩;
ヨウ化ホウ素、ヨウ化アルミニウム、ヨウ化亜鉛、ヨウ化チタン、ヨウ化銅、ヨウ化バナジウム、ヨウ化クロム、ヨウ化マンガン、ヨウ化ニッケル等のヨウ化物の軽金属塩又は重金属塩;
ヨウ化アンモニウム
b)その他の無機ヨウ素化合物
ヨウ素(I2)、ヨウ化水素、ヨウ素酸、ヨウ素酸ナトリウム、ヨウ素酸カリウム、ヨウ素酸カルシウム等
c)有機ヨウ化物塩
ヨウ化アンモニウム、ヨウ化テトラエチルアンモニウム、ヨウ化テトラブチルアンモニウム、ヨウ素酸アンモニウム等のヨウ化物のアンモニウム塩;
テトラブチルホスフィン、テトラフェニルホスフィン等のヨウ化物のホスホニウム塩;
ヨウ化トリメチルスルホキソニウム塩;
ヨウ化イミダゾリウム塩;
ヨウ化ピリジニウム塩;
ヨウ化スルホニウム塩
d)その他の有機ヨウ素化合物
ヨウ化メチル、ヨウ化エチル、ヨウ化ブチル等のヨウ化アルキル;
ヨードナフタレン、ヨードベンゼン、ヨード安息香酸、ヨードサリチル酸、ヨードフェノール等の芳香族ヨウ素化合物;
ヨード酢酸、ヨードプロピオン酸、2-ヨード酪酸、2-ヨード-2-フェニル酢酸
後で述べるように、硬化性組成物(S)は、好ましくは水系組成物である。硬化性組成物(S)が水系組成物である場合、ヨウ素化合物(B)は、該組成物への溶解性又は分散性の観点から、ヨウ化物塩であることが好ましく、無機ヨウ化物塩であることがより好ましい。同様の理由で、ヨウ素化合物(B)は、水溶性であることが好ましい。
硬化性組成物(S)は、カルボキシル基を有する化合物(C)及び化合物(C)の酸無水物から選択される少なくとも1つをさらに含むことができる。以下、カルボキシル基を有する化合物(C)を「化合物(C)」ともいう。
化合物(C)の酸無水物としては、カルボン酸無水物が挙げられる。カルボン酸無水物としては、無水酢酸、無水プロピオン酸、無水シュウ酸、無水コハク酸、無水マレイン酸、無水フタル酸、無水安息香酸等が挙げられる。
硬化性組成物(S)は、オキサゾリン基含有重合体(A)のオキサゾリン基と、カルボキシル基を有する化合物(C)のカルボキシル基との反応を促進させる化合物(D)をさらに含むことができる。以下、この化合物を「化合物(D)」ともいう。ここでいう促進には、該反応を開始させる場合も含まれる。
硬化性組成物(S)は、オキサゾリン基含有重合体(A)、ヨウ素化合物(B)、化合物(C)、化合物(C)の酸無水物及び化合物(D)以外のその他の成分を含むことができる。
硬化性組成物(S)は、溶剤を含むことが好ましい。溶剤としては、水、有機溶剤、又はこれらの混合物が挙げられる。溶剤は、好ましくは水を含むが、水と水溶性の有機溶剤とを併用してもよい。有機溶剤としては、エタノール、1-メトキシ-2-プロパノール等のアルコール溶剤が挙げられる。
本発明に係る光学積層体は、光学フィルムと、その少なくとも一方の面に積層される第1硬化物層(硬化性組成物(S)の硬化物から構成される硬化物層)とを含む。
光学積層体の層構成の例を図1~図5に示す。
図2に示される光学積層体は、光学フィルム30と、その一方の面に第1硬化物層15を介して積層貼合される第1熱可塑性樹脂フィルム10とを含む。第1硬化物層15は、光学フィルム30と第1熱可塑性樹脂フィルム10とを接着する接着剤層として機能することができる。
図3に示される光学積層体は、光学フィルム30と、その一方の面に第1硬化物層15を介して積層貼合される第1熱可塑性樹脂フィルム10と、光学フィルム30の他方の面に第2硬化物層25を介して積層貼合される第2熱可塑性樹脂フィルム20とを含む。すなわち、本発明に係る光学積層体は、第2熱可塑性樹脂フィルム20と第2硬化物層25と光学フィルム30と第1硬化物層15と第1熱可塑性樹脂フィルム10とをこの順に含むものであってもよい。第1硬化物層15及び第2硬化物層25はそれぞれ、光学フィルム30と第1熱可塑性樹脂フィルム10とを接着する接着剤層、光学フィルム30と第2熱可塑性樹脂フィルム20とを接着する接着剤層として機能することができる。
第2硬化物層25と第2熱可塑性樹脂フィルム20とは直接接していることが好ましい。
図4に示される光学積層体は、光学フィルム30と、その一方の面に積層される第1硬化物層15と、光学フィルム30の他方の面に第2硬化物層25を介して積層貼合される第2熱可塑性樹脂フィルム20とを含む。第1硬化物層15は、光学フィルム30の表面を被覆して保護するオーバーコート層、光学フィルム30に追加的に光学機能を付与する光学機能層等として機能することができる。第2硬化物層25は、光学フィルム30と第2熱可塑性樹脂フィルム20とを接着する接着剤層として機能することができる。
第2硬化物層25と第2熱可塑性樹脂フィルム20とは直接接していることが好ましい。
図5に示される光学積層体は、光学フィルム30と、その一方の面に積層される第1硬化物層15と、光学フィルム30の他方の面に積層される第2硬化物層25とを含む。第1硬化物層15及び第2硬化物層25は、光学フィルム30の表面を被覆して保護するオーバーコート層、光学フィルム30に追加的に光学機能を付与する光学機能層等として機能することができる。
光学フィルム30と第2硬化物層25とは直接接していることが好ましい。
偏光子は、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層又はフィルムである。
位相差フィルムとしては、透光性を有する熱可塑性樹脂を一軸延伸又は二軸延伸した延伸フィルム;ディスコティック液晶又はネマチック液晶等の液晶性化合物が配向固定されたフィルム;基材フィルム上に上記の液晶層が形成されたもの等が挙げられる。また、本明細書においては、ゼロレタデーションフィルムも位相差フィルムに含まれる。
Re=(nx-ny)×d
Rth=〔(nx+ny)/2-nz〕×d
で定義される。式中、nxはフィルム面内の遅相軸方向(x軸方向)の屈折率であり、nyはフィルム面内の進相軸方向(面内でx軸に直交するy軸方向)の屈折率であり、nzはフィルム厚み方向(フィルム面に垂直なz軸方向)の屈折率であり、dはフィルムの厚みである。
第一の形態:棒状液晶化合物が支持基材に対して水平方向に配向した位相差フィルム、
第二の形態:棒状液晶化合物が支持基材に対して垂直方向に配向した位相差フィルム、
第三の形態:棒状液晶化合物が面内で螺旋状に配向の方向が変化している位相差フィルム、
第四の形態:円盤状液晶化合物が傾斜配向している位相差フィルム、
第五の形態:円盤状液晶化合物が支持基材に対して垂直方向に配向した二軸性の位相差フィルムが挙げられる。
1≦Re(630)/Re(550) (2)
位相差フィルムが第一の形態でかつ逆波長分散性を有する場合、表示装置での黒表示時の着色が低減するため好ましく、式(1)において0.82≦Re(450)/Re(550)≦0.93であればより好ましい。さらに120≦Re(550)≦150が好ましい。
Re=(nx-ny)×d (4)
R50=(nx-ny’)×d/cos(φ) (5)
(nx+ny+nz)/3=n0 (6)
ここで、
φ=sin-1〔sin(40°)/n0〕
ny’=ny×nz/〔ny 2×sin2(φ)+nz 2×cos2(φ)〕1/2
位相差フィルムは、二以上の層を有する多層フィルムであってもよい。例えば、位相差フィルムの片面又は両面に保護フィルムが積層されたものや、二以上の位相差フィルムが粘着剤又は接着剤を介して積層されたものが挙げられる。
第1硬化物層15は、硬化性組成物(S)の硬化物から構成される硬化物層である。硬化性組成物(S)については上述のとおりである。硬化性組成物(S)は、例えば、熱によって硬化させることができる。
第1熱可塑性樹脂フィルム10及び第2熱可塑性樹脂フィルム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)等のポリオレフィン系樹脂;トリアセチルセルロース、ジアセチルセルロース等のセルロースエステル系樹脂;ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンテレフタレート等のポリエステル系樹脂;ポリカーボネート系樹脂;(メタ)アクリル系樹脂;ポリスチレン系樹脂;又はこれらの混合物、共重合物等からなるフィルムであることができる。
鎖状ポリオレフィン系樹脂としては、ポリエチレン樹脂、ポリプロピレン樹脂等の鎖状オレフィンの単独重合体のほか、2種以上の鎖状オレフィンからなる共重合体を挙げることができる。
第2硬化物層25を形成する硬化性組成物は、上述の硬化性組成物(S)であってもよいし、これとは異なる他の硬化性組成物であってもよい。第2硬化物層25は、光学積層体の湿熱耐久性等の観点から、硬化性組成物(S)の硬化物層であることが好ましい。
光学フィルム30の一方の面に第1硬化物層15を介して第1熱可塑性樹脂フィルム10を積層接着することにより、図2に示される構成の光学積層体を得ることができ、光学フィルム30の他方の面に第2硬化物層25を介して第2熱可塑性樹脂フィルム20をさらに積層接着することにより、図3に示される構成の光学積層体を得ることができる。
〔8-1〕光学機能性フィルム
光学積層体は、所望の光学機能を付与するための、光学フィルム30(例えば偏光子)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。
光学積層体は、粘着剤層を含むことができる。粘着剤層としては、光学積層体を液晶セルや有機EL表示素子等の画像表示素子、又は他の光学部材に貼合するための粘着剤層が挙げられる。該粘着剤層は、図1及び2に示される構成の光学積層体においては光学フィルム30の外面、図3に示される構成の光学積層体においては第1熱可塑性樹脂フィルム10又は第2熱可塑性樹脂フィルム20の外面、図4に示される構成の光学積層体においては第1硬化物層15又は第2熱可塑性樹脂フィルム20の外面、図5に示される構成の光学積層体においては第1硬化物層15又は第2硬化物層25の外面に積層することができる。
光学積層体は、その表面(典型的には、第1熱可塑性樹脂フィルム10、第2熱可塑性樹脂フィルム20、第1硬化物層15及び/又は第2硬化物層25の表面)を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光学積層体が貼合された後、それが有する粘着剤層ごと剥離除去される。
本発明に係る光学積層体は、画像表示装置に適用することができる。この場合、画像表示装置は、光学積層体と、画像表示素子とを含む。画像表示素子としては、液晶セル、有機EL表示素子等が挙げられる。これらの画像表示素子としては、従来公知のものを使用することができる。
厚さ60μmのポリビニルアルコールフィルム(平均重合度:約2,400、ケン化度:99.9モル%以上)を30℃の純水に浸漬した後、ヨウ素/ヨウ化カリウム/水の質量比が0.02/2/100である30℃の水溶液に浸漬した。その後、ヨウ化カリウム/ホウ酸/水の質量比が12/5/100である56.5℃の水溶液に浸漬した。引き続き、8℃の純水で洗浄した後、65℃で乾燥させて、ポリビニルアルコールフィルムにヨウ素が吸着配向された厚み23μmの偏光子を得た。延伸は、主にヨウ素染色及びホウ酸処理の工程で行い、トータル延伸倍率は5.5倍であった。
(1)硬化性組成物の調製
表1に示される成分を表1に示される配合量で、溶剤としての純水とともに混合して、硬化性組成物(接着剤水溶液)を調製した。表1に示される各成分の配合量の単位は質量部であり、各成分の配合量は固形分換算での量である。なお、実施例1において得られた硬化性組成物における(A)の濃度は4.0質量%とし、実施例2の硬化性組成物における(A)の濃度は5.0質量%、実施例3の硬化性組成物における(A)の濃度は6.0質量%、実施例4及び実施例5の硬化性組成物における硬化性組成物(A)の濃度は7.0質量%、実施例6の硬化性組成物における(A)の濃度は5.0質量%とした。比較例1において、硬化性組成物における(X)の濃度は3.0質量%とした。
トリアセチルセルロース(TAC)フィルム〔コニカミノルタオプト(株)製の商品名「KC4UAW」、厚み:40μm〕の片面にケン化処理を施した後、そのケン化処理面に上記(1)で調製した硬化性組成物をバーコータを用いて塗工するとともに、環状ポリオレフィン系樹脂からなるゼロ位相差フィルム〔日本ゼオン(株)製の商品名「ZEONOR」、厚み:23μm〕の片面にコロナ処理を施し、そのコロナ処理面に上記(1)で調製した硬化性組成物をバーコータを用いて塗工した。硬化性組成物層が偏光子側となるように、偏光子の一方の面にケン化処理済みTACフィルムを積層し、他方の面にコロナ処理済みゼロ位相差フィルムを積層して、ゼロ位相差フィルム/硬化性組成物層/偏光子/硬化性組成物層/TACフィルムの層構成を有する積層体を得た。この積層体に対して、熱風乾燥機で80℃、300秒間の加熱処理を行うことにより、ゼロ位相差フィルム/硬化物層/偏光子/硬化物層/TACフィルムの層構成を有する偏光板を作製した。作製した偏光板中の硬化物層の厚みは、一層につき20~60nmであった。
得られた偏光板を30mm×30mmの大きさに裁断した後、ゼロ位相差フィルム側に(メタ)アクリル系粘着剤を介してガラス基板に貼合し、測定サンプルを得た。測定サンプルの層構成は、ガラス基板/(メタ)アクリル系粘着剤層/ゼロ位相差フィルム/硬化物層/偏光子/硬化物層/TACフィルムである。ガラス基板には、無アルカリガラス基板〔コーニング社製の商品名「Eagle XG」〕を使用した。
偏光度(λ)=100×(Tp(λ)-Tc(λ))/(Tp(λ)+Tc(λ))
で定義される。
=100×|{(各例の|ΔPy|)-(比較例1の|ΔPy|)}|/(比較例1の|ΔPy|)
なお、いずれの実施例及び比較例においても、ΔPyは負の値を示した。
a1:株式会社日本触媒製の商品名「エポクロス WS-300」〔2-オキサゾリン基を側鎖として有するオキサゾリン基含有アクリル系重合体の水溶液、固形分濃度:10質量%、オキサゾリン価(理論値):130g solid/eq.、オキサゾリン基量(理論値):7.7mmol/g,solid、数平均分子量:4×104、重量平均分子量:12×104)〕
b1:ヨウ化亜鉛(ZnI2)
b2:ヨウ化チタン(TiI4)
c1:クエン酸
d1:硫酸
x1:日本合成化学工業株式会社製の商品名「ゴーセファイマー Z-200」〔アセトアセチル基変性ポリビニルアルコール、平均重合度:1100、ケン化度:98.5モル%以上〕
y1:グリオキザール
<実施例7~11>
(1)硬化性組成物の調製
表2に示される成分を表2に示される配合量で、溶剤としての純水とともに混合して、硬化性組成物(接着剤水溶液)を調製した。表2に示される各成分の配合量の単位は質量部であり、各成分の配合量は固形分換算での量である。実施例7において得られた硬化性組成物における(A)の濃度は8.0質量%とし、実施例8及び実施例10の硬化性組成物組成物における(A)の濃度は5.0質量%とし、実施例9及び実施例11の硬化性組成物における(A)の濃度は7.0質量%とした。
トリアセチルセルロース(TAC)フィルム〔コニカミノルタオプト(株)製の商品名「KC4UAW」、厚み:40μm〕の片面にケン化処理を施した後、そのケン化処理面に上記(1)で調製した硬化性組成物をバーコータを用いて塗工するとともに、環状ポリオレフィン系樹脂からなるゼロ位相差フィルム〔日本ゼオン(株)製の商品名「ZEONOR」、厚み:23μm〕の片面にコロナ処理を施し、そのコロナ処理面に上記(1)で調製した硬化性組成物をバーコータを用いて塗工した。硬化性組成物層が偏光子側となるように、偏光子の一方の面にケン化処理済みTACフィルムを積層し、他方の面にコロナ処理済みゼロ位相差フィルムを積層して、ゼロ位相差フィルム/硬化性組成物層/偏光子/硬化性組成物層/TACフィルムの層構成を有する積層体を得た。この積層体に対して、熱風乾燥機で80℃、300秒間の加熱処理を行うことにより、ゼロ位相差フィルム/硬化物層/偏光子/硬化物層/TACフィルムの層構成を有する偏光板を作製した。作製した偏光板中の硬化物層の厚みは、一層につき20~60nmであった。
得られた偏光板を30mm×30mmの大きさに裁断した後、ゼロ位相差フィルム側に(メタ)アクリル系粘着剤を介してガラス基板に貼合し、測定サンプルを得た。測定サンプルの層構成は、ガラス基板/(メタ)アクリル系粘着剤層/ゼロ位相差フィルム/硬化物層/偏光子/硬化物層/TACフィルムである。ガラス基板には、無アルカリガラス基板〔コーニング社製の商品名「Eagle XG」〕を使用した。
偏光度(λ)=100×(Tp(λ)-Tc(λ))/(Tp(λ)+Tc(λ))
で定義される。
=100×|{(各例の|ΔPy|)-(比較例1の|ΔPy|)}|/(比較例1の|ΔPy|)
a1:株式会社日本触媒製の商品名「エポクロス WS-300」〔2-オキサゾリン基を側鎖として有するオキサゾリン基含有アクリル系重合体の水溶液、固形分濃度:10質量%、オキサゾリン価(理論値):130g solid/eq.、オキサゾリン基量(理論値):7.7mmol/g,solid、数平均分子量:4×104、重量平均分子量:12×104)〕
b1:ヨウ化亜鉛(ZnI2)
b3:ヨウ化セシウム
b4:ヨウ化アンモニウム
c1:クエン酸
d1:硫酸
Claims (9)
- オキサゾリン基含有重合体(A)と、ヨウ素化合物(B)とを含む、硬化性組成物。
- カルボキシル基を有する化合物(C)及び化合物(C)の酸無水物からなる群より選択される少なくとも1つをさらに含む、請求項1に記載の硬化性組成物。
- オキサゾリン基含有重合体(A)のオキサゾリン基と、カルボキシル基を有する化合物(C)のカルボキシル基との反応を促進させる化合物(D)をさらに含む、請求項2に記載の硬化性組成物。
- 光学フィルムと、請求項1~3のいずれか1項に記載の硬化性組成物の硬化物から構成される第1硬化物層とを含む、光学積層体。
- 前記光学フィルムと、前記第1硬化物層と、第1熱可塑性樹脂フィルムとをこの順に含む、請求項4に記載の光学積層体。
- 第2熱可塑性樹脂フィルムと、第2硬化物層と、前記光学フィルムと、前記第1硬化物層と、前記第1熱可塑性樹脂フィルムとをこの順に含む、請求項5に記載の光学積層体。
- 前記光学フィルムが偏光子である、請求項4~6のいずれか1項に記載の光学積層体。
- 請求項4~7のいずれか1項に記載の光学積層体と、画像表示素子とを含む、画像表示装置。
- オキサゾリン基含有重合体(A)と、ヨウ素化合物(B)とを含む、偏光板用接着剤組成物。
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WO2020262067A1 (ja) * | 2019-06-25 | 2020-12-30 | 日東電工株式会社 | 偏光板および該偏光板の製造方法 |
WO2020262068A1 (ja) * | 2019-06-25 | 2020-12-30 | 日東電工株式会社 | 偏光板および該偏光板の製造方法 |
CN114026474A (zh) * | 2019-06-25 | 2022-02-08 | 日东电工株式会社 | 偏光膜、偏光板和该偏光膜的制造方法 |
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WO2020262213A1 (ja) * | 2019-06-25 | 2020-12-30 | 日東電工株式会社 | 偏光板の製造方法 |
WO2020262067A1 (ja) * | 2019-06-25 | 2020-12-30 | 日東電工株式会社 | 偏光板および該偏光板の製造方法 |
WO2020262068A1 (ja) * | 2019-06-25 | 2020-12-30 | 日東電工株式会社 | 偏光板および該偏光板の製造方法 |
JP2021004943A (ja) * | 2019-06-25 | 2021-01-14 | 日東電工株式会社 | 偏光板および該偏光板の製造方法 |
JP2021004944A (ja) * | 2019-06-25 | 2021-01-14 | 日東電工株式会社 | 偏光板および該偏光板の製造方法 |
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JP7300326B2 (ja) | 2019-06-25 | 2023-06-29 | 日東電工株式会社 | 偏光板および該偏光板の製造方法 |
JP7300325B2 (ja) | 2019-06-25 | 2023-06-29 | 日東電工株式会社 | 偏光板および該偏光板の製造方法 |
JP7312038B2 (ja) | 2019-06-25 | 2023-07-20 | 日東電工株式会社 | 偏光板の製造方法 |
Also Published As
Publication number | Publication date |
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JP7308759B2 (ja) | 2023-07-14 |
TW201927969A (zh) | 2019-07-16 |
KR20200093041A (ko) | 2020-08-04 |
JPWO2019116969A1 (ja) | 2021-01-21 |
CN111465657A (zh) | 2020-07-28 |
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