TW201838819A - Optical laminate - Google Patents

Abstract

The present invention provides an optical laminate capable of suppressing deterioration of polarizing performance of a polarizer even in a moist and hot environment. The optical laminate of the present invention comprises a cured layer of a curable resin composition on at least one side of a polarizer in which iodine is oriented in a polyvinyl alcohol resin, and after the optical laminate was placed in an environment at a temperature of 60 DEG C and a humidity of 90% for 500 hours, the content ratio of iodine element in the cured layer is 0.03 atomic% or less.

Description

   Optical laminate   

The present invention relates to an optical laminate.

Liquid crystal display devices are used in various display devices, taking advantage of low power consumption, low voltage operation, light weight and thinness. A liquid crystal panel constituting a liquid crystal display device has a configuration in which a pair of polarizing plates are laminated on both sides of a liquid crystal cell.

Conventional polarizers are those in which a protective film is laminated on both sides of a polarizer made of a polyvinyl alcohol resin, and a laminate of the protective film is widely used as a water-based adhesive such as a polyvinyl alcohol-based adhesive. However, when a protective film and a polarizer are laminated with an aqueous adhesive interposed therebetween, in order to remove the water contained in the aqueous adhesive and display the adhesive force, a drying step must be provided and the production step becomes troublesome.

Therefore, in recent years, it has been proposed to use an active energy ray hardening type adhesive instead of an aqueous adhesive. Patent Document 1 describes a polarizing plate in which a polarizer and a protective film are laminated with a hardening layer of an active energy ray-curable adhesive, and also describes that the active energy ray-curable adhesive has a (meth) acrylfluorenyl group. In this way, the drying step can be omitted by laminating the polarizer and the protective film by using an active energy ray-curable adhesive.

    [Prior technical literature]         [Patent Literature]    

[Patent Document 1] Japanese Patent Laid-Open No. 2013-174922

However, when a hardened layer of an active energy ray-curable adhesive is present on the polarizer, there is a problem that the polarizing performance of the polarizer is reduced in a hot and humid environment (for example, a temperature of 60 ° C. and a humidity of 90%).

[1] An optical laminate comprising a hardened layer of a curable resin composition on at least one side of a polarizer made of iodine oriented to a polyvinyl alcohol resin, and the optical laminate is placed at a temperature of 60 ° C and a relative humidity of 90 After 500 hours in a% environment, the iodine-containing ratio of the hardened layer was 0.03 atomic% or less.

[2] The optical laminated body according to [1], further comprising a protective film.

[3] The optical laminate according to [2], wherein the protective film is selected from the group consisting of a cyclic polyolefin resin film, a cellulose resin film, a polycarbonate resin film, a polyolefin resin film, and a polyester At least one layer of a resin film, an acrylic resin film, a brightness enhancement film, and a cured layer of a curable resin composition.

[4] The optical laminated body according to [2] or [3], wherein the moisture permeability of the protective film is 400 g / m ² . less than day.

[5] The optical multilayer body according to any one of [2] to [4], wherein the protective film has an in-plane phase difference, and an in-plane phase difference value R ₀ at a wavelength of 590 nm is 0 to 200 nm .

[6] The optical laminate according to any one of [2] to [5], wherein the protective film has a surface treatment layer on at least one side.

[7] The optical laminate according to any one of [1] to [6], which further has an adhesive layer.

[8] The optical laminate according to any one of [1] to [7], wherein the alicyclic ring contained in the curable resin composition is 100 parts by weight of the curable resin composition. The content ratio of the oxygen compound is 5 parts by weight or more and 60 parts by weight or less.

[9] A liquid crystal display device, wherein the optical laminated body according to any one of [1] to [8] is disposed in a liquid crystal cell.

According to the present invention, it is possible to suppress a decrease in the polarization performance of the polarizer even in a hot and humid environment.

1‧‧‧ Hardened layer of hardenable resin composition

2‧‧‧ polarizer

10, 11‧‧‧ protective film

20, 21‧‧‧ Adhesive layer

30‧‧‧ Adhesive layer

100, 101, 102, 103, 104, 105, 106, 107‧‧‧ optical laminated body

FIG. 1 is a schematic cross-sectional view showing an example of an optical multilayer body of the present invention.

Fig. 2 is a schematic cross-sectional view showing an example of an optical laminated body of the present invention.

Fig. 3 is a schematic cross-sectional view showing an example of an optical multilayer body of the present invention.

    [Forms for Implementing Invention]    

The optical laminated body of this invention is demonstrated, referring a suitable figure. The optical laminated system of the present invention includes a polarizer in which iodine is oriented to a polyvinyl alcohol-based resin, and a hardened layer (hereinafter, simply referred to as a hardened layer) of a curable resin composition.

As shown in FIG. 1 (a), the optical laminated body 100 has a structure in which a hardened layer 1 is laminated on one side of a polarizer 2.

The optical laminate may further include a protective film and an adhesive layer. The protective film which an optical laminated body may have, for example, the hardened layer of a curable resin composition, and a protective film are mentioned.

When a cured layer of a curable resin composition is used as a protective film, in one embodiment, as shown in FIG. 1 (b), the optical laminate 101 has a structure in which a cured layer 1 is laminated on both sides of a polarizer 2 . That is, the cured layers of the curable resin composition may be laminated on both sides of the polarizer.

When a protective film is used as the protective film, the optical laminate may be provided with the protective film only on one side of the polarizer.

In one embodiment, as shown in FIG. 2 (a), the optical laminated body 102 has a layer of the hardening layer 1 and an adhesive layer 21 sequentially on one side of the polarizer 2, and an adhesive layer 20 and a protective film. A structure in which 10 is sequentially laminated on the other side of the polarizer 2.

In one embodiment, as shown in FIG. 2 (b), the optical laminated body 103 has a layer of the hardened layer 1 and an adhesive layer 21 sequentially on one side of the polarizer 2, and the hardened layer 1 and the protective film 10 A structure in which the other surface of the polarizer 2 is sequentially laminated.

In one embodiment, as shown in FIG. 2 (c), the optical laminated body 104 has a layer of the polarizing plate 2 in order of the hardened layer 1 and the adhesive layer 21, and an adhesive layer 30 and a protective film. A structure in which 10 is sequentially laminated on the other side of the polarizer 2.

The adhesive layer 21 may be an adhesive layer for bonding an optical laminate to a liquid crystal cell. In the above example, the case where the adhesive layer 21 is laminated on the hardened layer 1 has been described, but of course the adhesive layer 21 may be laminated on the protective film 10.

When a protective film is used as the protective film, the optical laminate may be provided with protective films on both sides of the polarizer.

In one embodiment, as shown in FIG. 3 (a), the optical laminate 105 includes a hardening layer 1, a protective film 11, and an adhesive layer 21 sequentially laminated on one side of the polarizer 2, and an adhesive layer 20 and the protective film 10 are sequentially laminated on the other surface of the polarizer 2.

In one embodiment, as shown in FIG. 3 (b), the optical laminated body 106 includes a hardened layer 1, a protective film 11, and an adhesive layer 21 sequentially laminated on one side of the polarizer 2, and the hardened layer 1 The protective film 10 is sequentially laminated on the other surface of the polarizer 2.

In one embodiment, as shown in FIG. 3 (c), the optical laminated body 107 includes a hardened layer 1, a protective film 11, and an adhesive layer 21 sequentially laminated on one side of the polarizer 2, and an adhesive layer 30 and a protective film 1 are sequentially laminated on the other surface of the polarizer 2.

The adhesive layer 21 may be an adhesive layer for bonding an optical laminate to a liquid crystal cell. In the above example, the case where the adhesive layer 21 is laminated on the protective film 11 has been described, but of course the adhesive layer 21 It may be laminated on the protective film 10.

Hereinafter, each member which comprises the optical laminated body of this invention is demonstrated.

    [Polarizer]    

The polarizer used in the present invention is usually manufactured by the following steps: the step of uniaxially stretching the polyvinyl alcohol resin film; the polyvinyl alcohol resin film is dyed with iodine to adsorb the iodine. A step of treating a polyvinyl alcohol-based resin film having iodine adsorbed with an aqueous solution of boric acid; and a step of washing with water after treating with an aqueous solution of boric acid.

As the polyvinyl alcohol-based resin, one obtained by saponifying a polyvinyl acetate-based resin can be used. Polyvinyl acetate resins include copolymers of vinyl acetate and other copolymerizable monomers, in addition to polyvinyl acetate, which is a homopolymer of vinyl acetate. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.

The saponification degree of the polyvinyl alcohol-based resin is usually about 85 to 100 mol%, and preferably 98 mol% or more. This polyvinyl alcohol-based resin may be modified, and for example, polyvinyl acetal or polyvinyl acetal modified with aldehydes may be used. The degree of polymerization of the polyvinyl alcohol resin is usually about 1,000 to 10,000, and preferably about 1,500 to 5,000.

A polyvinyl alcohol-based resin can be used as the embryonic film of a polarizer. As a method for forming a polyvinyl alcohol-based resin into a film, a conventional method can be used for forming a film. When considering that the thickness of the obtained polarizer is 15 μm or less, the film thickness of the polyvinyl alcohol-based embryo membrane is preferably about 5 to 35 μm, and more preferably 5 to 20 μm. When the thickness of the germ film is 35 μm or more, it is necessary to increase the stretching ratio when manufacturing the polarizer, and the size shrinkage of the obtained polarizer tends to increase.

On the other hand, when the thickness of the germ membrane is 5 μm or less, the workability during stretching is reduced, and defects such as cutting are liable to occur during production.

The uniaxial stretching of the polyvinyl alcohol-based resin film may be performed before dyeing with iodine, simultaneously with dyeing, or after dyeing. When uniaxial stretching is performed after dyeing, the uniaxial stretching may be performed before or during a boric acid treatment. It is also possible to perform uniaxial extension in these plural stages.

When performing uniaxial stretching, uniaxial stretching can be performed between rollers with different peripheral speeds, or uniaxial stretching can be performed using hot rollers. The uniaxial stretching may be dry stretching in the air, or wet stretching using a solvent and stretching the polyvinyl alcohol resin film after swelling. The stretching ratio is usually about 3 to 8 times.

As a method of dyeing a polyvinyl alcohol-based resin film with iodine, for example, a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing iodine and potassium iodide can be adopted. The iodine content in the aqueous solution is usually about 0.01 to 1 part by weight per 100 parts by weight of water. The content of potassium iodide is usually about 0.5 to 20 parts by weight per 100 parts by weight of water.

The boric acid treatment after dyeing with iodine is usually performed by immersing the dyed polyvinyl alcohol-based resin film in an aqueous solution containing boric acid.

The amount of boric acid in the boric acid-containing aqueous solution is usually about 2 to 15 parts by weight, preferably 5 to 12 parts by weight, per 100 parts by weight of water. It is preferred that the boric acid-containing aqueous solution contains potassium iodide. The amount of potassium iodide in the boric acid-containing aqueous solution is usually about 0.1 to 15 parts by weight, preferably about 5 to 12 parts by weight, per 100 parts by weight of water.

The polyvinyl alcohol-based resin film after the boric acid treatment is usually washed with water. The water washing treatment system can be performed, for example, by immersing a boric acid-treated polyvinyl alcohol-based resin film in water. The water washing treatment may also use an aqueous potassium iodide solution. After washing with water, a polarizing plate can be obtained by drying. The drying process can be performed using a hot-air dryer and a far-infrared heater.

By the drying process, the moisture content of the polarizer is reduced to a practical level. Its moisture content is usually 5 to 20% by weight, preferably 8 to 15% by weight. When the moisture content is less than 5% by weight, the flexibility of the polarizer disappears, and the polarizer may be damaged or broken after it is dried.

When the moisture content is higher than 20% by weight, the thermal stability of the polarizer may be deteriorated.

Further, the stretching, dyeing, boric acid treatment, water washing step, and drying step of the polyvinyl alcohol-based resin film in the step of manufacturing the polarizer may be performed according to, for example, the method described in JP 2012-159778. The method described in this document is to form a polyvinyl alcohol-based resin layer as a polarizer by applying a polyvinyl alcohol-based resin to a base film.

The thickness of the polarizer can be generally 3 μm or more and 30 μm or less, preferably 15 μm or less, and more preferably 10 μm or less. Especially when the polarizer is 10 μm or less, the amount of iodine contained in the polarizer is smaller than that of a thick film. Therefore, as described later, the polarizing performance is likely to be reduced in a hot and humid environment. Even when such a polarizer with such a thin film is provided, it is possible to significantly suppress a reduction in polarization performance.

    [Curing layer of curable resin composition]    

The curing layer of the curable resin composition can be formed by applying a curable resin composition to a polarizer or the like, and then curing the curable resin composition. Examples of the curable resin composition include an active energy ray-curable resin composition and a thermosetting resin composition. The active energy ray-curable resin composition is preferred.

The hardened layer is shown, for example, in FIG. 3 (a), and may also be a layer for bonding a polarizer to a protective film (so-called adhesive layer). For example, shown in FIG. 2 (a), it may also be used to protect a polarizer Layer (the protective film described above).

When the hardened layer is provided with a function as an adhesive layer, the thickness of the hardened layer may be 0.01 μm or more and 3 μm or less, and preferably 0.01 μm or more and 2 μm or less. When the hardened layer is provided with a function as a protective film, the thickness of the hardened layer may be 1 μm or more and 10 μm or less, and preferably 1 μm or more and 7 μm or less.

    [Active energy ray-curable resin composition]    

The active energy ray-curable compound contained in the active energy ray-curable resin composition is preferably a cation polymerizable compound or a radical polymerizable compound.

    (Cationically polymerizable compound)    

Examples of the cationically polymerizable compound used in this embodiment include epoxy compounds and oxetane compounds.

The content of the cationically polymerizable compound is preferably 10 parts by weight or more and 99 parts by weight or less based on 100 parts by weight of the active energy ray-curable resin composition, and more preferably 40 parts by weight or more and 99 parts by weight or less.

An epoxy compound is a kind of cationically polymerizable compound, and can be hardened by irradiating active energy rays. The active energy ray-curable resin composition contains an epoxy compound, and preferably contains an alicyclic epoxy compound to improve adhesion to a polarizer.

Examples of the epoxy compound system include an aromatic epoxy compound, an epoxypropyl ether of a polyhydric alcohol having an alicyclic ring, an aliphatic epoxy compound, and an alicyclic epoxy compound.

Examples of the aromatic epoxy compound are bisphenol-type epoxy resins such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, and bisphenol S diglycidyl ether; Such as phenol novolac epoxy resin, cresol novolac epoxy resin and hydroxybenzaldehyde phenol novolac epoxy resin novolac type epoxy resin; such as tetrahydroxyphenylmethane epoxypropyl ether, tetrahydroxydibenzene Glycidyl ethers of ketones, polyfunctional epoxy resins epoxidized polyvinyl phenol, and the like.

Glycidyl ether of a polyhydric alcohol having an alicyclic ring includes a nuclear hydrogenated polyhydric compound obtained by selectively hydrogenating an aromatic ring in the presence of a catalyst under pressure and under pressure. , By etherification of glycidyl. Examples of the aromatic polyol include bisphenol compounds such as bisphenol A, bisphenol F, and bisphenol S; novolac resins such as phenol novolac resin, cresol novolac resin, and hydroxybenzaldehyde phenol novolac resin; Such as tetrahydroxydiphenylmethane, tetrahydroxydiphenyl ketone, polyvinylphenol and other multifunctional compounds.

It can be obtained by reacting epichlorohydrin with an alicyclic polyol to form an epoxypropyl ether, wherein the alicyclic polyol is obtained by hydrogenating an aromatic ring of these aromatic polyols.

Among the glycidyl ethers of polyhydric alcohols having such an alicyclic ring, preferred is a diglycidyl ether of hydrogenated bisphenol A.

Examples of the aliphatic epoxy compound include an aliphatic polyhydric alcohol or a polyoxypropylene ether of an alkylene oxide adduct thereof. Specific examples include 1,4-butanediol diglycidyl ether; 1,6-hexanediol diglycidyl ether; triglycidyl ether of glycerol; trimethylolpropane Glycidyl ether; Diglycidyl ether of polyethylene glycol; Diglycidyl ether of propylene glycol; Diglycidyl ether of neopentyl glycol; Glycol, such as by propylene glycol or glycerol A polyether polyol, such as a polyether polyol, obtained by adding one or two or more kinds of aliphatic polyols (ethylene oxide or propylene oxide) to an aliphatic polyol.

A monofunctional epoxy compound represented by the following formula (I) can also be cited as the aliphatic epoxy compound. R1 may be a branched alkyl group having 1 to 15 carbon atoms. The carbon number of the alkyl group is preferably 6 or more, and 6 to 10 is more preferable. Especially preferred are branched alkyl groups. Examples of the monofunctional epoxy compound represented by the formula (I) include 2-ethylhexyl glycidyl ether.

An alicyclic epoxy compound refers to a compound having a structure that forms at least one ethylene oxide ring with a carbon atom of an alicyclic ring in the molecule. Here, "the structure which forms an ethylene oxide ring with the carbon atom of an alicyclic ring" means the structure represented by following formula (II). N in the formula is an integer of 2 to 5.

A compound in which one or a plurality of hydrogen atoms in (CH ₂ ) _n in the formula (II) is removed and a compound bonded to another chemical structure is an alicyclic epoxy compound. One or more hydrogen atoms in (CH ₂ ) _n forming an alicyclic ring may be substituted by a linear alkyl group such as a methyl group or an ethyl group.

The epoxy compound is preferably an alicyclic epoxy compound. From the viewpoint of easily obtaining a protective layer having better adhesion to a polarizer, it is preferable to have an epoxy cyclohexane (in the above formula (II): n = 4), or epoxycycloheptane (n = 5 in the formula (II)).

The content of the epoxy compound is preferably 1 part by weight or more, more preferably 5 parts by weight or more, and also 10 parts by weight or more with respect to 100 parts by weight of the active energy ray-curable resin composition. The content of the epoxy compound is preferably less than 100 parts by weight.

In the active energy ray-curable resin composition, the epoxy compound may be used singly or in combination of two or more kinds.

In addition, the active energy ray-curable resin composition may contain an oxetane compound in addition to the epoxy compound as required. Examples of the oxetane compound include 3-ethyl-3-hydroxymethyloxetane and 1,4-bis [(3-ethyl-3-oxetane) methoxymethyl Phenyl] benzene, 3-ethyl-3- (phenoxymethyl) oxetane, bis [(3-ethyl-3-oxetanyl) methyl] ether, 3-ethyl 3- (2-ethylhexyloxymethyl) oxetane and the like. Among the oxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, di [(3-ethyl- 3-oxetanyl) methyl] ether.

These oxetane compounds are easily available in the market. Examples of commercially available products include the brand names "ARON OXETANE (registered trademark) OXT-101", "ARON OXETANE (registered trademark) OXT-121", and "ARON OXETANE (registered trademark)", both of which are sold by Toa Kosei Corporation. OXT-211 "," ARON OXETANE (registered trademark) OXT-221 "," ARON OXETANE (registered trademark) OXT-212 ", and the like.

The content of the oxetane compound is preferably 0 parts by weight or more and 50 parts by weight or less, more preferably 10 parts by weight or more and 40 parts by weight or less based on 100 parts by weight of the active energy ray-curable resin composition.

In the active energy ray-curable resin composition, the oxetane compound may be used alone or in combination of two or more.

    (Radical Polymerizable Compound)    

Furthermore, in addition to the cationically polymerizable compound such as the epoxy compound and the oxetane compound, a radical polymerizable compound may be contained.

Examples of the radically polymerizable compound include compounds having at least one (meth) acryloxy group in the molecule (hereinafter sometimes referred to as "(meth) acrylic compounds"), and having at least one in the molecule ( Methacrylamido compounds (hereinafter, sometimes referred to as "(meth) acrylamido compounds") and the like. In addition, the "(meth) acryloxy group" means methacryloxy or propyleneoxy, and the (meth) acrylamino group means methacrylamino or acrylic acid Amine.

Examples of the (meth) acrylic compound include a (meth) acrylic acid ester monomer having at least one (meth) acryloxy group in the molecule, and at least two (meth) acryloxy groups in the molecule. (Meth) acrylate oligomers and the like. These (meth) acrylic compounds may be used alone or in combination of two or more. When two or more kinds are used in combination, two or more kinds of (meth) acrylate monomers may be used, and two or more kinds of (meth) acrylate oligomers may be used. Of course, 1 of (meth) acrylate monomers may be used in combination. More than one kind of (meth) acrylate oligomer.

Examples of the (meth) acrylamido compound are N-substituted (meth) acrylamido compounds. The N-substituted (meth) acrylamide compound is a (meth) acrylamide compound having a substituent at the N-position. A typical example of the substituent is an alkyl group. The substituents at the N-position may be bonded to each other to form a ring, and -CH2- constituting the ring may be substituted with an oxygen atom. The carbon atoms constituting the ring may be bonded to a substituent such as an alkyl group or a pendant oxygen group (= O). N-substituted (meth) acrylamide is generally produced by reacting (meth) acrylic acid or a chloride thereof with a primary or secondary amine.

The content of the radical polymerizable compound is preferably 0 part by weight or more and 70 parts by weight or less with respect to 100 parts by weight of the active energy ray-curable resin composition.

In the active-energy-ray-curable resin composition, the radical polymerizable compound may be used alone or in combination of two or more.

    (Cationic polymerization initiator)    

When the active energy ray-curable resin composition contains the cationically polymerizable compound such as the oxetane compound, the epoxy compound, and the like, it is preferable to further contain a cation polymerization initiator. The cationic polymerization initiator generates a cationic species or a Lewis acid by irradiating active energy rays such as visible light, ultraviolet rays, X-rays, and electron rays to start a polymerization reaction of a cationic polymerizable compound. Examples of the cationic polymerization initiator include onium salts such as aromatic diazonium salts, aromatic iodonium salts, and aromatic sulfonium salts, and iron-aromatic hydrocarbon complexes.

Examples of the aromatic diazonium salt include benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, benzenediazonium hexafluoroborate, and the like.

Examples of the aromatic iodonium salt include diphenyliodonium (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, and bis (4- Nonylphenyl) iodonium hexafluorophosphate and the like.

Examples of the aromatic phosphonium salt include triphenylphosphonium hexafluorophosphate, triphenylphosphonium hexafluoroantimonate, triphenylphosphonium (pentafluorophenyl) borate, and 4,4'-bis [di Phenylfluorenyl] diphenylsulfide bishexafluorophosphate, 4,4'-bis [bis (β-hydroxyethoxy) phenylfluorenyl] diphenylsulfide bishexafluoroantimonate, 4 , 4'-bis [bis (β-hydroxyethoxy) phenylfluorenyl] diphenylsulfide dihexafluorophosphate, 7- [bis (p-tolylmethyl) fluorenyl] -2-isopropyl 9-oxo Hexafluoroantimonate, 7- [bis (p-tolylmethyl) fluorenyl] -2-isopropyl 9-oxosulfur (Pentafluorophenyl) borate, 4-phenylcarbonyl-4'-diphenylfluorenyl-diphenylsulfide hexafluorophosphate, 4- (p-third-butylphenylcarbonyl) -4 '-Diphenylfluorenyl-diphenylsulfide hexafluoroantimonate, 4- (p-tert-butylphenylcarbonyl) -4'-bis (p-tolylmethyl) fluorenyl-diphenylsulfide Ethyl ether (pentafluorophenyl) borate and the like.

Examples of the iron-arene complex include xylene-cyclopentadiene iron (II) hexafluoroantimonate, cumene-cyclopentadiene iron (II) hexafluorophosphate, xylene-cyclopentadiene Ferric (II) ginseng (trifluoromethylsulfonyl) methanide and the like.

These cationic polymerization initiators can be easily obtained commercially, for example, "KAYARAD (registered trademark) PCI-220" and "KAYARAD (registered trademark) PCI- "620", "UVI-6990" sold by Dow Chemical, "UVACURE (registered trademark) 1590" sold by DAICEL-CYTEC, and "ADEKA OPTOMER (registered trademark) SP-150" sold by ADEKA Corporation "And" ADEKA OPTOMER (registered trademark) SP-170 "," CI-5102 "," CIT-1370 "," CIT-1682 "," CIP-1866S "," CIP-2048S "sold by Japan's Soda Corporation And "CIP-2064S", "DPI-101", "DPI-102", "DPI-103", "DPI-105", "MPI-103", "MPI-105", "BBI-101", "BBI-102", "BBI-103", "BBI-105", "TPS-101", "TPS-102", "TPS-103", "TPS-105", "MDS -103 "," MDS-105 "," DTS-102 "and" DTS-103 "," PI-2074 "sold by Rhodia," CPI-100P "sold by SAN-APRO, etc.

Among these cationic polymerization initiators, aromatic sulfonium salts are preferred in that they can absorb light having a wavelength of 300 nm or more and obtain hardened materials having excellent hardening properties and good mechanical strength and adhesion. .

In the active energy ray-curable resin composition, the cationic polymerization initiator may be used alone or in combination of two or more.

    (Free radical polymerization initiator)    

When the active-energy-ray-curable resin composition contains the above-mentioned radically polymerizable compound, it is preferable to further contain a radical polymerization initiator. The radical polymerization initiator may be any polymer that can start polymerization of a radically polymerizable compound such as a (meth) acrylic compound by irradiating active energy rays, and a conventional one can be used.

Examples of the radical polymerization initiator include acetophenone, 3-methylacetophenone, benzyldimethylketal, and 1- (4-isopropylphenyl) -2-hydroxy-2-methyl. Propane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinylpropane-1-one, and 2-hydroxy-2-methyl-1-phenylpropane Acetophenone-based initiators for 1-one; such as diphenyl ketones, 4-chlorodiphenyl ketones, and 4,4'-diaminodiphenyl ketones; Benzoin ether initiators of benzoin propyl ether and benzoin ethyl ether; such as 4-isopropyl 9-oxosulfur 9-oxysulfur A starter; and Ketones, fluorenone, camphor quinone, benzaldehyde, anthraquinone, etc.

Free radical polymerization initiators are easily available in the market. For example, the respective trade names include "IRGACURE (registered trademark) 184", "IRGACURE (registered trademark) 907", and "DAROCUR (registered trademark)" manufactured by BASF. ) 1173 "," Lucirin (registered trademark) TPO ", etc.

In this composition, only one kind of radical polymerization initiator may be used alone, or two or more kinds may be used in combination.

    (Other additives)    

The active energy ray-curable resin composition may contain an antistatic agent, a photosensitizer, a solvent, a leveling agent, an antioxidant, a light stabilizer, and an ultraviolet absorbing agent, in addition to the above compounds, so long as the effects of the present invention are not impaired. Agent.

Examples of the photosensitizer system include a carbonyl compound, an organic sulfur compound, a persulfide, a redox compound, an azo compound, a diazo compound, a halogen compound, and a photoreducing dye.

Solvents are aliphatic hydrocarbons such as n-hexane and cyclohexane; aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, propanol, isopropanol, and n-butanol; such as acetone, methyl Ketones of ethyl ketone, methyl isobutyl ketone and cyclohexanone; such as esters of methyl acetate, ethyl acetate and butyl acetate; Lusu's Sailusu; such as halogenated hydrocarbons such as methylene chloride and chloroform.

As the leveling agent system, various compounds such as a polysiloxane system, a fluorine system, a polyether system, an acrylic copolymer system, and a titanate system can be used.

Examples of the antioxidant system include phenol-based and amine-based primary antioxidants and sulfur-based secondary antioxidants.

Examples of the light stabilizers include hindered amine light stabilizers (HALS). Examples of the ultraviolet absorber that can be used in this embodiment include a diphenyl ketone system, a benzotriazole system, and a benzoate system.

After the optical multilayer body of the present invention is left for 500 hours in an environment having a temperature of 60 ° C. and a humidity of 90%, the iodine-containing element ratio of the hardened layer is preferably 0.00 atomic% or more and 0.03 atomic% or less. From the viewpoint of further suppressing the reduction in polarization performance, it is preferably 0.025 atmic% or less, more preferably 0.020 atomic% or less, and also 0.015 atomic% or less. The ratio of the iodine-containing element in the hardened layer may be greater than 0.00 atomic%, and may be 0.005 atomic% or more. It is considered that when the amount of iodine (or iodine ion) contained in the hardened layer is within the above range, a decrease in the polarization performance of the polarizer can be suppressed.

The inventors have reasoned as follows, but this reasoning does not limit the present invention. A compound (for example, an antistatic agent, an alicyclic epoxy compound) contained in the active energy ray-curable resin composition may react with the iodine in the polarizer, and the iodine in the polarizer may be extracted. As a result, it is considered that the optical performance of the polarizer is deteriorated by the iodine moving into the hardened layer.

In addition, in this specification, the said ratio containing an iodine element means the one measured by the method as described in the Example mentioned later. When an optical multilayer system has hardened layers on both sides of a polarizer, the so-called iodine-containing ratio of the hardened layer refers to a ratio calculated from the sum of the content of iodine in each hardened layer.

The method of adjusting the content of the iodine element in the hardened layer to the above range includes, for example, a method of adjusting the amount of iodine (or iodide ion) that moves to the hardened layer over time. Of course, as long as the content of the iodine element is within the above range, iodide may be added to the curable resin composition.

A method of controlling the amount of iodine (or iodine ion) that moves to the hardened layer over time includes, for example, a method of adjusting the contents of the alicyclic epoxy compound and the antistatic agent contained in the hardening resin composition. From the viewpoint of suppressing a decrease in polarized light performance in a humid and hot environment, the content of the alicyclic epoxy compound is preferably 70 parts by weight or less with respect to 100 parts by weight of the solid content of the curable resin composition. It is more preferably 60 parts by weight or less, and may also be 50 parts by weight or less, and 30 parts by weight or less. On the other hand, from the viewpoint of improving the adhesion to the polarizer, the content of the alicyclic epoxy compound is preferably greater than 0 parts by weight based on 100 parts by weight of the solid content of the curable resin composition. It is 1 part by weight or more, and may be 5 parts by weight or more. The solid content of the curable resin composition means a total of components other than volatile components (such as solvents) in the curable resin composition. When the amount of the antistatic agent in the hardened layer is increased, the ratio of the iodine element in the hardened layer can be increased. When the amount of the antistatic agent is decreased, the ratio of the iodine element in the hardened layer can be decreased.

The iodide may be added to the curable resin composition in advance. Examples of the iodide added to the curable resin composition include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, and iodide. Tin, titanium iodide.

When the hardened layers are formed on both sides of the polarizer, the hardened layer of one and the hardened layer of the other may be formed of the same hardenable resin composition, or may be formed of hardenable resin compositions different from each other.

    [Protective film]    

The protective film is a resin film formed of a thermoplastic resin, or a film having optical functions such as a retardation film and a brightness enhancement film.

The thermoplastic resin forming the resin film may be, for example, a polyolefin resin such as a chain polyolefin resin (such as a polypropylene resin) or a cyclic polyolefin resin (such as a norbornene resin); such as cellulose triacetate 2, cellulose resins of cellulose diacetate; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; polycarbonate resins; such as (meth) acrylic resins Acrylic resin; polystyrene resin; polyvinyl chloride resin; acrylonitrile / butadiene / styrene resin; acrylonitrile / styrene resin; polyvinyl acetate resin; polyvinylidene chloride; Polyamine resins; Polyacetal resins; Modified polyphenylene ether resins; Polyfluorene resins; Polyether resins; Polyaromatic ester resins; Polyamide resins; Polyimide resins Resin, etc.

These resins may be used singly or in combination.

The resin film may be stretched to give a predetermined retardation. For example, the in-plane retardation value may be set to 0 to 200 nm. Specifically, the retardation value possessed by the resin film is, for example, an in-plane switching (IPS) mode liquid crystal panel, and a thin film having a retardation value of substantially zero can also be used. The substantially zero phase difference value means that the phase difference value is 10 nm or less in the plane of a wavelength of 590 nm, the absolute value of the phase difference value is 10 nm or less in the thickness direction of the wavelength 590 nm, and the phase difference is 480 to 750 nm in the thickness direction. The absolute value of the value is 15 nm or less. A phase difference of λ / 4 may be provided. At this time, the in-plane retardation value at a wavelength of 590 nm can be set to 100 to 200 nm.

The brightness enhancement film system may be, for example, a reflective polarizer. An example of a reflective polarizer is an anisotropic multiple film that transmits linearly polarized light in the vibration direction of one and reflects linearly polarized light in the vibration direction of the other. A specific example is DBEF (Japan Special) made by 3M Corporation. Kaiping No. 4-268505, etc.). Such a reflective polarizing plate is a reflective polarizing plate formed by extending a multilayer laminate composed of at least two layers of films having different refractive index anisotropy. Therefore, such a reflective polarizing plate has at least two thin films and the refractive index anisotropy of the extended at least two thin films is different.

In order to easily adjust the moisture permeability of a protective film described later, the protective film can be provided with a surface treatment layer on at least one side. The surface treatment layer is preferably a surface farther from the polarizer provided in the protective film. Examples of the surface treatment layer include a hard coat layer, an anti-glare layer, a light diffusion layer, and an anti-reflection layer. The thickness of the surface treatment layer can be set to 1 to 50 μm, and a desired function can be imparted to the protective film while controlling the moisture permeability of the protective film.

The moisture permeability of the protective film disposed on the side opposite to the side where the liquid crystal cell is attached is set to 400 g / m ² . It is preferable to be less than day. In view of the results of the items in the examples, the water vapor transmission rate is set to 300 g / m ² . Below day is better. The lower limit value is not particularly limited, but may be set to, for example, more than 0 g / m ² . day. Even under the influence of moisture in a hot and humid environment, the polarizing performance of the polarizer is easily reduced, but by setting the moisture permeability of the protective film to this range, the decrease in the polarizing performance in a hot and humid environment can be further reduced.

In this specification, the moisture permeability means a value measured at a temperature of 40 ° C. and a relative humidity of 90% in accordance with the cup method specified in JIS Z 0208.

When the optical laminated system has protective films on both sides of the polarizer, the same protective films can be used or different protective films can be used. Moreover, the optical laminated body may have an overlapping layer in which protective films are laminated with each other by an adhesive layer or an adhesive layer described later.

[Adhesive layer]

The adhesive layer is, for example, a layer for adhering a polarizer and a protective film, and examples of the adhesive forming the adhesive layer include an active energy ray-curable adhesive and an aqueous adhesive. Moreover, you may use the said curable resin composition.

When using a water-based adhesive, it is preferable to perform a step of removing the water contained in the water-based adhesive and drying it after laminating the polarizer and the protective film. After the drying step, an aging step may be performed, for example, at a temperature of about 20 to 45 ° C.

When an active energy ray-curable adhesive is used, a polarizing plate and a protective film are bonded, and then a drying step is performed as necessary. Next, a hardening step of curing the active energy ray-curable adhesive by irradiating the active energy ray is performed. . The light source system of the active energy ray is not particularly limited, and it is preferable to use ultraviolet light having a light emission distribution below a wavelength of 400 nm. Specifically, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a chemical lamp, a black light lamp, and a microwave can be used. Excite mercury lamps, metal halide lamps, etc.

When the polarizer and the protective film are bonded, a saponification treatment, a corona treatment, a plasma treatment, or the like may be performed on the bonding surface of at least any of these.

[Adhesive layer]

An adhesive layer can be used for laminating a polarizer and a protective film and bonding an optical laminate to a liquid crystal cell system. Examples of the adhesive layer system include acrylic adhesives, polysiloxane adhesives, and rubber adhesives. In terms of transparency, weather resistance, heat resistance, and processability, acrylic adhesives are preferred. .

Tackifiers, plasticizers, glass fibers, glass beads, metal powders, and fillers, pigments, colorants, fillers, antioxidants, Various additives such as ultraviolet absorbers, antistatic agents, and silane coupling agents.

The adhesive layer is usually formed by applying a solution of the adhesive to the release sheet and drying it. The coating on the release sheet may be, for example, a roll coating method such as reverse roll coating or gravure coating, a spin coating method, a screen coating method, a jet coating method, a dipping method, or a spray method. A release sheet provided with an adhesive layer can be used by a method such as transferring it.

The thickness of the adhesive layer disposed between the polarizer and the protective film (especially the brightness enhancement film) can be, for example, 3 to 15 μm. The thickness of the adhesive layer for bonding the optical laminate to the liquid crystal cell may be, for example, 5 to 30 μm.

[Liquid crystal display device]

In the liquid crystal display device of the present invention, the optical laminate is arranged on at least one side of the liquid crystal cell. The optical laminated body of the present invention may be arranged on the viewing side of the liquid crystal cell, or may be arranged on the back side of the liquid crystal cell. When the liquid crystal display device of the present invention is used, even in a humid and hot environment, it is possible to suppress a decrease in the polarization performance of the polarizer, and therefore it has excellent display quality.

    [Example]    

Hereinafter, the effects of the present invention will be made clearer by way of examples. The present invention is not limited to the following examples, and can be appropriately modified and implemented without changing the gist thereof.

    <Measurement of Iodine Contained Ratio>    

The protective film (resin film) provided in the optical laminate after the following wet heat durability test (that is, after being left for 500 hours in an environment having a temperature of 60 ° C and a humidity of 90%) was dissolved by a solvent to provide Remove. After exposing the hardened layer of the curable resin composition to the surface, the elemental ratio of iodine at each measurement point in the depth direction was calculated by X-ray photoelectric spectrometry (XPS) while the hardened layer was sputtered with Ar gas cluster ions. (atomic%).

The conditions for measuring XPS are as follows.

Device: K-alpha manufactured by Thermo Fisher Scientific

X-ray source: AlKα line

X-ray spot size: 400μm

Neutralizing gun

Ar gas cluster ion energy: 6keV

Grating size: 1mm × 2mm

Sputtering cycle: 30s

Pass energy: 150eV

Determination elements: C1s, O1s, B1s, I3d

The ratio of the iodine element in the hardened layer is calculated by averaging the ratio of the iodine element (atomic%) at each measurement point from the surface of the hardened layer to the interface between the hardened layer and the polarizer. When the elemental ratio (atomic%) of boron is greater than 0.5 atomic%, the interface between the hardened layer and the polarizer is considered, and the iodine element ratios at the previous measurement points are used to calculate the iodine element content ratio.

    <Evaluation of damp heat durability>    

The obtained optical laminate was cut into a size of 40 mm in length and 40 mm in width, and an adhesive layer of the optical laminate was bonded to an alkali-free glass to obtain a sample. This sample was placed in an autoclave at a temperature of 50 ° C. and a load of 5 kg for 20 minutes to cure the adhered state. Then, the sample was left to stand for 10 hours in an environment of a temperature of 23 ° C. and a relative humidity of 60%. Subsequently, the sample was set in a UV-Vis spectrophotometer V7100 made by JASCO Corporation, and the UV-Vis spectra of the polarizing plates in the transmission axis direction and the absorption axis direction were measured. The degree of polarization (corrected polarization for visual acuity) is calculated in accordance with JIS-Z872, and this is taken as the initial optical characteristics.

The sample was put into a constant temperature and humidity machine manufactured by ESPEC Co., Ltd., and subjected to a wet heat endurance test in which the temperature was 60 ° C and the relative humidity was 90% (in a hot and humid environment) for 500 hours. After the sample was taken out, it was left for 10 hours in an environment having a temperature of 23 ° C and a relative humidity of 60%. Then, the polarization degree was measured in the same manner as in the measurement of the initial optical characteristics.

Based on the obtained polarization degree, the polarization degree before the test is subtracted from the polarization degree after the test to determine the amount of polarization change.

    <Evaluation of adhesion: cross hatching test>    

The adhesive layer is laminated on a protective film and the optical laminated body is bonded to the glass via the adhesive layer, wherein the protective film is formed by interposing the active energy ray-curable resin composition of the optical laminated body (polarizing plate). The hardened layer is bonded. Use a cutter to sculpt 100 1mm square checkerboards on the surface of the protective film on the opposite side to the glass surface, and then attach cellophane tape to it. Then perform a peel test and follow the 100 checkerboards. The number of checkerboards that were not stripped and left was evaluated for adhesion. A case where the number of remaining checkerboards was 100/100 was evaluated as ○, and a case where 0 to 99/100 was evaluated as ×.

    <Production of polarizing plate with protective film on one side>    

Polyvinyl alcohol film with a thickness of 20 μm (average degree of polymerization of about 2,400, degree of saponification of 99.9 mol% or more) was uniaxially stretched to about 5 times by dry stretching, and then kept under tension, immersed in 60 After 1 minute of pure water at 0 ° C, it was immersed in an aqueous solution having a weight ratio of iodine / potassium iodide / water of 0.05 / 5/100 at 28 ° C for 60 seconds. Subsequently, it was immersed in an aqueous solution having a weight ratio of potassium iodide / boric acid / water at 8.5 / 8.5 / 100 at 72 ° C for 300 seconds. Next, it was washed with pure water at 26 ° C. for 20 seconds, and then dried at 65 ° C. to obtain a polarizer having a thickness of 7 μm in which the iodine was adsorbed and oriented on the polyvinyl alcohol film.

Next, 3 parts of carboxyl-modified polyvinyl alcohol [trade name "KL-318" obtained from KURARAY Co., Ltd.] was dissolved with respect to 100 parts of water, and a water-soluble epoxy resin polyamide epoxy was added to the aqueous solution. 1.5 parts of water-based additive [aqueous adhesive with a trade name of "Sumirez Resin (registered trademark) 650 (30) obtained from Taoka Chemical Industry Co., Ltd. and a solid content concentration of 30%]" is applied to one of the polarizers On the side, a 20 μm-thick cellulose triacetate (TAC) film [KC2CT ”manufactured by Konica Minolta Opto Co., Ltd. was laminated and dried to obtain a TAC film / aqueous adhesive layer / polarizer A polarizer with a protective film on one side.

    <Preparation of protective film>    

Prepare the following protective films. The moisture permeability is measured at a temperature of 40 ° C and a relative humidity of 90% in accordance with the cup method specified in JIS Z 0208.

Protective film S: A cyclic polyolefin resin film with a thickness of 25 μm [trade name "ZeonorFilm (registered trademark) G + 12-025" manufactured by Japan Zeon Corporation]. The moisture permeability is 20g / m ² . day.

Protective film T: acrylic resin film [trade name "OXIS (registered trademark)" manufactured by Okura Industrial Co., Ltd.]. The moisture permeability is 120g / m ² . day.

Protective film U: A thin film having a 15 μm hard coat layer made of an acrylic resin in a TAC film having a thickness of 25 μm. The moisture permeability is 280g / m ² . day.

    <Production of active energy ray-curable resin composition>    

The components shown below were prepared at the weight ratios shown in the examples to produce an active energy ray-curable resin composition.

[Active energy ray hardening compound]

"CELLOXIDE (registered trademark) 2021P": 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, obtained from DAICEL Corporation.

"DENACOL (registered trademark) EX-211": neopentyl glycol diglycidyl ether, obtained from NAGASE CHEMTEX Corporation.

[Photocationic polymerization initiator]

Triarylsulfonium salt-based photocationic polymerization initiator: Obtained as a 50% solution of propylene carbonate from SAN-APRO Co., Ltd. under the trade name "CPI-100P"

[Other ingredients]

"SH710": Polysiloxane based leveling agent, from TORAY. Obtained by DOWCORNING AG.

    <Example 1>    

The surface of the protective film S is subjected to a corona discharge treatment, and an active energy ray-curable resin composition (DENACOL EX-211: 95 parts by weight, CELLOXIDE 2021P: 5 parts by weight, photocationic polymerization initiator: 5.0 parts by weight, Leveling agent: 0.20 parts by weight) The corona discharge treated surface was applied using a bar coater so that the film thickness after curing became about 3 μm. Next, the polarizer surface of the above-mentioned polarizing plate with a protective film on one side is laminated on the active energy ray-curable resin composition layer. By using an ultraviolet irradiation device with a conveyor belt from the protective film S side [the lamp system uses "D Bulb" manufactured by Fusion UV Systems] and irradiating ultraviolet rays so that the cumulative light quantity from 280 nm to 320 nm becomes 200 mJ / cm2, The active energy ray-curable resin composition is cured. The adhesive layer is laminated on the TAC film bonded with the water-based adhesive to produce a hardened layer / polarizer / water-based adhesive layer / TAC film / adhesion of the protective film S / active energy ray-curable resin composition. Optical laminated body composed of an agent layer.

About the obtained optical laminated body, the evaluation of the wet heat durability, the measurement of the ratio containing an iodine element, and the evaluation of adhesiveness were performed. The evaluation result of adhesion was ○.

    <Example 2>    

Except for those containing DENACOL EX-211: 85 parts by weight, CELLOXIDE 2021P: 15 parts by weight, photocationic polymerization initiator: 5.0 parts by weight, and leveling agent: 0.20 parts by weight as the active energy ray-curable resin composition, The rest is the same as Example 1 to produce an optical laminate.

About the obtained optical laminated body, it carried out similarly to Example 1, evaluation of the wet heat durability, measurement of the ratio containing an iodine element, and evaluation of adhesiveness were performed. The evaluation result of adhesion was ○.

    <Example 3>    

An optical laminate was produced in the same manner as in Example 1 except that the protective film U was used as the protective film.

About the obtained optical laminated body, it carried out similarly to Example 1, and performed the evaluation of the wet heat durability, the measurement of the ratio containing an iodine element, and the evaluation of adhesiveness. The evaluation result of adhesion was ○.

    <Example 4>    

Except those containing DENACOL EX-211: 40 parts by weight, CELLOXIDE 2021P: 60 parts by weight, photocationic polymerization initiator: 5.0 parts by weight, and leveling agent: 0.20 parts by weight as active energy ray-curable resin compositions, The rest is the same as Example 1 to produce an optical laminate.

About the obtained optical laminated body, it carried out similarly to Example 1, and performed the evaluation of the wet heat durability, the measurement of the ratio containing an iodine element, and the evaluation of adhesiveness. The evaluation result of adhesion was ○.

    <Comparative example 1>    

Except those containing DENACOL EX-211: 20 parts by weight, CELLOXIDE 2021P: 80 parts by weight, photocationic polymerization initiator: 5.0 parts by weight, and leveling agent: 0.20 parts by weight as active energy ray-curable resin compositions, and An optical laminate was produced in the same manner as in Example 1 except that the protective film T was used as the protective film.

About the obtained optical laminated body, it carried out similarly to Example 1, and performed the evaluation of wet heat durability, the measurement of the ratio containing an iodine element, and the evaluation of adhesiveness. The evaluation result of adhesion was ○.

The above results are summarized in Table 1. The judgment was made when the change in the degree of polarization before and after the moist heat endurance test was -0.020% or more, and when the change in the degree of polarization before and after the moist heat endurance test was less than -0.020%.

As shown in Table 1, when the ratio of the iodine-containing element in the hardened layer satisfies the scope of the present invention, it is possible to reduce the reduction in the degree of polarization in a hot and humid environment.

    [Industrial availability]    

According to the present invention, it is useful to suppress a decrease in the polarization performance of the polarizer even in a humid and hot environment.

Claims (9)

    An optical laminated body is provided with a hardened layer of a curable resin composition on at least one side of a polarizer made of iodine oriented to a polyvinyl alcohol resin, and the optical laminated body is placed in an environment with a temperature of 60 ° C and a relative humidity of 90% After 500 hours, the iodine-containing ratio of the hardened layer was 0.03 atomic% or less.         According to the optical laminated body described in item 1 of the patent application scope, the optical laminated body further has a protective film.         The optical laminate according to item 2 of the scope of the patent application, wherein the protective film is selected from the group consisting of a cyclic polyolefin resin film, a cellulose resin film, a polycarbonate resin film, a polyolefin resin film, and a polyester. At least one layer of a resin film, an acrylic resin film, a brightness enhancement film, and a cured layer of a curable resin composition.     The optical laminated body according to item 2 or 3 of the scope of patent application, wherein the moisture permeability of the aforementioned protective film is 400 g / m ² . less than day. The optical multilayer body according to any one of claims 2 to 4, wherein the aforementioned protective film has an in-plane phase difference, and the in-plane phase difference value R ₀ at a wavelength of 590 nm is 0 to 200 nm.     The optical multilayer body according to any one of claims 2 to 5, wherein the protective film has a surface treatment layer on at least one side.         According to the optical laminated body described in any one of claims 1 to 6, the optical laminated body further has an adhesive layer.         The optical multilayer body according to any one of claims 1 to 7, wherein the content of the alicyclic epoxy compound contained in the curable resin composition is 100 parts by weight based on the curable resin composition. The ratio is 5 parts by weight or more and 60 parts by weight or less.         The invention relates to a liquid crystal display device, wherein the optical laminated body according to any one of claims 1 to 8 of the application scope is arranged in a liquid crystal cell.