KR102571177B1 - Laminates and Devices - Google Patents

Abstract

A laminate comprising a polarizing plate and a front plate laminated on one side of the polarizing plate, wherein the front plate includes a substrate layer, and the front plate has an oxygen permeability of 1300 cc/(m 2 24 h atm) or less.

Description

Laminates and Devices

This patent application claims priority under the Paris Convention to Japanese Patent Application No. 2017-178239 (filing date: September 15, 2017), and is incorporated herein by reference in its entirety.

The present invention relates to a laminate used in an image display device or the like, a device including the laminate, and a flexible image display device having the laminate.

As an optical member of an image display device such as a liquid crystal display device or an organic EL display device, a laminate or device including a polarizing plate or a retardation plate is used (for example, Patent Document 1). In recent years, the demand for thinning of image display devices has increased, and thinning is also required for members constituting laminates such as polarizing plates and retardation plates. A polarizing plate containing a conventional polyvinyl alcohol (PVA) resin stretched type polarizer or a resin film stretched type retardation film includes a polarizing plate containing a liquid crystal coating type polarizer or a liquid crystal coating type retardation layer It has been replaced by a retardation film that does.

Patent Document 1: Japanese Patent Publication 2011-251460

BACKGROUND OF THE INVENTION [0002] A portable image display device may be left in a high-temperature car or used outdoors under sunlight. However, according to the study of the present inventors, in particular, when a laminate having a member including a layer in which a liquid crystal compound is cured is exposed to a high-temperature environment, the polarization performance and the like tend to deteriorate, and the heat resistance may be insufficient. Could know.

Accordingly, an object of the present invention is to provide a laminate having excellent heat resistance, a device including the laminate, and a flexible image display device having the laminate.

As a result of intensive studies to solve the above problems, the inventors of the present invention have found that, in a laminate comprising a polarizing plate and a front plate laminated on one surface of the polarizing plate, the front plate includes a base material layer, and As long as the oxygen permeability of the front plate is 1300 cc/(m2·24h·atm) or less, it was found that the above object can be achieved, and the present invention has been completed. That is, the present invention includes the following.

[1] A polarizing plate and a front plate laminated on one side of the polarizing plate,

The front plate includes a substrate layer, and the oxygen permeability of the front plate is 1300 cc/(m 2 24 h atm) or less, a laminate.

[2] The laminate according to [1], wherein the front plate includes a hard coat layer, and the hard coat layer is disposed between the substrate layer and the polarizing plate and is adjacent to the substrate layer.

[3] The laminate according to [2], wherein the hard coat layer contains the first ultraviolet absorber.

[4] The laminate according to any one of [1] to [3], wherein the polarizing plate includes a polarizer, and the polarizer includes a layer in which a polymerizable liquid crystal compound is cured.

[5] The laminate according to [4], wherein the polarizing plate includes a retardation film, and the retardation film includes a layer in which a polymerizable liquid crystal compound is cured and disposed on a side opposite to the front plate side of the polarizer.

[6] The front plate has a ratio (A 405 /A ₄₃₀ ) of absorbance at a wavelength of 405 nm (A ₄₃₀ ) to absorbance at a wavelength of ₄₃₀ nm (A ₄₃₀ ) of 3.00 or more, [1] to [5] The laminate according to any one of the above.

[7] The laminate according to [2] or [3], wherein the front plate includes a gas barrier layer on the side opposite to the hard coat layer side of the substrate layer.

[8] The laminate according to [7], wherein at least one of the substrate layer and the gas barrier layer contains a second ultraviolet absorber.

[9] The laminate according to [7] or [8], wherein the gas barrier layer is a cured product of a curable composition containing a polyfunctional (meth)acrylate monomer (A) and a cationically polymerizable monomer (B).

[10] The laminate according to [9], wherein the cationically polymerizable monomer (B) contains a cyclic ether compound (B-1) having at least one epoxy group and/or at least one oxetanyl group.

[11] The laminate described in [10], wherein the cyclic ether compound (B-1) includes a bis cyclic ether compound (B-1-1) having two or more epoxy groups and/or two or more oxetanyl groups. sifter.

[12] The laminate according to [10] or [11], wherein the cyclic ether compound (B-1) includes a radically polymerizable cyclic ether compound (B-1-2).

[13] The content of the radically polymerizable cyclic ether compound (B-1-2) is 1 to 10 parts by mass based on 1 part by mass of the bis cyclic ether compound (B-1-1). sifter.

[14] The laminate according to any one of [3] to [13], wherein the first ultraviolet absorber is a compound represented by formula (I).

[Tue 1]

(In formula (I), A represents a methylene group, a secondary amino group, an oxygen atom or a sulfur atom, R ¹ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the alkyl group has at least one methylene group In this case, at least one of the methylene groups may be substituted with an oxygen atom or a sulfur atom, R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R ⁴ is 3 to 12 carbon atoms An alkyl group of 50, or an alkyl group of 3 to 50 carbon atoms having at least one methylene group, wherein at least one of the methylene groups represents an alkyl group substituted with an oxygen atom, and a carbon atom on the alkyl group may have a substituent bonded, X ¹ represents an electron-withdrawing group, Y ¹ represents -CO-, -COO-, -OCO-, -O-, -S-, -NR ⁵ -, -NR ⁶ CO-, or -CONR ⁷ -; R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group)

[15] The laminate according to any one of [1] to [14], including a touch sensor.

[16] The laminate according to any one of [1] to [15] for a flexible image display device.

[17] A device comprising the laminate according to any one of [1] to [16].

[18] A flexible image display device having the laminate according to [16].

The laminate of the present invention has excellent heat resistance.

1 is a schematic cross-sectional view showing an example of a layer configuration of a device of the present invention.

[Laminate]

The laminate of the present invention includes a polarizing plate and a front plate laminated on one side of the polarizing plate. The front plate includes a substrate layer and has an oxygen permeability of 1300 cc/(m 2 24 h atm) or less.

The inventors of the present invention, if the oxygen permeability of the front plate is 1300 cc / (m 2 24 h atm) or less, the laminate can have excellent heat resistance, and even when exposed to a high temperature environment, the polarization performance of the polarizing plate included in the laminate is reduced. I found something that can be effectively suppressed.

In the laminate of the present invention, the oxygen permeability of the front plate is preferably 1000 cc/(m 2 24 h atm) or less, more preferably 500 cc/(m 2 24 h atm) or less, and further Preferably it is 400 cc/(m 2 24 h atm) or less, more preferably 200 cc/(m 2 24 h atm) or less, particularly preferably 100 cc/(m 2 24 h atm) ) or less. When the oxygen permeability of the front plate is equal to or less than the above upper limit, the heat resistance of the layered product is easily improved, and the decrease in the polarization performance of the polarizing plate included in the layered product can be more effectively suppressed. The oxygen permeability of the front plate is usually more than 0 cc/(m 2 24 h atm). Oxygen permeability can be measured in accordance with JIS K 7126-1 (differential pressure method), for example, according to the method described in Examples. The oxygen permeability of the front plate can be adjusted by appropriately selecting the composition of the substrate layer, the hard coat layer, or the gas barrier layer included in the front plate, for example, the type or content of the resin or additive constituting each layer. In this way, the laminate of the present invention has low oxygen permeability and excellent oxygen barrier properties, and can exhibit excellent heat resistance.

In a preferred embodiment of the present invention, the laminate of the present invention may have excellent weather resistance. For this reason, even if the laminate of the present invention is exposed to light, for example, ultraviolet light or visible light for a long time, the polarization performance of the polarizing plate included in the laminate is reduced, and when the polarizing plate includes a retardation film, A decrease in the retardation characteristics of the retardation film can be effectively suppressed. The deterioration in the polarization performance of the polarizing plate may be evaluated, for example, by measuring the change in the visibility corrected polarization degree or the visibility corrected single transmittance before and after the heat resistance test or the light resistance test, and the smaller the change, the lower the polarization performance. indicates suppression. Also, in this specification, weather resistance is a concept including light resistance.

<substrate layer>

The base material layer contains resin. The resin preferably has transparency, and examples thereof include cellulosic polymers such as triacetyl cellulose and diacetyl cellulose, chain olefin polymers such as polypropylene, cyclic olefin polymers such as norbornene polymers, and methacrylic acid. (meth)acrylic polymers such as methyl acid polymers, polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, polycarbonate polymers, polyarylate polymers, polyether sulfone polymers, polyimide polymers, Amide type polymers etc. are mentioned. Among these, polyimide-based polymers or polyamide-based polymers are preferred because of their excellent heat resistance, flexible properties and rigidity. Since a laminate including a substrate layer made of a polyimide-based polymer has excellent flexible properties, it is particularly useful for an image display device including a flexible display. A single layer or a multi-layer may be sufficient as a base material layer. When the base material layer is a multi-layer, the same or different compositions may be sufficient as each layer.

A polyimide polymer is a polymer containing a repeating structural unit containing an imide group. Polymers containing repeating structural units containing amide groups in addition to imide groups are also preferred.

A polyimide-type polymer can be manufactured, for example, using a tetracarboxylic acid compound and a diamine compound as main raw materials. In one embodiment of the present invention, the polyimide-based polymer has a repeating structural unit represented by Formula (10). Here, G is a tetravalent organic group and A is a divalent organic group. In the polyimide polymer, structures represented by two or more types of formula (10) in which G and/or A are different may be included.

[Tue 2]

In addition, the polyimide-based polymer may contain one or more selected from the group consisting of structures represented by formulas (11) to (13) within a range that does not impair various physical properties of the substrate layer.

[Tue 3]

[Tuesday 4]

[Tuesday 5]

G and G ¹ are each independently a tetravalent organic group, preferably an organic group which may be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group. Examples of G and G ¹ include groups represented by formulas (20) to (29) and tetravalent C6 or less cyclic hydrocarbon groups.

[Tue 6]

In formulas (20) to (29),

* indicates a joining hand;

Z is a single bond, -O-, -CH ₂ -, -CH ₂ -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, - Ar-, -SO ₂ -, -CO-, -O-Ar-O-, -Ar-O-Ar-, -Ar-CH ₂ -Ar-, -Ar-C(CH ₃ ) ₂ -Ar- or -Ar-SO ₂ Represents -Ar-. Ar represents an arylene group having 6 to 20 carbon atoms which may be substituted with a fluorine atom, and a phenylene group is a specific example.

G ² is a trivalent organic group, preferably an organic group which may be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group. As G ² , a group in which any one of the bonds of the groups represented by formulas (20) to (29) is substituted with a hydrogen atom, and a trivalent C6 or less cyclic hydrocarbon group are exemplified.

G ³ is a divalent organic group, preferably an organic group which may be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group. Examples of G ³ include groups in which two non-adjacent bonds are substituted with hydrogen atoms among the bonds of groups represented by formulas (20) to (29), and cyclic hydrocarbon groups having 6 or less carbon atoms.

A, A ¹ , A ² and A ³ are each independently a divalent organic group, preferably an organic group which may be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group. Examples of A, A ¹ , A ² and A ³ include groups represented by formulas (30) to (38); groups in which hydrogen atoms thereof are substituted with methyl, fluoro, chloro, or trifluoromethyl groups; and a cyclic hydrocarbon group having 6 or less carbon atoms.

[Tue 7]

In Formulas (30) to (38), * represents a bonding hand,

Z ¹ , Z ² and Z ³ are each independently a single bond, -O-, -CH ₂ -, -CH ₂ -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ - , -C(CF ₃ ) ₂ -, -SO ₂ - or -CO-.

One example is that Z ¹ and Z ³ are -O-, and Z ² is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - or -SO ₂ -. It is preferable that the binding position to each ring of Z ¹ and Z ² and the binding position to each ring of Z ² and Z ³ are meta positions or para positions, respectively, with respect to each ring.

The substrate layer may contain the above polyimide-based polymer and polyamide-based polymer. A polyamide-based polymer is a polymer containing repeating structural units containing an amide group. The polyamide-based polymer related to the present embodiment is a polymer mainly composed of repeating structural units represented by formula (13). Preferred examples and specific examples are the same as G ³ and A ³ in the polyimide polymer. G ³ and/or A ³ may contain two or more different structures represented by Formula (13).

The polyimide polymer can be obtained, for example, by polycondensation of diamine and a tetracarboxylic acid compound (tetracarboxylic dianhydride, etc.), for example, Japanese Unexamined Patent Publication No. 2006-199945 or Japanese Patent It is compoundable according to the method described in Unexamined-Japanese-Patent No. 2008-163107. As commercially available products of polyimide, MITSUBISHI GAS CHEMICAL COMPANY, INC. No. Neopulim (registered trademark), Kawamura Sangyo Co.,Ltd. My KPI-MX300F and the like.

The weight average molecular weight of the polyimide polymer or polyamide polymer is preferably 10,000 to 500,000, more preferably 50,000 to 480,000, still more preferably 70,000 to 450,000, and particularly preferably 100,000 to 400,000. When the weight average molecular weight is equal to or greater than the above lower limit, the polyimide-based polymer can obtain high flexibility, and when the weight average molecular weight is equal to or less than the above upper limit, the viscosity of the polyimide varnish can be kept low, and the polyimide-based polymer can be obtained. Since the elongation of the polymer is easy, processability is good. In addition, a weight average molecular weight can be calculated|required by performing GPC measurement and standard polystyrene conversion.

In a preferred embodiment of the present invention, the polyimide-based polymer and the polyamide-based polymer included in the substrate layer may contain a halogen atom such as a fluorine atom that can be introduced by the aforementioned fluorine-based substituent or the like. Specific examples of the fluorine-containing substituent include a fluoro group and a trifluoromethyl group. Polyimide-based polymers and polyamide-based polymers contain halogen atoms, so that the modulus of elasticity of the base layer can be improved and the yellowness (YI value) can be reduced. It is preferable to include a halogen atom within. Further, from the viewpoints of reduction of yellowness (improvement of transparency), reduction of water absorption, and suppression of deformation of the substrate layer, the halogen atom is preferably a fluorine atom. In addition, when the halogen atom is a fluorine atom, when the laminate is folded and bent, it is difficult for a bending line to remain, and the flexible display is deformed by folding and bending. The laminate can be particularly usefully used. .

The content of halogen atoms in polyimide-based polymers and polyamide-based polymers is, from the viewpoint of improving hardness, improving elastic modulus, reducing yellowness (improving transparency), reducing water absorption, and suppressing deformation of the base layer, polyi It is preferably 1 to 40% by mass, more preferably 3 to 35% by mass, and even more preferably 5 to 32% by mass relative to 100% by mass of the mid-based polymer.

In a preferred aspect of the present invention, the substrate layer contains the polyimide-based polymer. The content of the polyimide-based polymer in the substrate layer is preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 70% by mass, and particularly preferably 90% by mass with respect to 100% by mass of the substrate layer. It is mass % or more, Preferably it is 100 mass % or less. When the content of the polyimide polymer is 40% by mass or more, the flexibility of the substrate layer becomes good.

In one embodiment of the present invention, the substrate layer may contain silica particles. When silica particles are included in the substrate layer, the content of the silica particles in the substrate layer is preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass based on 100% by mass of the substrate layer. % by mass or more, particularly preferably 40% by mass or more, preferably 60% by mass or less, and more preferably 50% by mass or less. When the content of silica is equal to or greater than the above lower limit, the gas permeation coefficient tends to decrease due to the labyrinth effect. Moreover, the flexibility of a base material layer becomes favorable as it is below the said upper limit.

The base layer may contain additives other than the silica particles and the second ultraviolet absorber described later. As another additive, the additive etc. illustrated by the page of <gas barrier layer> are mentioned, for example. These other additives may be used alone or in combination of two or more. When the substrate layer contains other additives, the content of the other additives can be appropriately selected depending on the type of additive, and is preferably 0.1 to 20% by mass, more preferably 1 to 20% by mass relative to 100% by mass of the total amount of the substrate layer. It is 10 mass %.

The thickness of the substrate layer is appropriately adjusted depending on the application, but may be, for example, 10 to 1000 μm, preferably 15 to 500 μm, more preferably 20 to 400 μm, and still more preferably 25 to 300 μm. Further, the thickness of the substrate layer may be, for example, 5 to 1000 μm, preferably 10 to 500 μm, more preferably 15 to 200 μm, and still more preferably 20 to 100 μm. When the thickness of the substrate layer is within the above range, the flexibility is good, and at the same time, it can advantageously contribute to the thinning of the device.

<Polarizer>

A polarizing plate may be a layer containing at least a polarizer. The polarizing plate may have a resin film laminated or bonded to at least one surface of the polarizer. The polarizing plate may be a single-sided protective polarizing plate in which a resin film is laminated or bonded to one surface of a polarizer, or a double-sided protective polarizing plate in which a resin film is laminated or bonded to both surfaces of a polarizer. The resin film and retardation film of the polarizing plate may be laminated or bonded to the polarizer through an adhesive layer or an adhesive layer. In addition, the resin film on the visual recognition side may also serve as the above-mentioned front plate. A preferable polarizing plate is an application type polarizing plate.

A polarizer is a film having a property of absorbing linearly polarized light having a vibration plane parallel to the absorption axis and transmitting linearly polarized light having a vibration plane orthogonal to the absorption axis (parallel to the transmission axis). It may be a layer including a layer in which a liquid crystal compound is cured (sometimes referred to as a cured layer). To impart polarization performance, a dichroic dye may be oriented in the cured layer, a polymerizable liquid crystal compound exhibiting dichroism may be used, or a film composed of a dichroic dye and a polymer compound may be used. In addition, a film in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol-based resin film can be used. Examples of the dichroic dye include iodine and dichroic organic dyes. It is preferable that the light polarizer contains the layer in which the polymeric liquid crystal compound was hardened from a viewpoint of easily improving the heat resistance of a laminated body.

A polymerizable liquid crystal compound is a compound containing a mesogen capable of exhibiting liquid crystallinity and a polymerizable group involved in a polymerization reaction. The polymerizable group is preferably a photopolymerizable group. The photopolymerizable group refers to a group capable of participating in a polymerization reaction by an active radical or an acid generated from a photopolymerization initiator.

The liquid crystal of the polymerizable liquid crystal compound may be a thermotropic liquid crystal or a lyotropic liquid crystal. For mixing with the dichroic dye, it is preferably a thermotropic liquid crystal. When the polymerizable liquid crystal compound is a thermotropic liquid crystal compound, it may be a liquid crystal compound exhibiting a nematic liquid crystal phase or a liquid crystal compound exhibiting a smectic liquid crystal phase. In order to express a polarizing function as a cured film by polymerization, it is preferable that it is a liquid crystal compound exhibiting a smectic liquid crystal phase.

As the smectic liquid crystal phase, smectic A phase, smectic B phase, smectic D phase, smectic E phase, smectic F phase, smectic G phase, smectic H phase, smectic I phase, smectic J phase, A smectic K phase, a smectic L phase, etc. are mentioned. Especially, smectic B phase, smectic F phase, and smectic I phase are preferable, and smectic B phase is more preferable. When the liquid crystal phase exhibited by the polymerizable liquid crystal compound is such a liquid crystal phase, higher polarization characteristics can be obtained.

As such a polymerizable liquid crystal compound, specifically, a compound represented by the following formula (1) (hereinafter sometimes referred to as compound (1)) and the like are exemplified.

U ¹ -V ¹ -W ¹ -X ¹ -Y ¹ -X ² -Y ² -X ³ -W ² -V ² -U ² (1)

[In Formula (1), X ¹ , X ² and X ³ each independently represent a 1,4-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent. However, at least one of X ¹ , X ² and X ³ is a 1,4-phenylene group which may have a substituent. -CH ₂ - constituting the cyclohexane-1,4-diyl group may be substituted with -O-, -S- or -NR-. R represents an alkyl group or phenyl group having 1 to 6 carbon atoms.

Y ¹ and Y ² are each independently -CH ₂ CH ₂ -, -CH ₂ O-, -COO-, -OCOO-, a single bond, -N=N-, -CR ^a =CR ^b -, - represents C≡C- or -CR ^a =N-. R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

U ¹ and U ² represent a hydrogen atom or a polymerizable group, and at least one of them is a polymerizable group.

W ¹ and W ² each independently represent a single bond, -O-, -S-, -COO- or -OCOO-.

V ¹ and V ² independently represent an alkane diyl group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - constituting the alkane diyl group is -O-, -S- or -NH It may be substituted with -.]

In compound (1), at least one of X ¹ , X ² and X ³ is preferably a 1,4-phenylene group which may have a substituent. The 1,4-phenylene group which may have a substituent is preferably unsubstituted. The cyclohexane-1,4-diyl group which may have a substituent is preferably a trans-cyclohexane-1,4-diyl group which may have a substituent, and the trans-cyclohexane-1,4-diyl group which may have a substituent -The diyl group is preferably unsubstituted. As a substituent, C1-C4 alkyl groups, such as a methyl group, an ethyl group, and a butyl group, a cyano group, or a halogen atom are mentioned.

Y ¹ is preferably -CH ₂ CH ₂ -, -COO- or a single bond, and Y ² is -CH ₂ CH ₂ - or -CH ₂ O-.

U ² is a hydrogen atom or a polymerizable group. U ¹ is a hydrogen atom or a polymerizable group, preferably a polymerizable group. U ¹ and U ² are preferably a polymerizable group together, and preferably a photopolymerizable group together. A polymerizable liquid crystal compound having a photopolymerizable group is advantageous in that it can polymerize under lower temperature conditions. The polymerizable groups represented by U ¹ and U ² may be different from each other, but are preferably the same. Examples of the polymerizable group include a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group, an oxiranyl group, and an oxetanyl group. . Especially, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxiranyl group, or an oxetanyl group is preferable, and an acryloyloxy group is more preferable.

As the alkane diyl group represented by V ¹ and V ² , a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1, 5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, decane-1,10-diyl group, tetradecane-1,14-diyl group , icosane 1,20-diyl group, etc. are mentioned. V ¹ and V ² are preferably an alkane diyl group having 2 to 12 carbon atoms, more preferably an alkane diyl group having 6 to 12 carbon atoms. Examples of substituents that the alkane diyl group having 1 to 20 carbon atoms may include include a cyano group and a halogen atom. is more preferable.

W ¹ and W ² are each independently preferably a single bond or -O-.

As a polymeric liquid crystal compound represented by Formula (1), the compound etc. represented by the following formula are mentioned, for example. When compound (1) has a cyclohexane-1,4-diyl group, the cyclohexane-1,4-diyl group is preferably trans.

[Tue 8]

[Tue 9]

[Tue 10]

[Tue 11]

Among the exemplified compound (1), formula (1-2), formula (1-3), formula (1-4), formula (1-6), formula (1-7), formula (1-8), At least one selected from the group consisting of compounds represented by formulas (1-13), formulas (1-14) and formulas (1-15) is preferred. As compound (1), you may use a commercial item, for example, Paliocolor LC242 (BASF Corporation) is mentioned.

The exemplified compound (1) can be used alone or in combination. Moreover, when combining 2 or more types of polymerizable liquid crystal compounds, it is preferable that at least 1 type is compound (1), and it is more preferable that 2 or more types are compound (1). By combining two or more types of polymerizable liquid crystal compounds, liquid crystallinity can be temporarily maintained even at a temperature below the liquid crystal-crystal phase transition temperature in some cases. The mixing ratio in the case of combining two types of polymerizable liquid crystal compounds is usually 1:99 to 50:50, preferably 5:95 to 50:50, and more preferably 10:90 to 50:50. do.

The content of the polymerizable liquid crystal compound in the polarizer is usually 70 to 99.5 parts by mass, preferably 80 to 99 parts by mass, more preferably 80 to 94 parts by mass with respect to 100 parts by mass of the solid content of the composition for forming the polarizer. and more preferably 80 to 90 parts by mass. Here, solid content refers to the total amount of components excluding the solvent from the composition for forming a polarizing layer.

A dichroic dye refers to a dye having a property in which the absorbance in the direction of the major axis of the molecule and the absorbance in the direction of the minor axis of the molecule are different. The dichroic dye may be a dye or a pigment, may exhibit liquid crystallinity, and is preferably a non-liquid crystalline dichroic dye. The dichroic dye may contain one having a polymerizable group or may contain one having no polymerizable group. As the dichroic dye, it is more preferable to have an absorption maximum wavelength (λ _max ) in the range of 300 to 700 nm. Examples of such dichroic dyes include acridine dyes, oxazine dyes, cyanine dyes, naphthalene dyes, azo dyes, anthraquinone dyes, and the like, and among these, azo dyes are preferable. Examples of the azo dye include a monoazo dye, a bisazo dye, a trisazo dye, a tetrakisazo dye, and a stilbenazo dye, and preferably a bisazo dye or a trisazo dye. The dichroic dyes may be used alone or in combination of two or more, but in order to obtain absorption over the entire visible light range, it is preferable to combine three or more dichroic dyes, and it is preferable to combine three or more azo dyes. more preferable

The content of the dichroic dye (the total amount when a plurality of species are included) is preferably 0.1 to 30 parts by mass, and preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound in the polarizer, from the viewpoint of obtaining good light absorption characteristics. It is more preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and particularly preferably 0.1 to 5 parts by mass. When the content of the dichroic dye is within this range, the alignment of the liquid crystal of the polymerizable liquid crystal compound is less likely to be disturbed, so it is preferable.

In a film obtained by adsorbing and orienting a dichroic dye on a polyvinyl alcohol-based resin film, the polyvinyl alcohol-based resin can be obtained by saponifying the polyvinyl acetate-based resin. Examples of the polyvinyl acetate-based resin include polyvinyl acetate, which is a homopolymer of vinyl acetate, and monomers copolymerizable with vinyl acetate (eg, unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, having an ammonium group ( and copolymers of meth)acrylamide and the like) and vinyl acetate.

The degree of saponification of the polyvinyl alcohol-based resin is usually 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol-based resin may be modified, for example, polyvinyl formal or polyvinyl acetal modified with aldehydes. The average degree of polymerization of the polyvinyl alcohol-based resin is usually 1000 to 10000, preferably 1500 to 5000. In addition, the average polymerization degree of polyvinyl alcohol-type resin can be calculated|required based on JIS "K" 6726.

Usually, what formed into a film of polyvinyl alcohol-type resin is used as an original film of a polarizer. Polyvinyl alcohol-type resin can be formed into a film by a well-known method. The thickness of the original film is usually 1 to 150 μm, and considering ease of stretching and the like, it is preferably 10 μm or more.

A polarizer including a cured layer in which a polymerizable liquid crystal compound is cured is, for example, a step of applying a composition for forming a polarizer containing a polymerizable liquid crystal compound to an alignment film formed on a support, an active energy ray (e.g., ultraviolet rays). ) is irradiated to the coating film, and it is manufactured through a process of curing the polymerizable liquid crystal compound. Further, the polarizer formed by adsorbing and orienting the dichroic dye on the polyvinyl alcohol-based resin film is, for example, a step of uniaxially stretching the original film, a step of dyeing the film with the dichroic dye and adsorbing the dichroic dye. , the process of treating the film with an aqueous solution of boric acid, and the process of washing the film with water, and finally dried. The thickness of the polarizer is usually 1 to 30 μm, and from the viewpoint of thinning, it is preferably 20 μm or less, more preferably 15 μm or less, particularly 10 μm or less, and may be 4 μm or less.

A polarizer obtained by adsorbing and orienting a dichroic dye on a polyvinyl alcohol-based resin film, 1) using a single film of a polyvinyl alcohol-based resin film as an original film, and performing a uniaxial stretching treatment and a dyeing treatment of a dichroic dye on this film. In addition to the method of carrying out, 2) After coating and drying a coating solution (such as an aqueous solution) containing a polyvinyl alcohol-based resin on the support to obtain a support having a polyvinyl alcohol-based resin layer, this is uniaxially stretched as a whole, and after stretching It can also be obtained according to the method of performing the dyeing process of the dichroic dye with respect to a polyvinyl alcohol-type resin layer, and then peeling and removing a support body. As the support, a commonly used resin, preferably polyester-based resins such as polyethylene terephthalate, polycarbonate-based resins, cellulose-based resins such as triacetyl cellulose, cyclic polyolefin-based resins such as norbornene-based resins, and polystyrene A film made of a base resin or the like is exemplified. If the method 2) is used, it is easy to manufacture a thin film polarizer, for example, it is also easy to manufacture a polarizer having a thickness of 7 μm or less.

The resin film is made of a common resin and may contain a common additive. Further, the resin film may be either an unstretched film or a uniaxially or biaxially stretched film. In addition, the resin film may be a protective film that plays a role of protecting the polarizer, or may be a protective film having optical functions such as retardation.

The thickness of the resin film is preferably 1 to 150 μm, more preferably 5 to 100 μm, more preferably 50 μm or less, and particularly preferably 30 μm or less.

In one embodiment of the present invention, the polarizing plate included in the laminate of the present invention preferably includes a retardation film, and the retardation film is preferably disposed on the side opposite to the front plate side of the polarizer.

The retardation film preferably contains a layer in which a polymerizable liquid crystal compound is cured (sometimes referred to as a cured layer) from the viewpoint of thinning the polarizing plate. In this specification, the cured layer is sometimes referred to as a retardation layer, and the retardation layer includes a layer providing a retardation of λ/2, a layer (positive A layer) and a positive C layer providing a retardation of λ/4, and the like. it means. In addition, the retardation film may contain an alignment film described later.

The layer providing a retardation of λ/2 preferably means a layer having an in-plane retardation value of 200 to 280 nm at a wavelength of 550 nm, more preferably a layer having an in-plane retardation value of 215 to 265 nm. do. The layer providing a retardation of λ/4 preferably means a layer having an in-plane retardation value of 100 to 160 nm at a wavelength of 550 nm, more preferably a layer having an in-plane retardation value of 110 to 150 nm. do. The positive C layer may be a layer whose refractive index exhibits a relationship of nx≒y<nz. The retardation value of the positive C layer in the thickness direction may be -50 nm to -150 nm or -70 nm to -120 nm at a wavelength of 550 nm. The wavelength dispersion of the retardation layer may be forward wavelength dispersion or reverse wavelength dispersion, and it is particularly preferable that the layer providing a retardation of λ/4 has reverse wavelength dispersion.

The layer in which the polymerizable liquid crystal compound is cured is formed, for example, on an alignment film provided on a support. The base material has a function of supporting the alignment film and may be a long support body. This support functions as a releasable support and can support the retardation layer for transfer. In addition, it is preferable that the surface has adhesive strength to the extent that peeling is possible. Examples of the support include polymers as resins included in the substrate layer.

The type of polymerizable liquid crystal compound used in the present embodiment is not particularly limited, but can be classified into rod-shaped liquid crystal compounds (rod-shaped liquid crystal compounds) and disk-shaped liquid crystal compounds (discotic liquid crystal compounds) based on their shape. there is. In addition, there are a low molecular type and a high molecular type, respectively. Polymers generally refer to those having a degree of polymerization of 100 or more (see Polymer Physics and Phase Transition Dynamics, Masao Doi, page 2, Iwanami Bookstore, 1992).

In this embodiment, any polymerizable liquid crystal compound may be used. A polymerizable liquid crystal compound may be used in combination of two or more types. In that case, at least one type has two or more polymerizable groups in the molecule. That is, the layer in which the polymerizable liquid crystal compound is cured is preferably a layer formed by fixing a liquid crystal compound having a polymerizable group through polymerization. In this case, after becoming a layer, it is not necessary to exhibit liquid crystallinity any longer.

A polymerizable liquid crystal compound has a polymerizable group capable of undergoing a polymerization reaction. As the polymerizable group, a functional group capable of undergoing an addition polymerization reaction such as a polymerizable ethylenically unsaturated group or a ring polymerizable group is preferable. More specifically, as a polymeric group, a (meth)acryloyl group, a vinyl group, a styryl group, an allyl group etc. are mentioned, for example. Especially, a (meth)acryloyl group is preferable.

The layer in which the polymerizable liquid crystal compound is cured can be formed by coating a composition containing the polymerizable liquid crystal compound on, for example, an alignment layer and irradiating with active energy rays. The composition may contain components other than the polymerizable liquid crystal compound described above. For example, it is preferable that a polymerization initiator and a solvent are contained in the said composition. The polymerization initiator to be used is selected from, for example, a thermal polymerization initiator or a photopolymerization initiator depending on the type of polymerization reaction. It is preferable that it is 0.01-20 mass % with respect to the total solid content in the said coating liquid, and, as for the usage-amount of a polymerization initiator, it is more preferable that it is 0.5-5 mass %.

The thickness of the retardation layer is preferably 0.5 μm or more. Further, the thickness of the retardation layer is preferably 10 μm or less, and more preferably 5 μm or less. In addition, the upper limit value and the lower limit value mentioned above can be combined arbitrarily. When the thickness of the retardation layer is equal to or greater than the lower limit, sufficient durability is obtained. When the thickness of the retardation layer is equal to or less than the above upper limit, it can contribute to thinning the circular polarizing plate. The thickness of the retardation layer can be adjusted so that the desired in-plane retardation value of the layer providing a retardation of λ/4, the layer providing a retardation of λ/2, or the positive C layer and the retardation value in the thickness direction are obtained.

The retardation film may contain one layer of a layer in which a polymerizable liquid crystal compound is cured, or may include two or more layers in which a polymerizable liquid crystal compound is cured. When the retardation film includes two layers of a layer in which a polymerizable liquid crystal compound is cured, the two layers are a layer providing a retardation of λ/4 and a positive C layer, or a layer providing a retardation of λ/4 and λ/2 It is preferable that it is a layer providing a phase difference of . When the retardation film includes two layers in which the polymerizable liquid crystal compound is cured, each layer in which the polymerizable liquid crystal compound is cured is prepared on an alignment film, and the two layers are laminated with an adhesive layer or an adhesive layer interposed therebetween. may be manufactured. After laminating both, the substrate and alignment film can be peeled off. It is preferable that it is 3-30 micrometers, and, as for the thickness of retardation film, it is more preferable that it is 5-25 micrometers.

The pressure-sensitive adhesive layer may be laminated on the surface of the retardation film on the opposite side to the polarizer side. The pressure-sensitive adhesive layer can be composed of a pressure-sensitive adhesive composition containing a resin such as (meth)acrylic, rubber, urethane, ester, silicone, or polyvinyl ether as a main component. Especially, the adhesive composition which uses (meth)acrylic-type resin excellent in transparency, weather resistance, heat resistance, etc. as a base polymer is suitable. The pressure-sensitive adhesive composition may be of an active energy ray curing type or a heat curing type. The thickness of the pressure-sensitive adhesive layer is usually 3 to 30 μm, preferably 3 to 25 μm.

A layered product preferred in the present invention includes a separate film (peeling film) on the surface of the polarizing plate on the opposite side to the front plate side. The separation film is preferably laminated in contact with the pressure-sensitive adhesive layer of the polarizing plate. The separation film is usually peeled off when using the laminate of the present invention, for example, when using an image display device or the like. As a separator film, the film which consists of polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyarate, etc. is mentioned, for example. These films may be used alone or in combination of two or more. The separation film may be one in which release treatment was performed on the surface on the side of the polarizing plate.

The polarizing plate may further include other films or layers. Examples thereof include, for example, a brightness enhancing film, an antiglare film, an antireflection film, a diffusion film, a condensing film, an adhesive layer, and a coating layer. Each layer constituting the polarizing plate is laminated with an adhesive or a pressure-sensitive adhesive. The adhesive may be a water-based adhesive or an active energy ray curable adhesive.

<Hard coat layer>

The front plate included in the laminate of the present invention preferably further includes a hard coat layer (sometimes referred to as layer (I)) from the viewpoint of heat resistance and weather resistance, and the hard coat layer is a substrate layer and It is more preferable to arrange|position between polarizing plates. That is, when the laminate of this invention has a hard-coat layer, it is preferable to arrange|position in order of a base material layer, a hard-coat layer, and a polarizing plate. This positional relationship is effective because it prevents the polarization performance of the polarizing plate from deteriorating in a high-temperature environment. Under a high-temperature environment, the dichroic dye contained in the polarizer constituting the polarizing plate diffuses and the polarization performance decreases, but because the front plate is provided with a hard coat layer, the hard coat layer can prevent the dichroic dye from diffusing. am. In addition, depending on the composition of the hard coat layer, the oxygen permeability of the front plate may be further reduced, and the heat resistance of the laminate may be improved.

Moreover, a polarizer may be arrange|positioned adjacent to a hard-coat layer. That is, a polarizer can be formed on the hard coat layer. By setting it as such a structure, the adhesiveness of a polarizer and a front plate can be improved.

The hard coat layer preferably contains a (meth)acrylic resin from the viewpoint of easily improving heat resistance. When the hard coat layer contains a (meth)acrylic resin, the hard coat layer is selected from (meth)acrylate monomers, urethane (meth)acrylates, polyester (meth)acrylates, and epoxy (meth)acrylates It is preferable that it is a hardened|cured material of the curable composition [it may call a curable composition (Y) or composition for hard-coat layer formation] containing at least 1 sort(s) of (meth)acrylate compound which becomes.

A (meth)acrylate monomer means a compound having one or more (meth)acryloyl groups in a molecule, preferably a (meth)acryloyloxy group, and examples thereof include one (meth)acryloyl group in a molecule. A monofunctional (meth)acrylate monomer having a monofunctional (meth)acryloyloxy group, preferably a (meth)acryloyloxy group, and a polyfunctional (meth)acryloyloxy group having two or more (meth)acryloyl groups in the molecule, preferably a (meth)acryloyloxy group. A (meth)acrylate monomer is mentioned. Moreover, monofunctional or polyfunctional may be sufficient also for urethane (meth)acrylate, polyester (meth)acrylate, and epoxy (meth)acrylate.

Examples of the monofunctional (meth)acrylate monomer include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, and isobutyl (meth)acrylate. , tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth) Acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, trimethylolpropane mono(meth)acrylate Rate, pentaerythritol mono(meth)acrylate, ethyl carbitol (meth)acrylate, 2-phenoxyethyl (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, 2-(N,N-dimethylamino) ) Ethyl (meth)acrylate, 2-carboxyethyl (meth)acrylate, 1-[2-(meth)acryloyloxyethyl]phthalic acid, 1-[2-(meth)acryloyloxyethyl]hexahydro Phthalic acid, 1-[2-(meth)acryloyloxyethyl]succinic acid and 4-[2-(meth)acryloyloxyethyl]trimellitic acid, tetrahydrofurfuryl (meth)acrylate, dicyclopentanyl ( meth)acrylate and dicyclopentenyl (meth)acrylate acid; and the like. Monofunctional (meth)acrylate monomers can be used alone or in combination of two or more.

As a polyfunctional (meth)acrylate monomer, the polyfunctional (meth)acrylate monomer (A) illustrated on the page of <gas barrier layer> is mentioned, for example. A polyfunctional (meth)acrylate monomer can be used individually or in combination of 2 or more types.

The curable composition (Y) constituting the hard coat layer preferably contains a polyfunctional (meth)acrylate monomer from the viewpoint of heat resistance. In one embodiment of the present invention, the curable composition (Y) is more preferably composed of a trifunctional (meth)acrylate monomer and a tetrafunctional (meth)acrylate monomer. The content of the tetrafunctional (meth)acrylate monomer is preferably from 0.1 to 5 parts by mass, more preferably from 0.5 to 5 parts by mass, still more preferably from 0.5 to 1 part by mass of the trifunctional (meth)acrylate monomer. ~ 3 parts by mass.

In one embodiment of the present invention, the curable composition (Y) contains a bifunctional (meth)acrylate monomer, a trifunctional (meth)acrylate monomer, and a tetrafunctional (meth)acrylate monomer from the viewpoint of easily improving heat resistance. It may contain, and may contain trifunctional (meth)acrylate monomer and hexafunctional urethane (meth)acrylate. Further, from the viewpoint of easily improving gas barrier properties and heat resistance, a 10 or more functional (meth)acrylate may be included.

In one embodiment of the present invention, the curable composition (Y) is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 85% by mass relative to the mass of the solid content of the curable composition (Y). % or more of (meth)acrylate compounds. In addition, in this specification, the solid content of a composition shows the total amount of the component remove|excluding the solvent from a composition. Moreover, the upper limit of content of a (meth)acrylate compound is 100 mass % or less, Preferably it is 98 mass % or less.

The hard coat layer, that is, the curable composition (Y) constituting the hard coat layer preferably contains a first ultraviolet absorber. In the laminate of the present invention, since the hard coat layer is located outside the polarizing plate, the polarization performance due to light that can be absorbed by the first ultraviolet absorber is deteriorated, or the retardation film or display element is included inside the hard coat layer. In a device, since deterioration of performance of the said retardation film or a display element can be suppressed, high weather resistance can be expressed.

The first ultraviolet absorber is not particularly limited as long as it is a compound capable of absorbing ultraviolet rays, and may be, for example, a known ultraviolet absorber or the like. As the ultraviolet absorber, Orient Chemical Industries Co., Ltd. Bonasorb (registered trademark) manufactured by BASF Co., Ltd., TinuVin CarboProtect (registered trademark) manufactured by BASF, and the like. The first ultraviolet absorber is a compound having excellent light absorption selectivity and affinity for the hydrophobic substance included in the layer (I), and a solvent may be used when forming the layer (I), so various solvents are used. A compound having excellent solubility in is preferred. From this point of view, in the present invention, a compound represented by formula (I) (sometimes referred to as compound (I)) is preferably used as the first ultraviolet absorber.

[Tue 12]

(In Formula (I),

A represents a methylene group, a secondary amino group, an oxygen atom or a sulfur atom;

R ¹ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and when the alkyl group has at least one methylene group, at least one of the methylene groups may be substituted with an oxygen atom or a sulfur atom;

R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms;

R ⁴ is an alkyl group having 3 to 50 carbon atoms, or an alkyl group having 3 to 50 carbon atoms having at least one methylene group, wherein at least one of the methylene groups represents an alkyl group substituted with an oxygen atom, and a carbon atom on the alkyl group has a substituent may be combined,

X ¹ represents an electron-withdrawing group;

Y ¹ represents -CO-, -COO-, -OCO-, -O-, -S-, -NR ⁵ -, -NR ⁶ CO-, or -CONR ⁷ -, R ⁵ , R ⁶ and R ⁷ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group each independently.)

In formula (I), A represents a methylene group, a secondary amino group, an oxygen atom, or a sulfur atom, and preferably represents a methylene group, a secondary amino group, or an oxygen atom from the viewpoint of exhibiting high photoselective absorptivity.

In formula (I), R ¹ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and preferably has 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms, from the viewpoint of exhibiting high photoselective absorptivity. Preferably, an alkyl group having 1 to 3 carbon atoms is shown. Here, when the alkyl group has at least one methylene group, at least one of the methylene groups may be substituted with an oxygen atom or a sulfur atom. Examples of such an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl, n-octyl, n-decyl, methoxy, ethoxy, and the like. A period, and an isopropoxy group, etc. are mentioned.

In formula (I), R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and preferably contain a hydrogen atom or 1 to 10 carbon atoms from the viewpoint of exhibiting high photoselective absorbability. of an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, still more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and particularly preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

In formula (I), R ⁴ represents an alkyl group having 3 to 50 carbon atoms or an alkyl group having 3 to 50 carbon atoms having at least one methylene group, wherein at least one of the methylene groups is substituted with an oxygen atom.

The alkyl group of 3 to 50 carbon atoms in R ⁴ preferably has 8 to 45 carbon atoms (for example, 10 to 45), from the viewpoint of affinity with hydrophobic substances, solubility in hydrophobic solvents, and economy in production. It is preferably 12 to 40, more preferably 13 to 35, and particularly preferably 14 to 30. Further, a substituent may be bonded to the carbon atom on the alkyl group.

The alkyl group having 3 to 50 carbon atoms and having at least one methylene group in R ⁴ preferably has 3 to 40 carbon atoms, more preferably from the viewpoints of affinity with hydrophobic substances, solubility in hydrophobic solvents and economical efficiency in production. represents an alkyl group of 4 to 35, particularly preferably 5 to 30. Here, in an alkyl group having 3 to 50 carbon atoms and having at least one methylene group, at least one of the methylene groups is substituted with an oxygen atom, and examples thereof include an ethoxy group, a propoxy group, and a 2-methoxyethoxymethyl group. can Moreover, polyethylene glycol groups, such as a diethylene glycol group and a triethylene glycol group, and polypropylene glycol, such as a dipropylene glycol group and a tripropylene glycol group, etc. are mentioned.

In addition, a substituent may be bonded to the carbon atom on the alkyl group of R ⁴ . Examples of the substituent include a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, an alkyl sulfinyl group having 1 to 6 carbon atoms, an alkylsulfonyl group having 1 to 6 carbon atoms, a carboxyl group, and a fluoro group having 1 to 6 carbon atoms. Alkyl group, C1-6 alkoxy group, C1-6 alkylthio group, C1-6 N-alkylamino group, C2-12 N,N-dialkylamino group, C1-6 N-alkyl A sulfamoyl group, a C2-C12 N,N-dialkyl sulfamoyl group, etc. are mentioned.

When R ⁴ is an alkyl group having 3 to 50 carbon atoms, from the viewpoint of affinity with hydrophobic substances and solubility in hydrophobic solvents, R ⁴ is more preferably an alkyl group having a branched structure of 3 to 12 carbon atoms, and 6 carbon atoms. It is more preferably an alkyl group having a branched structure of ~10.

Here, the alkyl group having a branched structure refers to an alkyl group in which at least one of the carbon atoms of the alkyl group is tertiary carbon or quaternary carbon. Specific examples of the alkyl group having a branched structure of 3 to 12 carbon atoms include an alkyl group having the following structure.

[Tue 13]

* indicates a connection part.

In formula (I), X ¹ represents an electron-withdrawing group. From the viewpoint of improving photoselective absorption, X ¹ is -NO ₂ , -CN, -COR ⁸ , -COOR ⁹ , -OR ¹⁰ , a halogen atom (-F, -Cl, -Br, -I), -CSR ¹¹ , -CSOR ¹² , or -CSNR ¹³ is preferable, a nitro group, a cyano group, or -COOR ⁹ is more preferable, and a cyano group or -COOR ⁹ is still more preferable. Here, R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, for example, an alkyl group having 2 to 5 carbon atoms, or a phenyl group.

In formula (I), Y ¹ represents -CO-, -COO-, -OCO-, -O-, -S-, -NR ⁵ -, -NR ⁶ CO-, -CONR ⁷ -, or -CS- From the viewpoint of improving photoselective absorption, preferably -CO-, -COO-, -OCO-, or -O-, more preferably -CO-, -COO-, or -OCO- indicate Here, R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, for example, an alkyl group of 2 to 5 carbon atoms, or a phenyl group.

In a preferred embodiment of the present invention, the compound represented by formula (I) is represented by formula (I-I).

[Tue 14]

Such a compound (I-I) is preferable from the viewpoint of excellent affinity with various compounds included in the hard coat layer and/or excellent solubility in various solvents.

In formula (II), the carbon number of R ^4-1 is an alkyl group of 2 to 20 carbon atoms, preferably an alkyl group of 3 to 20 carbon atoms, from the viewpoint of excellent affinity with the above various compounds and excellent solubility in various solvents. An alkyl group, more preferably an alkyl group having 4 to 20 carbon atoms, more preferably a branched alkyl group having 4 to 20 carbon atoms. Moreover, when the number of carbon atoms is within the above range, the light absorbency per 1 part by mass is improved, and weather resistance is more easily expressed.

A, R ¹ , R ² and R ³ are the same as those in formula (I).

In a more preferred embodiment of the present invention, the compound represented by formula (I) is more preferably represented by formula (I-II).

[Tuesday 15]

If the compound represented by formula (I) is a compound represented by formula (I-II), it is excellent in affinity with various compounds contained in the hard coat layer and/or solubility in various solvents, so the compound ( When compound (I-II) is included in the hard coat layer because it is easy to uniformly dissolve I-II) in a solvent, and at the same time, it has excellent affinity with various compounds and exhibits amphiphilicity. It is difficult to cause bleed-out, and the light absorption function can be exhibited stably, so that excellent light resistance can be expressed.

In formula (I-II), R ^4-1 and n are the same as those in formula (II).

Compound (I) is excellent in solubility in various solvents. Examples of such a solvent include alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, 1-butanol, 2-butanol, propylene glycol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether. ; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol monomethyl ether acetate, and ethyl lactate; ketone solvents such as acetone, 2-butanone, cyclopentanone, cyclohexanone, methyl amyl ketone, and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; Aromatic hydrocarbon solvents, such as toluene, xylene, and mesitylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran, dimethoxyethane, 1,4-dioxane, and propylene glycol monomethyl ether; and chlorinated hydrocarbon solvents such as dichloromethane, chloroform, and chlorobenzene.

These solvents include hydrophilic solvents and hydrophobic solvents. For example, an alcohol solvent is generally a solvent having hydrophilicity, although it varies depending on the number of carbon atoms. On the other hand, aliphatic hydrocarbon solvents such as pentane, hexane, and heptane are generally hydrophobic solvents. Among these solvents, those that are soluble in hydrophilic solvents or hydrophobic solvents are preferable, and those that are soluble in hydrophilic solvents and hydrophobic solvents, that is, amphipathic It is more preferable to have

Compound (I) preferably satisfies formula (a).

ε(420)　/　ε(400)　≤　0.4　(a)

In formula (a), the value of ε(420)/ε(400) represents the intensity of absorption at a wavelength of 400 nm relative to the intensity of absorption at a wavelength of 420 nm. Compared to the reverse absorption, it indicates that there is specific absorption in the wavelength region around 400 nm. The smaller this value is, the less yellow it is, and the more transparent the compound becomes. Further, when an organic EL display element is used as a display element, light emission of the organic EL display element is difficult to be hindered. In addition, there is a tendency that the deterioration of the polarization performance due to the decomposition of the dichroic dye is easily suppressed and the weather resistance can be improved.

When the compound (I) satisfying the formula (a) is included in the layer (I), a member constituting the laminate or device, in particular, a polarizer, a retardation film, a display element such as an organic EL element or a liquid crystal display element, etc. It is possible to suppress performance deterioration due to light having a wavelength of around 400 nm, and the weather resistance of the laminate or device can be further improved. By containing such a 1st ultraviolet absorber, deterioration of a polarizer, retardation film, and a display element can be protected effectively especially. In particular, when the polarizing plate includes a coating type polarizer, since the first ultraviolet absorber can absorb light in a wavelength range that promotes the decomposition of the dichroic dye, the decrease in polarization performance can be more effectively suppressed. there is a tendency

The value of ε(420)/ε(400) in Compound (I) is preferably 0.4 or less, more preferably 0.25 or less, still more preferably 0.2 or less, particularly preferably 0.15 or less, It is especially preferably 0.1 or less, very preferably 0.05 or less, for example 0.03 or less. Although the lower limit is not particularly limited, it is usually preferably 0.005 or more from the viewpoint of maintaining the absorption ability of the compound (I) around 400 nm. In one suitable embodiment of the present invention, the value of ε(420)/ε(400) is between 0.01 and 0.1.

In addition, compound (I) preferably satisfies formula (b) and formula (c) in addition to formula (a).

λmax　＜　420nm　　(b)

ε(400)　 ≥　40　　(c)

In Formula (b), λmax represents the maximum absorption wavelength of Compound (I). In formula (c), ε(400) represents the gram extinction coefficient at a wavelength of 400 nm, and the unit of the gram extinction coefficient is defined as L/(g·cm).

When formulas (b) and (c) are satisfied, the maximum absorption of compound (I) is on the shorter wavelength side than 420 nm, and it can be said that the compound exhibits high absorption at a wavelength of around 400 nm. When compound (I) satisfies this formula, the layer (I) containing such compound (I) can have high weather resistance. In the present invention, the maximum absorption λmax of Compound (I) is more preferably 415 nm or less, and even more preferably 410 nm or less.

In addition, when compound (I) satisfies formula (c), since it has high light absorption, even if the amount of compound contained in layer (I) is small, it can express a high light absorption selection function and improve weather resistance. there is. As for the value of epsilon (400), it is more preferable that it is 60 or more, it is still more preferable that it is 80 or more, and it is especially preferable that it is 100 or more. Moreover, the value of epsilon (400) is normally 500 or less.

The compound represented by formula (I-II), for example, converts 2-methylpyrroline into a 1,2-dimethylpyrrolinium salt with a methylating agent, and subsequently reacts with N,N'-diphenylformamidine and, finally, reacting an active methylene compound in the presence of acetic anhydride and an amine catalyst. Moreover, you may use what is marketed as such a compound. Compounds represented by formulas (I) and (I-I) can be similarly produced.

The content of the first ultraviolet absorber is preferably 0.01 to 100 parts by mass of the resin contained in the layer (I) or the curable monomer (for example, (meth)acrylate monomer) contained in the curable composition (Y). It may be 10 parts by mass, more preferably 0.1 to 8 parts by mass, preferably 0.1 to 20 parts by mass, and more preferably 1 to 15 parts by mass. When the content of the first ultraviolet absorber is equal to or greater than the above lower limit, the light absorbing performance of the layer (I) can be effectively developed and the weather resistance can be improved. If it is below the said upper limit, reduction of the mechanical properties of layer (I), etc. can be suppressed.

The hard coat layer, that is, the curable composition (Y) constituting the hard coat layer may further contain a conventional additive in addition to the (meth)acrylate monomer and the first ultraviolet absorber. Examples of additives include photopolymerization initiators, infrared absorbers, organic dyes, pigments, inorganic dyes, antioxidants, antistatic agents, surfactants, lubricants, dispersants, heat stabilizers, inorganic materials, and reactive polymers such as reactive urethane polymers. can be heard As an inorganic material, silicon compounds, such as a quaternary alkoxysilane, such as tetraethyl orthosilicate (TEOS), etc. other than the above-mentioned inorganic particle are mentioned, It is preferable that it is an inorganic particle, especially a silica particle. The inorganic particles may be bonded to each other by molecules having a siloxane bond (-SiOSi-). The content of the additive can be appropriately selected depending on the type of the additive, based on 100 parts by mass of the resin contained in the layer (I) or the curable monomer (for example, (meth)acrylate monomer) contained in the curable composition (Y). , Preferably it is 0.1-20 mass parts, More preferably, it is 1-10 mass parts.

The thickness of the layer (I) can be appropriately set depending on the thickness of the substrate layer and the gas barrier layer, and is, for example, preferably 1 to 20 μm, more preferably 3 to 15 μm, still more preferably 3 to 10 μm. .

<Gas barrier layer>

The laminate of the present invention may include a gas barrier layer. It is preferable that the said gas barrier layer is arrange|positioned on the surface of the base material layer on the opposite side to the polarizing plate side. That is, in this aspect, the laminate is arranged in the order of the gas barrier layer, the substrate layer, and the polarizing plate. By including the gas barrier layer, the oxygen permeability of the front plate can be reduced and the heat resistance of the laminate can be improved. In a preferred embodiment of the present invention, when the laminate of the present invention includes a hard coat layer, the gas barrier layer is preferably disposed on the surface of the substrate layer opposite to the hard coat layer. That is, in this aspect, the laminate is arranged in the order of the gas barrier layer, the base material layer, the hard coat layer, and the polarizing plate. In a preferred embodiment of the present invention, since the gas barrier layer is located outside the polarizing plate in the laminate of the present invention, performance deterioration of the polarizing plate due to oxygen can be suppressed and high weather resistance can be expressed.

The gas barrier layer is preferably a cured product of a curable composition (sometimes referred to as curable composition (X) or a composition for forming a gas barrier layer). The curable composition (X) preferably contains a polyfunctional (meth)acrylate monomer (A) and a cationically polymerizable monomer (B).

(1) multifunctional (meth)acrylate monomer (A)

The polyfunctional (meth)acrylate monomer (A) means a compound having two or more (meth)acryloyl groups, preferably (meth)acryloyloxy groups in the molecule, and examples thereof include (metha)acryloyloxy groups in the molecule. ) A bifunctional (meth)acrylate monomer having two acryloyl groups, preferably (meth)acryloyloxy groups, having three (meth)acryloyl groups, preferably three (meth)acryloyloxy groups in the molecule A trifunctional or higher than trifunctional (meth)acrylate monomer etc. which have more than one are mentioned. In addition, in this specification, the term “(meth)acrylate” means “acrylate” or “methacrylate”, and the term “(meth)acryloyl” is similarly referred to as “acryloyl” or “methacrylic acid”. Royle” means.

Examples of the bifunctional (meth)acrylate monomer include ethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, and 1,6 - Alkylene glycol di(meth)acrylates such as hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate and neopentyl glycol di(meth)acrylate; Diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, poly polyoxyalkylene glycol di(meth)acrylates such as propylene glycol di(meth)acrylate and polytetramethylene glycol di(meth)acrylate; di(meth)acrylates of halogen-substituted alkylene glycols such as tetrafluoroethylene glycol di(meth)acrylate; di(meth)acrylates of aliphatic polyols such as trimethylolpropanedi(meth)acrylate, ditrimethylolpropanedi(meth)acrylate, and pentaerythritol di(meth)acrylate; di(meth)acrylates of hydrogenated dicyclopentadiene or tricyclodecanedialkanol, such as hydrogenated dicyclopentadienyl di(meth)acrylate and tricyclodecane dimethanol di(meth)acrylate; di(meth)acrylates of dioxane glycol or dioxane dialkanol, such as 1,3-dioxane 2,5-diyldi(meth)acrylate [alias: dioxane glycol di(meth)acrylate]; di(meth)acrylates of alkylene oxide adducts of bisphenol A or bisphenol F, such as bisphenol A ethylene oxide adduct diacrylate products and bisphenol F ethylene oxide adduct diacrylate products; epoxydi(meth)acrylates of bisphenol A or bisphenol F, such as acrylic acid adducts of bisphenol A diglycidyl ether and acrylic acid adducts of bisphenol F diglycidyl ether; silicon di(meth)acrylate; di(meth)acrylate of hydroxy pivalic acid neopentyl glycol ester; 2,2-bis[4-(meth)acryloyloxy ethoxy ethoxyphenyl]propane; 2,2-bis[4-(meth)acryloyloxy ethoxy ethoxy cyclohexyl]propane; di(meth)acrylate of 2-(2-hydroxy-1,1-dimethylethyl)-5-ethyl-5-hydroxymethyl-1,3-dioxane; tris(hydroxyethyl) isocyanurate di(meth)acrylate; and the like. These bifunctional (meth)acrylate monomers can be used alone or in combination of two or more.

Although it does not specifically limit as a trifunctional or more than trifunctional (meth)acrylate monomer, For example, a trifunctional - 8 functional (meth)acrylate monomer is mentioned, a trifunctional (meth)acrylate monomer, a tetrafunctional (meth)acrylate monomer Acrylate monomers are particularly preferred.

The trifunctional (meth)acrylate monomer is a monomer having three (meth)acryloyl groups in the molecule, preferably a (meth)acryloyloxy group, and examples thereof include glycerin tri(meth)acrylate, trime Tyrolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, reaction product of pentaerythritol tri(meth)acrylate and acid anhydride, caprolactone-modified trimethylol Examples include propane tri(meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, isocyanurate tri(meth)acrylate, reaction product of caprolactone-modified pentaerythritol tri(meth)acrylate and acid anhydride. can Among these, trimethylolpropane tri(meth)acrylate is preferable from the viewpoints of surface hardness, heat resistance, flexibility, oxygen barrier properties, and warpage resistance of the laminate. These trifunctional (meth)acrylate monomers can be used alone or in combination of two or more. In the present specification, oxygen barrier property means a property that is difficult to transmit oxygen, and the higher the oxygen barrier property, the lower the oxygen permeability or oxygen permeability.

The tetrafunctional (meth)acrylate monomer is a monomer having four (meth)acryloyl groups in the molecule, preferably a (meth)acryloyloxy group, and examples thereof include ditrimethylolpropanetetra(meth)acryl Rate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, tripentaerythritol tetra(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified tripentaerythritol tetra (meth)acrylate etc. are mentioned. Among these, pentaerythritol tetra(meth)acrylate is preferable from the viewpoints of the surface hardness, heat resistance, flexibility, oxygen barrier properties, and bending resistance of the laminate. These tetrafunctional (meth)acrylate monomers can be used alone or in combination of two or more.

As a pentafunctional (meth)acrylate monomer, for example, dipentaerythritol penta(meth)acrylate, tripentaerythritol penta(meth)acrylate, dipentaerythritol penta(meth)acrylate and acid anhydride reactant, capro Lactone-modified dipentaerythritol penta(meth)acrylate, caprolactone-modified tripentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate, and a reaction product of an acid anhydride, and the like are exemplified. These 5 functional (meth)acrylate monomers can be used alone or in combination of two or more.

Examples of the hexafunctional (meth)acrylate monomer include dipentaerythritol hexa(meth)acrylate, tripentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and caprolactone-modified Tripentaerythritol hexa(meth)acrylate etc. are mentioned. These 6-functional (meth)acrylate monomers can be used alone or in combination of two or more.

Examples of the 7-functional (meth)acrylate monomer include tripentaerythritol hepta(meth)acrylate, a reaction product of tripentaerythritol hepta(meth)acrylate and an acid anhydride, and caprolactone-modified tripentaerythritol hepta(meth)acrylate. and a reaction product of caprolactone-modified tripentaerythritol hepta(meth)acrylate and an acid anhydride. These 7 functional (meth)acrylate monomers can be used alone or in combination of two or more.

The octafunctional (meth)acrylate monomer is a monomer having eight (meth)acryloyl groups, preferably (meth)acryloyloxy groups, in the molecule, and examples thereof include tripentaerythritol octa (meth)acrylate; caprolactone-modified tripentaerythritol octa(meth)acrylate; and the like. Among these, tripentaerythritol octa (meth)acrylate is preferable from the viewpoints of the surface hardness, heat resistance, flexibility, oxygen barrier properties, and bending resistance of the laminate. These 8 functional (meth)acrylate monomers can be used alone or in combination of two or more.

In one embodiment, the curable composition (X) is a trifunctional (meth) acrylate monomer, a tetrafunctional (meth) acrylate monomer, from the viewpoint of surface hardness, heat resistance, flexibility, oxygen barrier property, bending resistance, etc. of the laminate. And at least two selected from the group consisting of octa-functional (meth) acrylate monomers, tri-functional (meth) acrylate monomers, tetra-functional (meth) acrylate monomers, and octa-functional (meth) acrylate monomers in total. The mass may be 50 parts by mass or more with respect to 100 parts by mass of the polyfunctional (meth)acrylate monomer (A). The total mass of the trifunctional (meth)acrylate monomer, tetrafunctional (meth)acrylate monomer and octafunctional (meth)acrylate monomer in the curable composition (X) is preferably 60 parts by mass or more, more preferably It is 70 parts by mass or more, more preferably 80 parts by mass or more, particularly preferably 90 parts by mass or more, and most preferably 100 parts by mass. When the total mass of the trifunctional (meth)acrylate monomer, tetrafunctional (meth)acrylate monomer, and octafunctional (meth)acrylate monomer is in the above range, the surface hardness, heat resistance, flexibility, oxygen barrier property, resistance of the laminate It is advantageous from the point of view of bendability and the like.

In a preferred embodiment of the present invention, the multifunctional (meth)acrylate monomer in the curable composition (X) is composed of a trifunctional (meth)acrylate monomer and a tetrafunctional (meth)acrylate monomer. Combining a trifunctional (meth)acrylate monomer and a tetrafunctional (meth)acrylate monomer is often advantageous from the viewpoints of surface hardness, heat resistance, flexibility, oxygen barrier properties, and bending resistance of the laminate.

The content of the tetrafunctional (meth)acrylate monomer is preferably from 0.5 to 5 parts by mass, more preferably from 1 to 3 parts by mass with respect to 1 part by mass of the trifunctional (meth)acrylate monomer. When the content of the tetrafunctional (meth)acrylate monomer is within the above range, the surface hardness, flexibility, heat resistance, oxygen barrier properties, warpage resistance and the like of the laminate are easily improved.

Moreover, curable composition (X) may also contain the monofunctional (meth)acrylate monomer of an illustration in the page of <hard-coat layer>.

(2) cationically polymerizable monomer (B)

The cationically polymerizable monomer (B) means a compound having a cationically polymerizable group in its molecule. The cationically polymerizable monomer (B) is a cyclic ether compound having at least one epoxy group and/or at least one oxetanyl group (B It is preferable to include at least 1 sort(s) chosen from -1) and a vinyloxy compound (B-2).

(I) cyclic ether compound (B-1)

As the cyclic ether compound (B-1), for example, an epoxy compound having one or more epoxy groups in a molecule [referred to as epoxy compound (b)], an oxetane compound having one or more oxetanyl groups in a molecule [oxetane compound referred to as (b)], a radically polymerizable cyclic ether compound (B-1-2) having one or more radically polymerizable functional groups, and the like. The epoxy compound (b), the oxetane compound (b), and the radically polymerizable cyclic ether compound (B-1-2) may be used alone or in combination of two or more.

The epoxy group in the epoxy compound (b) is preferably unsubstituted or a group modified with a hydrocarbon group having 6 or less carbon atoms, preferably 3 or less, and more preferably unsubstituted. As the epoxy compound (b), an aliphatic epoxy compound (b1), an alicyclic epoxy compound (b2), or an aromatic epoxy compound (b3) is preferably used. These epoxy compounds (b) can be used alone or in combination of two or more.

The aliphatic epoxy compound (b1) is a compound having at least one, preferably at least two, epoxy groups bonded to aliphatic carbon atoms in a molecule. Examples of the aliphatic epoxy compound (b1) include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, and neopentyl glycol diglycidyl ether. bifunctional epoxy compounds such as cydyl ether; trifunctional or higher functional epoxy compounds such as trimethylolpropane triglycidyl ether and pentaerythritol tetraglycidyl ether; and the like. Among these, 2 epoxy groups bonded to aliphatic carbon atoms such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and neopentyl glycol diglycidyl ether have two epoxy groups in the molecule. A functional epoxy compound (aliphatic diepoxy compound) is preferred. Moreover, these aliphatic epoxy compounds (b1) can be used individually or in combination of 2 or more types.

The alicyclic epoxy compound (b2) is a compound having at least one epoxy group bonded to an alicyclic ring in a molecule, preferably a compound having two or more epoxy groups in a molecule, more preferably a compound having two epoxy groups in a molecule. (An alicyclic diepoxy compound (b2)). "Epoxy group bonded to an alicyclic ring" is the following formula (a):

[Tue 16]

It means the oxygen atom -O- of the bridge in the structure represented by In said Formula (a), m is an integer of 2-5.

An alicyclic epoxy compound (b2) can be a compound in which two or more groups in the form of (CH ₂ ) _m in the above formula (a) in which one or a plurality of hydrogen atoms have been removed are bonded to different chemical structures. . One or a plurality of hydrogen atoms in (CH ₂ ) _m may be appropriately substituted with a linear alkyl group such as a methyl group or an ethyl group.

Among these, an alicyclic epoxy compound having an epoxy cyclopentane structure (m = 3 in the formula (a)) or an epoxycyclohexane structure (m = 4 in the formula (a)) is preferable.

Examples of the alicyclic epoxy compound (b2) include 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate and 3,4-epoxy-6-methylcyclohexylmethyl 3,4-epoxy-6. -Methylcyclohexanecarboxylate, ethylenebis(3,4-epoxycyclohexanecarboxylate), bis(3,4-epoxycyclohexylmethyl) adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, diethylene glycol bis(3,4-epoxycyclohexylmethyl ether), ethylene glycol bis(3,4-epoxycyclohexylmethyl ether), and the like. Among these, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate is more preferable from the viewpoints of the surface hardness, heat resistance, flexibility, oxygen barrier properties, warpage resistance and the like of the laminate. Moreover, an alicyclic epoxy compound (b2) can be used individually or in combination of 2 or more types.

Examples of the aromatic epoxy compound (b3) include monovalent phenols having at least one aromatic ring such as phenol, cresol, and butylphenol, or mono/polyglycidyl ether compounds of alkylene oxide adducts thereof; For example, bisphenol A, bisphenol F, or a glycidyl ether compound of a compound obtained by further adding an alkylene oxide to these or an epoxy novolak resin; glycidyl ethers of aromatic compounds having two or more phenolic hydroxyl groups such as resorcinol, hydroquinone, and catechol; mono/polyglycidyl ether compounds of aromatic compounds having two or more alcoholic hydroxyl groups such as benzene dimethanol, benzene diethanol, and benzene dibutanol; glycidyl esters of polybasic acid aromatic compounds having two or more carboxylic acids such as phthalic acid, terephthalic acid, and trimellitic acid; Glycidyl esters of benzoic acids, such as benzoic acid, toluic acid, and naphthoic acid; An epoxide of styrene oxide or divinyl benzene, etc. are mentioned. These aromatic epoxy compounds (b3) can be used individually or in combination of 2 or more types.

Among the epoxy compounds (b), an alicyclic epoxy compound (b1) is preferable, and the inclusion of an alicyclic epoxy compound (b1) is advantageous from the viewpoints of surface hardness, heat resistance, flexibility, oxygen barrier property, warpage resistance, etc. of the laminate. do.

The oxetanyl group in the oxetane compound (b) is preferably unsubstituted or a group modified with a hydrocarbon group of 6 or less carbon atoms, preferably 1 to 3 carbon atoms, and more preferably a group modified with a hydrocarbon group of 1 to 3 carbon atoms.

Examples of the oxetane compound (b) include 3-ethyl-3-hydroxymethyloxetane (sometimes referred to as oxetane alcohol), 2-ethylhexyloxetane, 1,4-bis[{(3 -Ethyloxetan-3-yl)methoxy}methyl]benzene (sometimes referred to as xylylenebisoxetane), 3-ethyl-3-(phenoxymethyl)oxetane, 3-(cyclohexyloxy) ) monofunctional oxetane compounds such as methyl-3-ethyloxetane; bifunctional oxetane compounds such as 3-ethyl-3[{(3-ethyloxetan-3-yl)methoxy}methyl]oxetane; and the like. Among these oxetane compounds (b), a bifunctional oxetane compound is preferable.

The radically polymerizable cyclic ether compound (B-1-2) has one or more radically polymerizable functional groups in the molecule. Examples of the radically polymerizable functional group include a vinyl group and a (meth)acryloyl group, preferably a (meth)acryloyl group, and more preferably a methacryloyl group. The radically polymerizable cyclic ether compound may be an epoxy compound having a radically polymerizable functional group, an oxetane compound having a radically polymerizable functional group, or the like, and is preferably an epoxy compound having a radically polymerizable functional group. The epoxy compound having a radically polymerizable functional group may be any one of alicyclic, aliphatic and aromatic, but alicyclic is particularly preferred. Since the radically polymerizable cyclic ether compound (B-1-2) has a radically polymerizable group and a cationically polymerizable group (e.g., epoxy group, oxetanyl group, etc.), it can cause both radical polymerization and cationic polymerization. .

Specific examples of the radically polymerizable cyclic ether compound (B-1-2) include epoxy compounds having a vinyl group such as 1,2-epoxy-4-vinylcyclohexane; epoxy compounds having (meth)acryloyl groups such as 3,4-epoxycyclohexylmethyl (meth)acrylate and glycidyl (meth)acrylate; and oxetane compounds having a (meth)acryloyl group, such as (meth)acrylic acid (3-ethyl-3-oxetanyl)methyl. These radically polymerizable cyclic ether compounds can be used alone or in combination of two or more.

The cyclic ether compound (B-1) is a biscyclic ether compound having two or more epoxy groups and/or two or more oxetanyl groups (B- 1-1) is preferably included. As the biscyclic ether compound (B-1-1), among the above epoxy compound (b) and the above oxetane compound (b), an epoxy compound having two or more epoxy groups, an oxetane compound having two or more oxetanyl groups, etc. can be heard

Further, the cyclic ether compound (B-1) preferably contains a radically polymerizable cyclic ether compound (B-1-2). By containing the radically polymerizable cyclic ether compound (B-1-2), the surface hardness, flexibility, heat resistance, oxygen barrier properties, warpage resistance and the like of the laminate can be further improved.

When the curable composition (X) contains the radically polymerizable cyclic ether compound (B-1-2), the content of the radically polymerizable cyclic ether compound (B-1-2) is the biscyclic ether compound (B-1-2). 1) With respect to 1 part by mass, it is preferably 1 to 10 parts by mass, more preferably 1.5 to 7 parts by mass, still more preferably 1.5 to 5 parts by mass. When the content of the radically polymerizable cyclic ether compound (B-1-2) is within the above range, a laminate having better surface hardness, flexibility, heat resistance, oxygen barrier properties, warpage resistance and the like can be formed.

(II) vinyloxy compound (B-2)

The vinyloxy compound (B-2) means a compound having one or more vinyloxy groups in the molecule. In particular, the vinyloxy compound (B-2) is preferably a compound having two or more vinyloxy groups. These vinyloxy compounds (B-2) can be used alone or in combination of two or more. The vinyloxy compound (B-2) may be a monomer or an oligomer, but is preferably a monomer.

Examples of the vinyloxy compound (B-2) include 2-ethylhexyl vinyl ether, dodecyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, triethylene glycol divinyl ether, and adipine. Aliphatic vinyl ether compounds, such as acid divinyl; alicyclic vinyl ether compounds such as cyclohexyl vinyl ether and cyclohexanedimethanol divinyl ether; Aromatic vinyl ether compounds, such as phenyl vinyl ether and benzenedimethanol divinyl ether, etc. are mentioned. These vinyloxy compounds (B-2) can be used alone or in combination of two or more. Among the vinyloxy compounds (B-2), from the viewpoints of surface hardness, flexibility, heat resistance, oxygen barrier properties, warpage resistance and the like of the laminate, an alicyclic vinyl ether compound is preferable.

In the curable composition (X), the cationically polymerizable monomer (B) containing the vinyloxy compound (B-2) is advantageous from the viewpoints of surface hardness, flexibility, heat resistance, oxygen barrier properties, warpage resistance, etc. of the resulting laminate. do. When the curable composition (X) contains the vinyloxy compound (B-2), the content of the vinyloxy compound (B-2) is the polyfunctional (meth)acrylate monomer (A) and the cationically polymerizable monomer (B) It is preferably 3 to 50 parts by mass, more preferably 10 to 40 parts by mass, still more preferably 15 to 35 parts by mass with respect to 100 parts by mass of the total amount of. When the content of the vinyloxy compound (B-2) is within the above range, the surface hardness, flexibility, heat resistance, oxygen barrier properties, warpage resistance and the like of the laminate can be further improved.

In the curable composition (X), the content of the vinyloxy compound (B-2) is preferably 0.1 to 3 parts by mass, more preferably 0.5 to 2.5 parts by mass, based on 1 part by mass of the cyclic ether compound (B-1). Part by mass, more preferably 0.5 to 2.0 part by mass. When the content of the vinyloxy compound (B-2) is within the above range, the surface hardness, flexibility, heat resistance, oxygen barrier properties, warpage resistance and the like of the laminate can be further improved.

The content of the cationically polymerizable monomer (B) is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass, still more preferably based on 1 part by mass of the polyfunctional (meth)acrylate monomer (A). is 0.5 to 1.5 parts by mass, particularly preferably 0.8 to 1.2 parts by mass. When the content of the cationically polymerizable monomer (B) is within the above range, it is advantageous from the viewpoints of surface hardness, flexibility, heat resistance, oxygen barrier properties, and bending resistance of the laminate.

In one preferred embodiment of the present invention, the content of the polyfunctional (meth)acrylate monomer (A) is preferably 5 to 80% by mass, more preferably 10 to 60% by mass, still more preferably 20 to 50% by mass. % by mass, particularly preferably 25 to 40% by mass, and the content of the cyclic ether compound (B-1) is preferably 5 to 80% by mass, more preferably 7 to 60% by mass, still more preferably 10 to 50% by mass, particularly preferably 10 to 40% by mass, and the content of the vinyloxy compound (B-2) is preferably 3 to 60% by mass, more preferably 5 to 40% by mass, still more preferably is 10 to 30% by mass. Here, the said content is based on 100 mass % of solid content of a curable composition. When the contents of the polyfunctional (meth)acrylate monomer (A), the cyclic ether compound (B-1), and the vinyloxy compound (B-2) are within the above ranges, surface hardness, flexibility, heat resistance, oxygen barrier properties, and resistance It is easy to form a laminate excellent in warpability.

In a preferred embodiment of the present invention, the content of the polyfunctional (meth)acrylate monomer (A) is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, still more preferably 20 to 40% by mass. % by mass, and the content of the biscyclic ether compound (B-1-1) is preferably 3 to 20% by mass, more preferably 5 to 15% by mass, and the radical polymerizable cyclic ether compound (B-1-1 The content of 2) is preferably 10 to 40% by mass, more preferably 15 to 40% by mass, still more preferably 15 to 35% by mass. Here, the said content is based on 100 mass % of solid content of a curable composition. When the contents of the polyfunctional (meth)acrylate monomer (A), the biscyclic ether compound (B-1-1), and the radically polymerizable cyclic ether compound (B-1-2) are within the above ranges, surface hardness, flexibility, It is easy to form a laminate having better heat resistance, oxygen barrier properties, warpage resistance, and the like.

(3) Additives

The curable composition (X) may also contain a radical polymerization initiator (C) and a cationic polymerization initiator (D). It is preferable to contain a photoradical polymerization initiator (C) and a photocationic polymerization initiator (D) from a viewpoint of being easy to harden quickly. When the photo-radical polymerization initiator is contained in the curable composition, the polyfunctional (meth)acrylate monomer (A), which is a radically polymerizable compound, can be rapidly cured. The photo-radical polymerization initiator is not particularly limited as long as it can initiate curing of the radically polymerizable compound by irradiation of active energy rays such as visible rays, ultraviolet rays, X-rays, and electron beams, and specific examples include acetophenone, 3-methylacetophenone, benzyl dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-methyl-1-[4-(methylthio)phenyl]- acetophenone-based initiators such as 2-morpholinopropan-1-one and 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzophenone-based initiators such as benzophenone, 4-chlorobenzophenone, and 4,4'-diaminobenzophenone; alkylphenone-based initiators such as 2,2-dimethoxy-1,2-diphenylethan-1-one and 1-hydroxy-cyclohexyl-phenyl-ketone; benzoin ether-based initiators such as benzoin propyl ether and benzoin ethyl ether; thioxanthone-based initiators such as 4-isopropylthioxanthone; acylphosphine oxide-based initiators such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; In addition, xanthone, fluorenone, camphaquinone, benzaldehyde, anthraquinone, etc. are mentioned. These photo-radical polymerization initiators may be used alone or in combination of two or more. Among these photo-radical polymerization initiators, alkylphenone-based initiators, acylphosphine oxide-based initiators, and the like are preferable.

Moreover, when a photocationic polymerization initiator is contained in a curable composition, the cationically polymerizable monomer (B) which is a cationically polymerizable compound can be rapidly hardened. The photocationic polymerization initiator is not particularly limited as long as it can initiate curing of the cationically polymerizable monomer by generating a cationic species or Lewis acid upon irradiation with active energy rays, and specific examples thereof include aromatic diazonium salts, For example, benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, benzenediazonium hexafluoroborate; Aromatic iodonium salts such as diphenyliodonium tetrakis(pentafluorophenyl) borate, (4-methylphenyl)[4-(2-methylpropyl)phenyl]iodonium hexafluorophosphate, diphenyliodonium hexa fluorophosphate, diphenyliodonium hexafluoroantimonate, bis(4-nonyl phenyl) iodonium hexafluorophosphate; Aromatic sulfonium salts such as triphenyl sulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenyl sulfonium tetrakis (pentafluorophenyl) borate, 4,4'-bis(di phenylsulfonio) diphenylsulfide bishexafluorophosphate, 4,4'-bis[di(β-hydroxyethoxy) phenylsulfonio]diphenylsulfidebishexafluoroantimonate, 4, 4′-bis[di(β-hydroxyethoxy)phenylsulfonio]diphenylsulfide bishexafluorophosphate, 7-[di(p-toluyl)sulfonio]-2-isopropylthioxane Tonehexafluoroantimonate, 7-[di(p-toluyl)sulfonio]-2-isopropylthioxanthone tetrakis(pentafluorophenyl)borate, 4-phenylcarbonyl-4'-di Phenylsulfoniodiphenylsulfide hexafluorophosphate, 4-(p-tert-butylphenyl carbonyl)-4'-diphenylsulfoniodiphenylsulfide hexafluoroantimonate, 4-(p-tert- butylphenyl carbonyl)-4'-di(p-toluyl) sulfoniodiphenylsulfide tetrakis(pentafluorophenyl) borate; iron-arene complexes such as xylene-cyclopentadienyl iron(II) hexafluoroantimonate, cumene-cyclopentadienyl iron(II) hexafluorophosphate, xylene-cyclopentadienyl iron(II) tris( trifluoromethylsulfonyl) methanide; and the like. These photocationic polymerization initiators can be used individually or in combination of 2 or more types. Among these photocationic polymerization initiators, aromatic iodonium salts and aromatic sulfonium salts are preferred. Further, since the radically polymerizable cyclic ether compound (B-1-2) has a radically polymerizable group and a cationically polymerizable group (e.g., epoxy group, oxetanyl group, etc.), both radical polymerization and cationic polymerization can occur. there is. For this reason, when a photoradical polymerization initiator and a photocationic polymerization initiator are used together, it is easy to cure more rapidly.

Since the curable composition (X) contains a polyfunctional (meth)acrylate monomer, which is a radical polymerizable compound, and a cationically polymerizable monomer, which is a cationically polymerizable compound, the curable composition contains a photocationic polymerization initiator and a photoradical polymerization initiator. It is preferable, and by using a photocationic polymerization initiator and a photoradical polymerization initiator together, a layered product having more excellent surface hardness, flexibility, heat resistance, oxygen barrier properties, and warping resistance can be formed.

When the curable composition contains a radical polymerization initiator, the content of the radical polymerization initiator (C) is preferably 1 to 15 parts by mass, more preferably 1 to 15 parts by mass, based on 100 parts by mass of the polyfunctional (meth)acrylate monomer (A). is 3 to 12 parts by mass. The content of the cationic polymerization initiator (D) is preferably 1 to 15 parts by mass, more preferably 3 to 10 parts by mass, based on 100 parts by mass of the cationically polymerizable monomer (B). When the content of the radical polymerization initiator or the cationic polymerization initiator is within the above range, the curability is further enhanced, and the surface hardness, flexibility, heat resistance, oxygen barrier properties, and warpage resistance can be further improved.

The curable composition (X) may further contain inorganic particles from the viewpoint of increasing the surface hardness of the layered product. Examples of inorganic particles include silica particles, reactive silica particles, alumina particles, reactive alumina particles, talc particles, clay particles, calcium carbonate particles, magnesium carbonate particles, barium sulfate particles, aluminum hydroxide particles, titanium dioxide particles, oxide A zirconium particle etc. are mentioned. Inorganic particles can be used alone or in combination of two or more. In a preferred aspect, the curable composition (X) further contains reactive silica particles. When reactive silica particles are contained in the curable composition, a cross-linked structure can be formed with a compound having a reactive group or a reactive site included in the curable composition, and a laminate having particularly excellent oxygen barrier properties can be obtained. Examples of the reactive group include an acryloyl group, a hydroxyl group, an alkoxy group (eg, a methoxy group, an ethoxy group, etc.), a carboxyl group, a thiol group, an amino group, a nitro group, an acyl group, an epoxy group, and the like. . Among these, it reacts with the acryloyl group of the polyfunctional acrylate monomer (A) or the radical polymerizable group of the radically polymerizable cyclic ether compound (B-1-2) to form a crosslinked structure, particularly improving the oxygen permeability of the laminate. From the point of view, an acryloyl group is most preferred. Inorganic particles can be used alone or in combination of two or more.

The average particle diameter of the reactive silica particles is preferably 1 to 100 nm, more preferably 3 to 50 nm, still more preferably 5 to 30 nm, from the viewpoint of the oxygen barrier properties of the laminate, transparency, and particle aggregation suppression. is nm. The average particle diameter can be measured using a conventional method such as a laser diffraction method.

When the curable composition contains reactive silica particles, the content of the reactive silica particles is preferably 1 to 70% by mass, based on the mass of the solid content of the curable composition (X), from the viewpoint of oxygen barrier properties and flexibility. It is preferably 5 to 65% by mass, more preferably 5 to 60% by mass, particularly preferably 10 to 50% by mass, particularly 15 to 45% by mass.

The curable composition (X) may further contain a leveling agent. The leveling agent has a function of adjusting the fluidity of the curable composition and making the cured film obtained by applying the curable composition more flat, examples thereof being silicone-based such as polydimethylsiloxane, polyacrylate-based, and perfluoroalkyl-based. of surfactants, and the like. The content of the leveling agent is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass with respect to the mass of the solid content of the curable composition (X).

From the viewpoint of imparting antistatic ability to the layered product, an antistatic agent may be contained in the curable composition. As the antistatic agent, metal oxides and metal salts are preferable. Examples of the metal oxide include ITO (indium-tin composite oxide), ATO (antimony-tin composite oxide), tin oxide, antimony pentoxide, zinc oxide, zirconium oxide, titanium oxide, and aluminum oxide. As a metal salt, zinc antimonate etc. are mentioned. When the curable composition (X) contains an antistatic agent, the content of the antistatic agent varies depending on the required antistatic performance, but the total amount of the polyfunctional (meth)acrylate monomer (A) and the cationically polymerizable monomer (B) 100 Regarding parts by mass, it is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass.

In a preferred embodiment of the present invention, the substrate layer and/or the gas barrier layer contain a second ultraviolet absorber. In this aspect, in the laminate of the present invention, since the substrate layer and/or the gas barrier layer containing the second ultraviolet absorber are located outside the polarizing plate, the performance of the polarizing plate by the light that can be absorbed by the second ultraviolet absorber Deterioration or performance deterioration of the display element can be suppressed and high weather resistance can be expressed in a device including a display element on the inside of the substrate layer and/or the gas barrier layer.

Examples of the second ultraviolet absorber include organic ultraviolet absorbers and fine powder type sunscreens. As the organic UV absorber, for example, a benzotriazole-based, triazine-based, acrylonitrile-based, benzophenone-based, aminobutadiene-based, salicylate-based, etc. can be used. Among these ultraviolet absorbers, a benzotriazole-based or triazine-based ultraviolet absorber is preferable from the viewpoint of having high ultraviolet absorbency and being able to express high ultraviolet ray-cutting ability even when used in an image display device. In order to widen the width of ultraviolet absorption, ultraviolet absorbers having different maximum absorption wavelengths may be used alone or in combination of two or more types.

The second ultraviolet absorber is preferably an ultraviolet absorber having good absorption selectivity for light around a wavelength of 380 nm. When such a second ultraviolet absorber is contained in the substrate layer and/or the gas barrier layer, deterioration of the members constituting the laminate or device, in particular, performance deterioration of the display element due to ultraviolet rays having a wavelength of around 380 nm can be effectively suppressed. Therefore, the weather resistance of the laminate or device can be further improved.

In the second ultraviolet absorber, examples of the benzotriazole type include 2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6[(2H-benzotriazole-2- yl) phenol]], 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl) phenol, 2-[5-chloro(2H)-benzotriazole -2-yl] -4-methyl-6- (tert-butyl) phenol; and the like.

The representative commercial products of the benzotria zolge ultraviolet absorber include Sumisorb 200, Sumisorb 250, Sumisorb 300, Sumisorb 340, Sumisorb 350, Sumisorb 400, BASF Tinuvin Tinuvin 99-2, Tinuvin 384 -2, TINUVIN'900, TINUVIN'928, TINUVIN'1130, ADEKASTAB'LA-24, ADEKASTAB'LA-29, ADEKASTAB'LA-31, ADEKASTAB'LA-32, and ADEKASTAB'LA-36 from ADEKA.

As a triazine system, 2-(4,6-diphenyl- 1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol etc. are mentioned, for example.

Typical commercially available triazine-based organic ultraviolet absorbers include BASF TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 477, TINUVIN 479, ADEKA Corp. ADEKASTAB LA-46, ADEKASTAB LA-F70, and the like.

In addition, a HALS agent having a deterioration prevention function equivalent to that of an ultraviolet ray inhibitor may be used, for example, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, poly[[6-(1, 1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl) imino]hexa Methylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], dibutylamine 1,3,5-triazine N, N-bis (2,2,6, and polycondensates of 6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl) butylamine.

Representative commercially available products made by HALS include BASF's TINUVIN 111, TINUVIN 123, TINUVIN 144, TINUVIN 292, TINUVIN 5100, ADEKA Corp. My ADEKASTAB LA-52, ADEKASTAB LA-57, ADEKASTAB LA-63P, ADEKASTAB LA-68, ADEKASTAB LA-72, ADEKASTAB LA-77, ADEKASTAB LA-81, ADEKASTAB LA-82 A-87, ADEKASTAB LA-402 , ADEKASTAB, LA-502, etc. are mentioned.

As the fine powder type sunscreen agent, a fine particle metal oxide is preferable, and it is more preferable that the average primary particle size thereof is in the range of 1 to 100 nm and has an ultraviolet protection effect. Examples of the metal oxide include titanium oxide, zinc oxide, cerium oxide, iron oxide, and magnesium oxide. One or more of these particulate metal oxides, preferably two or more, may be combined. Further, the shape of the particulate metal oxide is not particularly limited, such as spherical, acicular, rod, spindle, irregular, or plate-like, and the crystal form is not particularly limited, such as amorphous, rutile, or anatase.

The particulate metal oxide is a conventionally known surface treatment such as fluorine compound treatment, silicone treatment, silicone resin treatment, pendant treatment, silane coupling agent treatment, titanium coupling agent treatment, oil treatment, N-acylated lysine treatment, polyacrylic acid Treatment, metal soap treatment, amino acid treatment, inorganic compound treatment, plasma treatment, mechanochemical treatment, etc. are preferred to be surface treated in advance, and in particular, a kind selected from silicon, silane, fluorine compounds, amino acid compounds, and metal soaps. It is preferable to have water repellent treatment with the above surface treatment agent.

A typical commercial product of fine particle metal oxide is SUMITOMO OSAKA CEMENT Co., Ltd. HMZD-50 etc. are mentioned.

When a second ultraviolet absorber is included in the substrate layer and/or gas barrier layer, the content of the second ultraviolet absorber can be appropriately selected according to the ultraviolet transmittance or the absorbance of the ultraviolet absorber, and is preferably 0.1 to 10 parts by mass. am. When the content of the second ultraviolet absorber is equal to or greater than the lower limit, the ultraviolet absorbency of each layer can be effectively developed and the weather resistance can be improved. If it is below the said upper limit value, reduction of the mechanical characteristics of each layer, etc. can be suppressed. In addition, the content of the second ultraviolet absorber is 100 parts by mass of the resin contained in the base layer, or a curable monomer contained in the curable composition (X) forming the gas barrier layer [for example, a polyfunctional (meth)acrylate monomer ( A) and cationically polymerizable monomer (B)] based on 100 parts by mass.

The curable composition (X) may contain a solvent. The solvent should just be able to dissolve the curable composition (X), and examples thereof include methanol, ethanol, 1-propanol, 2-propanol (isopropyl alcohol), 1-butanol, 2-butanol (sec-butyl alcohol), alcohol solvents such as 2-methyl-1-propanol (isobutyl alcohol) and 2-methyl-2-propanol (tert-butyl alcohol); alkoxy alcohol solvents such as 2-ethoxyethanol, 2-butoxyethanol, 3-methoxy-1-propanol, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; ketol solvents such as diacetone alcohol; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; aromatic hydrocarbon solvents such as toluene and xylene; Ester solvents, such as ethyl acetate and butyl acetate, etc. are mentioned. These solvents can be used alone or in combination of two or more.

The curable composition (X) may further contain other additives within a range not impairing oxygen barrier properties. Examples of other additives include antioxidants, release agents, stabilizers, bluing agents, flame retardants, pH adjusters, and thickeners. These other additives may be used alone or in combination of two or more. When the curable composition contains other additives, the content of the other additives is preferably from 0.01 to 20% by mass, more preferably from 0.1 to 10% by mass, based on the mass of the solid content of the curable composition.

The curable composition (X) is a component contained in the composition, a polyfunctional (meth)acrylate monomer (A), a cationically polymerizable monomer (B), a radical polymerization initiator, a cation polymerization initiator, inorganic particles, and a second It can be obtained by mixing a UV absorber, a leveling agent, and other additives by a conventional method, for example, and the order of mixing is not particularly limited. Depending on the composition of the hard coat layer, gas barrier properties may be exhibited. In this case, the hard coat layer may be used as the gas barrier layer. That is, you may use curable composition (Y) as a composition which forms a gas barrier layer.

As described later, the gas barrier layer may be obtained by applying the curable composition (X) to the substrate layer, functional layer or primer layer to form a coating film and curing the coating film.

The thickness of the gas barrier layer can be appropriately selected depending on the thickness of the hard coat layer and the substrate layer, etc., and is preferably 1 to 50 μm, more preferably 2 to 30 μm.

The layered product of the present invention may have other layers between the layers constituting the layered product. In one embodiment of the present invention, another layer such as a primer layer may be included between the polarizing plate and the hard coat layer or between each layer.

For example, a primer layer may be disposed between the substrate layer and the gas barrier layer. The primer layer is a layer formed of a primer, and can improve the adhesion between the substrate layer and the gas barrier layer. The compound included in the primer layer may be chemically bonded to a resin included in the base layer, preferably a polyimide-based polymer, at the interface.

As the primer agent, there is, for example, an ultraviolet curing type, a heat curing type, or a two-component curing type epoxy compound primer agent. The primer agent may be a polyamic acid. These are suitable in order to improve the adhesiveness of a base material layer and a gas barrier layer.

The primer agent may contain a silane coupling agent. A silane coupling agent may chemically bond with the silicon compound which may be contained in a base material layer by a condensation reaction. A silane coupling agent can be suitably used especially when the compounding ratio of the silicon compound which can be contained in a base layer is high.

The silane coupling agent is a compound having a silicon atom and an alkoxy silyl group having 1 to 3 alkoxy groups covalently bonded to the silicon atom. A compound containing a structure in which two or more alkoxy groups are covalently bonded to a silicon atom is preferable, and a compound containing a structure in which three alkoxy groups are covalently bonded to a silicon atom is more preferable. As said alkoxy group, a methoxy group, an ethoxy group, an isopropoxy group, n-butoxy group, t-butoxy group etc. are mentioned, for example. Among these, a methoxy group and an ethoxy group are preferable because they can enhance reactivity with silicon materials.

It is preferable that the silane coupling agent has a substituent with high affinity for the substrate layer and the gas barrier layer. From the viewpoint of affinity with the polyimide-based polymer that can be included in the substrate layer, the substituent of the silane coupling agent is preferably an epoxy group, amino group, ureido group or isocyanate group. When the substrate layer contains (meth)acrylates, it is preferable that the silane coupling agent used in the primer layer has an epoxy group, a methacrylic group, an acryl group, an amino group, or a styryl group because affinity increases. . Among these, a silane coupling agent having a substituent selected from a methacrylic group, an acryl group, and an amino group, when the substrate layer includes a polyimide-based polymer, the substrate layer and the gas barrier layer have excellent affinity. desirable because

The thickness of the primer layer is appropriately adjusted according to the thickness of the gas barrier layer, but is, for example, 0.01 nm to 20 μm. In the case of using an epoxy-based compound primer, the thickness of the primer layer is preferably 0.01 to 20 μm, more preferably 0.1 to 10 μm. When using a silane coupling agent, the thickness of the primer layer is preferably 0.1 nm to 1 μm, more preferably 0.5 nm to 0.1 μm.

In one embodiment of the present invention, the laminate of the present invention may further include a functional layer in addition to the polarizing plate, the hard coat layer, the substrate layer, and the gas barrier layer. As a functional layer, the layer which has various functions, such as an ultraviolet absorption layer, an adhesive layer, a color adjustment layer, and a refractive index adjustment layer, is mentioned. The laminate of the present invention may have one or more functional layers. In addition, one functional layer may have a plurality of functions.

The ultraviolet absorbing layer is a layer having an ultraviolet absorbing function, and includes, for example, a main material selected from ultraviolet curable transparent resins, electron beam curable transparent resins, and thermosetting transparent resins, and an ultraviolet absorber dispersed in the main material. consists of The ultraviolet ray absorbing layer may contain the first or second ultraviolet ray absorbent.

The pressure-sensitive adhesive layer is a layer having an adhesive function, and has a function of adhering the laminate to another member. As a material for forming the pressure-sensitive adhesive layer, a commonly known material can be used. For example, a thermosetting resin composition or a photocurable resin composition can be used.

The pressure-sensitive adhesive layer may be composed of a resin composition containing a component having a polymerizable functional group. In this case, strong adhesion can be achieved by further polymerizing the resin composition constituting the pressure-sensitive adhesive layer after the laminate is bonded to another member. The adhesive strength between the layered product and the pressure-sensitive adhesive layer may be 0.1 N/cm or more, or 0.5 N/cm or more.

The pressure-sensitive adhesive layer may contain a thermosetting resin composition or a photocurable resin composition as a material. In this case, the resin composition can be polymerized and cured by supplying energy ex post facto.

The pressure-sensitive adhesive layer may be a layer called a pressure-sensitive adhesive (PSA) and adhered to the object by pressing. The pressure-sensitive adhesive may be an adhesive that is “a substance that has adhesiveness at room temperature and adheres to adherends with light pressure” (JIS K6800), or “a specific component is contained in a protective film (microcapsule), and appropriate means A capsule-type adhesive that can maintain stability until the film is destroyed by (pressure, heat, etc.)" (JIS K6800) may be used.

A color adjustment layer is a layer that has a function of color adjustment and is a layer that can adjust a laminate to a target color. A color adjusting layer is a layer containing resin and a coloring agent, for example. Examples of the coloring agent include inorganic pigments such as titanium oxide, zinc oxide, bengala, titanium oxide fired pigments, ultramarine blue, cobalt aluminate, and carbon black; Organic pigments such as azo-based compounds, quinacridone-based compounds, anthraquinone-based compounds, perylene-based compounds, iso-indolinone-based compounds, phthalocyanine-based compounds, quinophthalone-based compounds, threnic compounds, and diketopyrrolopyrrole-based compounds ; extender pigments such as barium sulfate and calcium carbonate; and dyes such as basic dyes, acid dyes, and mordant dyes.

The refractive index adjustment layer is a layer having a refractive index adjustment function, and has, for example, a refractive index different from that of the base material layer, and is a layer capable of imparting a predetermined refractive index to the laminate. The refractive index adjustment layer may be, for example, a resin layer containing an appropriately selected resin and, in some cases, a pigment, or may be a metal thin film.

Examples of the pigment for adjusting the refractive index include silicon oxide, aluminum oxide, antimony oxide, tin oxide, titanium oxide, zirconium oxide and tantalum oxide. The average primary particle size of the pigment may be 0.1 μm or less. By setting the average primary particle diameter of the pigment to 0.1 µm or less, irregular reflection of light passing through the refractive index adjusting layer can be prevented, and a decrease in transparency can be prevented.

Examples of the metal used in the refractive index adjustment layer include metal oxides such as titanium oxide, tantalum oxide, zirconium oxide, zinc oxide, tin oxide, silicon oxide, indium oxide, titanium oxynitride, titanium nitride, silicon oxynitride, and silicon nitride. or metal nitrides.

Further, for example, the primer layer may be disposed between the base material layer and the functional layer.

In the laminate or device of the present invention, when the layer (I) contains the compound represented by formula (I) as the first ultraviolet absorber (preferably containing the compound (I) having light absorption in the vicinity of 400 nm wavelength) In this case), since the first ultraviolet absorber is decomposed and deteriorated by oxygen, and the light absorbency in the vicinity of 400 nm wavelength in the layer (I) decreases, especially the performance of the polarizer, retardation film, display element, etc. included in the device There are cases where this deteriorates. However, in the laminate or device of the present invention, since the gas barrier layer is provided outside the layer (I), penetration of oxygen into the inside of the gas barrier layer is effectively suppressed, and the first agent contained in the layer (I) is prevented. Decomposition deterioration of the ultraviolet absorber of 1 can be prevented. In addition, the first ultraviolet absorber may be decomposed and deteriorated by ultraviolet rays (particularly, ultraviolet rays having a wavelength of around 380 nm), and thereby the light absorbency of the layer (I) around a wavelength of 400 nm may decrease. However, in the laminate or device of the present invention in which the substrate layer and/or the gas barrier layer contain the second ultraviolet absorber, outside the layer (I), the substrate layer containing the second ultraviolet absorber and/or gas Since the barrier layer is provided, transmission of ultraviolet rays (particularly, ultraviolet rays having a wavelength of around 380 nm) to the inside of the substrate layer and/or gas barrier layer is effectively suppressed, and decomposition and deterioration of the first ultraviolet absorber included in layer (I) are prevented. can prevent Therefore, the laminate or device of the present invention can effectively suppress not only performance deterioration of the polarizing plate but also performance deterioration of retardation film or display element, etc., and can express excellent weather resistance.

On the front plate constituting the laminate, the ratio of the absorbance at a wavelength of 405 nm (A ₄₀₅ ) to the absorbance at a wavelength of 430 nm (A ₄₃₀ ) (A ₄₀₅ /A ₄₃₀ ) (expressed as the absorbance ratio A ₄₀₅ /A ₄₃₀ Since the amount of light with a wavelength of 405 nm that reaches the polarizing plate can be reduced as the value of the polarizing plate increases, the deterioration in the polarization performance of the polarizing plate and the interference with light emission of the organic EL display element due to light around 405 nm can be effectively suppressed. can do. In particular, when the polarizing plate includes a coating type polarizer, it is possible to absorb light in a wavelength range that promotes the decomposition of the dichroic dye, so there is a tendency that deterioration in polarization performance can be more effectively suppressed.

The front plate constituting the laminate of the present invention has an absorbance ratio A ₄₀₅ /A ₄₃₀ of preferably 3.00 or more, more preferably 6.00 or more, still more preferably 8.00 or more. For this reason, it is easy to effectively suppress the deterioration of the polarization performance of a polarizing plate and the obstruction of light emission of an organic electroluminescent display element. The absorbance ratio A ₄₀₅ /A ₄₃₀ is, for example, the type or content of the first ultraviolet absorber included in the gas barrier layer and/or the base layer, the type or content of the second ultraviolet absorber included in the hard coat layer, or It can be adjusted according to the content and the like, and preferably it may be adjusted according to the type or content of the second ultraviolet absorber. In addition, absorbance can be measured with a spectrophotometer.

In one embodiment of the present invention, the laminate of the present invention has excellent oxygen barrier properties. The oxygen permeability of the laminate is 1300 cc/(m 2 24 h atm) or less, preferably 1000 cc/(m 2 24 h atm) or less, more preferably 500 cc/(m 2 24 h atm) or less, more preferably 400 cc/(m 2 24 h atm) or less, even more preferably 200 cc/(m 2 24 h atm) or less, particularly preferably 100 cc/(m 2 ) 24 h atm) or less, preferably 800 cc/(m 2 24 h atm) or less, more preferably 600 cc/(m 2 24 h atm) or less, still more preferably 400 cc/( m 2 24 h atm), particularly preferably 300 cc/(m 2 24 h atm) or less. When the oxygen permeability is equal to or less than the above upper limit, performance deterioration of the polarizing plate due to oxygen and performance deterioration of the retardation film or display element of the device including the laminate can be effectively suppressed, so that both excellent oxygen barrier properties and weather resistance can be achieved. there is. Moreover, it is easy to improve the heat resistance of a laminated body. Oxygen permeability can be measured in accordance with JIS K 7126-1 (differential pressure method), for example, according to the method described in Examples.

In a preferred embodiment of the present invention, the laminate of the present invention may have excellent flexibility. Preferably, the laminate of the present invention does not break when bent with a bending radius of 3 mm in a mandrel test. Particularly preferably, no splitting occurs even when bent with a bending radius of 1 mm. Since the laminate of the present invention has such excellent flexibility, it can be used for a flexible display.

In a preferred embodiment of the present invention, the laminate of the present invention preferably has a pencil hardness of H or higher, more preferably 2H or higher, still more preferably 3H or higher. Since the layered product of the present invention has such an excellent surface hardness, scratches on the surface of the layered product or a device including the layered product can be effectively suppressed.

[Method of manufacturing laminate]

The laminate of the present invention can be manufactured by laminating the front plate on one surface of the polarizing plate according to a conventional method. In addition, the functional layer and the primer layer may be laminated at an arbitrary position according to a conventional method. An example of a method for producing a laminate having a polarizing plate/hard coat layer/substrate layer/gas barrier layer in this order, which is a preferred embodiment of the present invention, is shown below.

In a preferable aspect of the present invention, the laminate of the present invention is, for example, the following steps:

(a) a step of applying a curable composition (X) to one side of the substrate layer and a curable composition (Y) to the other side to form a coating film (sometimes referred to as a coating film formation step)

(b) Step of irradiating each coating film formed in step (a) with high energy rays to cure the coating film to form a laminate composed of a hard coat layer/substrate layer/gas barrier layer (curing step)

(c) Step of laminating or bonding the laminate comprising the hard coat layer/substrate layer/gas barrier layer obtained in step (b) to a polarizing plate (lamination step)

can be produced by

In the coating film formation step, the curable composition (X) and the curable composition (Y) dissolved in a solvent may be applied to the substrate, respectively. As the solvent, those exemplified in the pages of the gas barrier layer can be used appropriately.

You may dry the coating film formed on the base material layer. Drying of the coating film can be performed by evaporating the solvent at a temperature of 50°C to 150°C, and the drying time is usually 30 seconds to 180 seconds. Drying may be performed under air, under an inert atmosphere, or under reduced pressure.

Moreover, you may provide the extending|stretching process of extending|stretching a base material layer after a coating film formation process. Although the stretching may be uniaxial stretching or biaxial stretching, it is preferable to perform stretching of the substrate layer by uniaxial stretching from the viewpoint of uniformity of in-plane retardation distribution. When performing biaxial stretching, simultaneous biaxial stretching may be sufficient as biaxial stretching, and successive biaxial stretching may be sufficient as it.

In the curing step, the coating film is irradiated with high energy rays (eg active energy rays) to cure the coating film to form a layer (cured film). The irradiation intensity is appropriately determined by the composition of the curable composition and is not particularly limited, but irradiation in a wavelength range effective for activating the photocationic polymerization initiator and the photoradical polymerization initiator is preferable. The irradiation intensity is preferably 0.1 to 6000 mW/cm 2 , more preferably 10 to 1000 mW/cm 2 , and still more preferably 20 to 500 mW/cm 2 . When the irradiation intensity is within the above range, an appropriate reaction time can be secured, and yellowing or deterioration of the resin due to heat radiated from the light source and heat generated during the curing reaction can be suppressed. The irradiation time may be appropriately selected depending on the composition of the curable composition, and is not particularly limited, but the cumulative amount of light expressed as the product of the irradiation intensity and the irradiation time is preferably from 10 to 10000 mJ/cm 2 , more preferably from 50 to 50 mJ/cm 2 . It is set to be 1000 mJ/cm 2 , more preferably 80 to 500 mJ/cm 2 . When the cumulative amount of light is within the above range, a sufficient amount of active species derived from the photocationic polymerization initiator or the photoradical polymerization initiator can be generated, the curing reaction can proceed more reliably, and the irradiation time does not become too long and good productivity can be maintained. can Moreover, since the hardness of a cured film can further be raised by passing through the irradiation process in this range, it is useful.

In the lamination step, when the polarizing plate is formed of a coating type polarizer, an alignment film is formed on the hard coat layer of the laminate composed of the hard coat layer/base layer/gas barrier layer, and a polymerizable liquid crystal compound and a polymerizable liquid crystal compound are formed on the alignment film. You may laminate|stack a polarizing plate by apply|coating and hardening the composition for polarizer formation containing a dichroic dye etc. Alternatively, a laminate composed of a hard coat layer/substrate layer/gas barrier layer may be bonded to one surface of a polarizing plate through a conventional method, for example, an adhesive.

[device]

The present invention includes a device including the above laminate. The device of the present invention has a form in which the polarizing plate side of the laminate is laminated or bonded to an optical member of an image display device, for example, a retardation film, a display element, a touch sensor film, or the like. In a preferable aspect, a device can be obtained by arrange|positioning an adhesive layer on the polarizing plate side of a laminated body, and laminating|stacking or bonding this adhesive layer to an optical member. Since the device of the present invention includes the above laminate, it has excellent heat resistance. Further, the device of the present invention may have excellent oxygen barrier properties and weather resistance. 1 is a schematic cross-sectional view showing an example of the layer structure of the device of the present invention. The device 1 shown in FIG. 1 includes, in order from the surface side (visible side), a gas barrier layer (2)/substrate layer (3)/hard coat layer (4)/polarizing plate (5)/adhesive layer (6). / It has a structure called retardation film 7.

The gas barrier layer 2, the base layer 3, the hard coat layer 4, the polarizing plate 5, and the pressure-sensitive adhesive layer 6 are the gas barrier layer, the base layer, the hard coat layer, the polarizing plate, and the pressure-sensitive adhesive described above. It is the same as the floor. The retardation film 7 may be the same as the retardation film described on the page of <polarization layer>, or may be a conventional stretched film.

Such a device can be used for an image display apparatus. Examples of image display devices include televisions, smart phones, mobile phones, car navigation systems, tablet PCs, portable game machines, electronic paper, indicators, bulletin boards, watches, and wearable devices such as smart watches.

[Flexible image display device]

The laminate of the present invention is excellent in flexibility. For this reason, the laminate of the present invention is useful as a laminate for a flexible image display device (sometimes referred to as a laminate for a flexible image display device). Further, the present invention includes a flexible image display device having a laminate for a flexible image display device. In one embodiment of the present invention, a flexible image display device is made of a laminate for a flexible image display device and an organic EL display panel, and the laminate for a flexible image display device is disposed on the viewer side with respect to the organic EL display panel to be bent. It is structured so that The laminate for the flexible image display device may contain a front plate, a polarizing plate, and a touch sensor, and the order of such lamination is arbitrary, but the order of the front plate, polarizing plate, touch sensor, or front plate, touch sensor, and polarizing plate from the viewer side It is preferable to be laminated with. When the polarizing plate is present on the viewing side of the touch sensor, the pattern of the touch sensor is difficult to be visually recognized, and the visibility of the displayed image is improved, which is preferable. Each member may be laminated using an adhesive, a pressure-sensitive adhesive, or the like. In addition, a light blocking pattern formed on at least one surface of any one layer of the front plate, the polarizer, and the touch sensor may be provided.

[Touch sensor]

The laminate of the present invention may include a touch sensor as in the form described above. A touch sensor is used as an input means. As the touch sensor, various modes such as a resistive film method, a surface acoustic wave method, an infrared method, an electromagnetic induction method, and a capacitance method have been proposed, and any method may be used. Among them, the capacitance method is preferable. The capacitive touch sensor is divided into an active area and an inactive area located outside the active area. The active area is an area corresponding to the area (display unit) where the screen is displayed on the display panel, and is an area where the user's touch is sensed. . The touch sensor includes a substrate having a flexible property; a sensing pattern formed on an active area of the substrate; Each sensing line formed in the inactive region of the substrate and connected to an external driving circuit through the sensing pattern and the pad part may be included. As the substrate having flexible characteristics, the same material as the transparent substrate of the window can be used. The substrate of the touch sensor preferably has a toughness of 2,000 MPa% or more from the viewpoint of suppressing cracks in the touch sensor. More preferably, the toughness may be 2,000 MPa% to 30,000 MPa%.

The sensing pattern may include a first pattern formed in a first direction and a second pattern formed in a second direction. The first pattern and the second pattern are disposed in different directions. The first pattern and the second pattern must be electrically connected to each other in order to sense a touched point formed on the same layer. In the first pattern, each unit pattern is connected to each other through a seam, but in the second pattern, each unit pattern is separated from each other in the form of an island, so a separate bridge electrode is required to electrically connect the second pattern. need. A known transparent electrode material may be used for the sensing pattern. Examples include indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), indium zinc tin oxide (IZTO), cadmium tin oxide (CTO), poly(3,4-ethylenedioxythiophene) (PEDOT) , carbon nanotubes (CNT), graphene, metal wires, and the like, and these may be used alone or in combination of two or more. Preferably, ITO can be used. The metal used for the metal wire is not particularly limited, and examples thereof include silver, gold, aluminum, copper, iron, nickel, titanium, ruthenium, and chromium. These can be used individually or in mixture of 2 or more types.

The bridge electrode may be formed on the insulating layer through an insulating layer on the sensing pattern, and the bridge electrode may be formed on the substrate, and the insulating layer and the sensing pattern may be formed thereon. The bridge electrode may be formed of the same material as the sensing pattern, or may be formed of a metal such as molybdenum, silver, aluminum, copper, palladium, gold, platinum, zinc, tin, titanium, or an alloy of two or more of these. Since the first pattern and the second pattern must be electrically insulated, an insulating layer is formed between the sensing pattern and the bridge electrode. The insulating layer may be formed only between the seam of the first pattern and the bridge electrode, or may be formed in a structure covering the sensing pattern. In the latter case, the bridge electrode may connect the second pattern through a contact hole formed in the insulating layer. The touch sensor is a means for appropriately compensating for a difference in transmittance between a pattern area where a pattern is formed and a non-pattern area where a pattern is not formed, specifically, a difference in light transmittance caused by a difference in refractive index in this area. As it may further include an optical control layer between the substrate and the electrode, the optical control layer may include an inorganic insulating material or an organic insulating material. The optical control layer may be formed by coating a photocurable composition including a photocurable organic binder and a solvent on a substrate. The photocurable composition may further include inorganic particles. The refractive index of the optical control layer may be increased by the inorganic particles.

The photocurable organic binder may include, for example, a copolymer of each monomer such as an acrylate-based monomer, a styrene-based monomer, or a carboxylic acid-based monomer. The photocurable organic binder may be, for example, a copolymer containing different repeating units such as an epoxy group-containing repeating unit, an acrylate repeating unit, or a carboxylic acid repeating unit. The inorganic particles may include, for example, zirconia particles, titania particles, alumina particles, and the like. The photocurable composition may further include additives such as a photopolymerization initiator, a polymerizable monomer, and a curing aid.

[shading pattern]

The light blocking pattern may be applied as at least a part of a bezel or a housing of the flexible image display device. Wiring disposed at the edge of the flexible image display device is hidden by the light-shielding pattern to make it difficult to see, thereby improving the visibility of the image. The light-shielding pattern may be in the form of a single layer or a multi-layer. The color of the light-shielding pattern is not particularly limited, and has various colors such as black, white, and metallic color. The light-shielding pattern may be formed of a pigment for realizing color and a polymer such as an acrylic resin, an ester resin, an epoxy resin, polyurethane, or silicone. You may use these individually or in mixture of 2 or more types. The light-shielding pattern can be formed by various methods such as printing, lithography, and inkjet. The thickness of the light-shielding pattern may be 1 μm to 100 μm, preferably 2 μm to 5 μm. In addition, it is also preferable to give a shape such as an inclination in the thickness direction of the light pattern.

Example

Hereinafter, the present invention will be described more specifically by showing Examples and Comparative Examples, but the present invention is not limited by these examples. Hereinafter, unless otherwise specified, parts and % showing usage amount and content are based on mass.

(1) Oxygen permeability of front plate

Oxygen permeability of front plates obtained in Examples and Comparative Examples in accordance with JIS K 7126-1 (differential pressure method) using a differential pressure type gas permeability measuring device "GTR-30 AS type" (manufactured by GTR Technologies, Inc.) [cc/(m2·24h·atm)] was measured.

(2) Permeability of front panel

Based on JIS "Z" 0208, the water vapor transmission rate of the front plates obtained in Examples and Comparative Examples was measured. The temperature and humidity conditions were 40 degrees and 90% RH.

(3) heat resistance test

The layered products obtained in Examples and Comparative Examples were placed in an oven at a temperature of 85°C for 240 hours. Before and after putting into the oven, the visibility correction polarization degree (Py) (%) and visibility correction single transmittance (Ty) (%) of each laminate were measured. The degree of change in polarization performance Δ (%) was calculated according to the following formula.

Gradient Δ=(ΔPy ² +ΔTy ² ) ^1/2

ΔPy = Py after test - Py before test

ΔTy = Ty after test - Ty before test

(4) Light fastness test

The laminates obtained in Examples and Comparative Examples were irradiated with light under the following conditions. Before and after irradiation with light, the visibility corrected polarization degree (Py) (%) and the visibility corrected single transmittance (Ty) (%) of each laminate were measured. The degree of change in polarization performance Δ (%) was calculated according to the following formula.

Gradient Δ=(ΔPy ² +ΔTy ² ) ^1/2

ΔPy = Py after test - Py before test

ΔTy = Ty after test - Ty before test

Light irradiation conditions are as follows.

Apparatus used: SUNTEST XLS+ made by ATLAS

A use light source: Xenon arc lamp

Dosage：96120kJ/㎡

Time: 100 hours

Temperature: 45 degrees Celsius

(5) Absorbance ratio

For the entire surfaces obtained in Examples and Comparative Examples, absorbance at a wavelength of 405 nm (A ₄₃₀ ) (Abs) and absorbance at a wavelength of 405 nm (A ₄₀₅ ) by a spectrophotometer U-4100 (manufactured by Hitachi, Ltd.) (Abs) was measured, respectively, and the absorbance ratio (A ₄₀₅ /A ₄₃₀ ) was calculated.

(6) Flexibility test

The laminates obtained in Examples and Comparative Examples were cut into 1 cm × 8 cm to obtain measurement samples. The operation of winding the measurement sample on each roll of 2 mm (radius R = 1 mm) in the direction in which the C-POL laminated surface becomes in-folding and out-folding, and then returning it to its original state is performed continuously for 10 did it once

Based on the presence or absence of occurrence of cracking in the cured film, the flexibility was determined as follows. The determination results are shown in Tables 1 and 2.

(Determination of Flexibility)

0: No cracks occurred, and the appearance was good.

Δ: 1 to 4 cracks occurred.

In addition, for the laminate obtained in the Example, when the operation of winding the measurement sample on each roll of 4 mm (radius R = 2 mm) and then returning it to its original state was performed 10 times in a row, both in-folding and out-folding appearances was good

<Preparation of composition for polarizer formation>

The composition for polarizer formation was obtained by mixing the following components and stirring at 80 degreeC for 1 hour. As the dichroic dye, the azo dye described in Examples of Japanese Unexamined Patent Publication No. 2013-101328 was used.

・Polymerizable liquid crystal compound:

(A-6) 90 copies

(A-7) 10 copies

・Dichroic pigment:

azo pigment;

(Dichroic dye A) 　　　　　　　2.5 parts

(Dichroic Dye B) 　　　　　　2.5 parts

(Dichroic Dye C) 　　　　　　2.5 parts

・Polymerization initiator:

2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one (IRGACURE 369; manufactured by Ciba Specialty Chemicals Co., Ltd.) 6 parts

・Leveling agent:

Polyacrylate compound (BYK-361N; manufactured by BYK-Chemie) 1.2 parts

·solvent:

o-xylene = 400 parts

<Preparation of Composition for Forming Alignment Film>

A composition for forming a photo-alignment film was obtained by mixing the following components described in Japanese Unexamined Patent Publication No. 2013-033249 and stirring the resulting mixture at 80°C for 1 hour.

・Photo-alignable polymer:

Part 2

·solvent:

o-xylene　　　　　　　　　　　　　　　98 parts

[1] Example 1

[1-1] Preparation of a composition for forming a hard coat layer

Dendrimer acrylate having an 18-functional acryloyl group (sometimes referred to as an acryl group) (Miramer SP1106, Miwon Speciality Chemical Co.) 2.0 parts by mass, urethane acrylate having a hexafunctional acryl group (Miramer PU-620D, Miwon Speciality Chemical Co.) 10.0 parts by mass, an acrylate monomer having a trifunctional acrylic group (M340, Miwon Speciality Chemical Co.) 8 parts by mass, a photopolymerization initiator (IRGACURE (registered trademark) 184, manufactured by BASF) 2 parts by mass, and a leveling agent ( 0.1 parts by mass of BYK-UV3530, Byk-chemie Japan K.K.) was dissolved in 70 parts by mass of methyl ethyl ketone (MEK), stirred and mixed to obtain composition A for hard coat layer formation.

[1-2] Fabrication of front panel

A polyethylene terephthalate film was prepared as a substrate layer. The thickness of the substrate layer was 50 μm.

The composition A for forming a hard coat layer was coated on one surface of the substrate layer to form a coating film. The coating film was dried at a temperature of 80 ° C. for 5 minutes, and using an ultraviolet irradiation device (SPOT, CURE, SP-7, manufactured by USHIO INC.), ultraviolet rays with a cumulative light amount of 500 mJ / cm 2 (based on a wavelength of 365 nm) were irradiated to form a hard coat layer. has formed In addition, the thickness of the hard coat layer was 10.0 μm. In this way, a front plate composed of the hard coat layer and the substrate layer was obtained.

[1-3] Production of laminated body

After corona treatment was applied to the surface of the hard coat layer in the front plate, the composition for forming an alignment film was applied and dried at 120°C for 1 minute to obtain a dried film. Polarized UV was irradiated on this dried film to form a photo-alignment film, and a film having a photo-alignment film was obtained. The polarized UV treatment was performed using a UV irradiation device (SPOT, CURE, SP-7; manufactured by USHIO INC.) under the condition that the amount of integrated light measured at a wavelength of 365 nm was 100 mJ/cm 2 .

A composition for forming a polarizer is coated on an alignment film, and the polymerizable liquid crystal compound is phase-transformed into a liquid phase by heating and drying in a drying oven at 120° C. for 1 minute, and then the polymerizable liquid crystal compound is phase-transferred into a smectic liquid-crystal state by cooling to room temperature. made it Then, by using a UV irradiator (SPOT CURE SP-7; manufactured by USHIO INC.), ultraviolet rays having an exposure amount of 1000 mJ/cm2 (based on 365 nm) are irradiated to the layer formed of the composition for forming a polarizing film, The polymerizable liquid crystal compound contained in the dry film was polymerized while maintaining the smectic liquid crystal state of the polymerizable liquid crystal compound, and a polarizer was formed from the dried film. In this way, a laminate was produced in which a polarizer, a hard coat layer, and a base material layer were laminated in this order.

[2] Example 2

A laminate was manufactured in the same manner as in Example 1 except that a polyethylene naphthalate film was used as the substrate layer. This substrate layer had a thickness of 25 μm.

[3] Example 3

A laminate was manufactured in the same manner as in Example 1, except that a cyclic olefin resin film was used as the substrate layer. This substrate layer had a thickness of 23 µm.

[4] Example 4

As a substrate layer, a triacetyl cellulose film was prepared. The thickness of the substrate layer was 25 μm.

The composition A for forming a hard coat layer was coated on one surface of the substrate layer to form a coating film. The coating film was dried at a temperature of 80° C. for 5 minutes, and using an ultraviolet irradiation device (SPOT, CURE, SP-7, manufactured by USHIO INC.), ultraviolet rays of 500 mJ/cm 2 (wavelength 365 nm standard) were irradiated to form a hard coat layer. formed Further, the composition A for forming a hard coat layer was similarly coated on the other surface of the base material layer, and cured in the same manner as above to form a hard coat layer (gas barrier layer). In addition, the thickness of all hard-coat layers was 10.0 micrometer. In this way, a front plate composed of the hard coat layer, the substrate layer, and the gas barrier layer was obtained.

On the hard coat layer in the front plate, it was carried out similarly to Example 1, and the polarizer was formed and the laminated body was obtained. In the laminate, a polarizer, a hard coat layer, a substrate layer, and a gas barrier layer were laminated in this order.

[5] Example 5

A triacetyl cellulose film having a retardation value of about 0 nm in the thickness direction was prepared as the substrate layer. The thickness of the substrate layer was 25 μm. Except having used this base material layer, it carried out similarly to Example 4, and manufactured the laminated body.

[6] Example 6

[6-1] Preparation of composition for forming hard coat layer

18 parts by mass of urethane acrylate having a hexafunctional acrylic group (Miramer PU-620D, Miwon Speciality Chemical Co.), 10 parts by mass of an acrylate monomer having a trifunctional acrylic group (M340, Miwon Speciality Chemical Co.), a photopolymerization initiator (IRGACURE ( 2 parts by mass of (registered trademark) 184, manufactured by BASF) and 0.1 part by mass of a leveling agent (BYK-UV3530, Byk-chemie Japan K.K.) were dissolved in 70 parts by mass of methyl ethyl ketone (MEK), stirred and mixed, and hard coated. A composition B for layer formation was obtained.

[6-2] Fabrication of front panel

As a substrate layer, a triacetyl cellulose film was prepared. The thickness of the substrate layer was 25 μm.

Composition B for forming a hard coat layer was coated on one surface of the substrate layer to form a coating film. The coating film was dried at a temperature of 80° C. for 5 minutes, and using an ultraviolet irradiation device (SPOT, CURE, SP-7, manufactured by USHIO INC.), ultraviolet rays of 500 mJ/cm 2 (wavelength 365 nm standard) were irradiated to form a hard coat layer. formed In addition, the thickness of the hard coat layer was 10.0 μm. In this way, a front plate composed of the hard coat layer and the substrate layer was obtained.

[6-3] Production of laminated body

It carried out similarly to Example 1, and formed the polarizer on the hard-coat layer. In this way, a laminate was produced in which a polarizer, a hard coat layer, and a base material layer were laminated in this order.

[7] Example 7

A triacetyl cellulose film having a retardation value of about 0 nm in the thickness direction was prepared as the substrate layer. The thickness of the substrate layer was 25 μm. Except having used this base material layer, it carried out similarly to Example 6, and manufactured the laminated body.

[8] Example 8

[8-1] Preparation of composition for forming hard coat layer

24.4 parts by mass of tetrafunctional acrylate (A-TMMT: pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), trifunctional acrylate (A-TMPT: trimethylolpropane triacrylate, Shin-Nakamura Chemical Co., Ltd.) Chemical Co., Ltd.) 48.8 parts by mass, bifunctional acrylate (A-400 polyethylene glycol # 400 diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 24.4 parts by mass, photopolymerization initiator (IRGACURE (registered trademark) ) 184, manufactured by BASF) 1.61 parts by mass, and a photopolymerization initiator (IRGACURE (registered trademark) 819, manufactured by BASF) 0.73 parts by mass, dissolved in propylene glycol monomethyl ether, stirred and mixed to obtain composition C for forming a hard coat layer got it

[8-2] Fabrication of front panel

Kawamura Sangyo Co.,Ltd. A substrate layer was prepared using a solution containing polyimide "KPI-MX300F (100)" of the present invention, Sumisorb 340 (ultraviolet ray absorber), and γ-butyrolactone as a flexible film. The amount of the ultraviolet absorber was 3 parts by mass with respect to 100 parts by mass of polyimide. The thickness of the substrate layer was 50 µm.

On one surface of the substrate layer, composition C for forming a hard coat layer was coated with a bar coater, and cured by irradiation with ultraviolet rays to form a hard coat layer. In addition, the thickness of the hard coat layer was 10.0 μm. In this way, a front plate composed of the hard coat layer and the substrate layer was obtained.

[8-3] Production of laminated body

It carried out similarly to Example 1, and formed the polarizer on the hard-coat layer. In this way, a laminate was produced in which a polarizer, a hard coat layer, and a base material layer were laminated in this order.

[9] Example 9

[9-1] Preparation of a composition for forming a gas barrier layer

18.9 parts by mass of tetrafunctional acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMMT, pentaerythritol tetraacrylate), trifunctional acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMPT: trimethylolpropane triacrylate) 9.5 parts by mass, biscyclic ether compound (manufactured by Daicel Corporation, CELLOXIDE 2021P: 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate) 9.5 parts by mass, radically polymerizable cyclic Ether compound (manufactured by Daicel Corporation, Cyclomer M100: 3,4-epoxy cyclohexylmethyl methacrylate) 18.9 parts by mass, acryloyl-modified silica particles (manufactured by Nissan Chemical Industries, Ltd., PGM-2140Y, average particle size 10 to 15 nm) 40 parts by mass, photocationic polymerization initiator (IRGACURE (registered trademark) 250, manufactured by BASF, (4-methylphenyl) [4- (2-methylpropyl) phenyl] 3 of iodonium hexafluorophosphate and propylene carbonate: 1 (mass ratio) mixture) 1.0 parts by mass, photoradical polymerization initiator (IRGACURE (registered trademark) 184, manufactured by BASF) 2.2 parts by mass, and a leveling agent (manufactured by Byk-chemie Japan K.K., "BYK-307", silicone-based leveling Fifth) 0.1 part by weight was dissolved in propylene glycol monomethyl ether and stirred and mixed to obtain a composition for forming a gas barrier layer.

[9-2] Preparation of composition for forming hard coat layer

23.8 parts by mass of tetrafunctional acrylate (A-TMMT: pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), trifunctional acrylate (A-TMPT: trimethylolpropane triacrylate, Shin-Nakamura Chemical Co., Ltd.) Chemical Co., Ltd.) 47.6 parts by mass, bifunctional acrylate (A-400 polyethylene glycol # 400 diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 23.8 parts by mass, ultraviolet absorber (Japanese Patent Laid-Open 2017 120430 by reference) 2.43 parts by mass, photopolymerization initiator (IRGACURE (registered trademark) 184, manufactured by BASF) 1.57 parts by mass, photopolymerization initiator (IRGACURE (registered trademark) 819, manufactured by BASF) 0.71 parts by mass, propylene It was dissolved in glycol monomethyl ether and stirred and mixed to obtain composition D for forming a hard coat layer.

The ultraviolet absorber is a compound represented by formula (I-II) in which R ^4-1 is a 2-ethylhexyl group.

[9-2]Fabrication of front panel

Kawamura Sangyo Co.,Ltd. A substrate layer was prepared using a solution containing polyimide "KPI-MX300F (100)" of the present invention, Sumisorb 340 (ultraviolet ray absorber), and γ-butyrolactone as a flexible film. The amount of the ultraviolet absorber was 3 parts by mass with respect to 100 parts by mass of polyimide. The thickness of the substrate layer was 50 µm.

Composition D for forming a hard coat layer was applied to one side of the substrate layer and the composition for forming a gas barrier layer was applied to the other side by a bar coater, respectively, and dried at 80° C. for 3 minutes. The coating film was cured by irradiation with ultraviolet rays (high pressure mercury lamp: cumulative light amount of 500 mJ/cm 2 , irradiation intensity of 200 mW/cm 2 ) in a nitrogen atmosphere. In this way, a front plate composed of the hard coat layer, the substrate layer, and the gas barrier layer was obtained. The thickness of the hard coat layer was 6 μm, and the thickness of the gas barrier layer was 16 μm.

[9-3] Fabrication of laminated body

It carried out similarly to Example 1, and formed the polarizer on the hard-coat layer. In this way, a laminate was prepared in which the polarizer, the hard coat layer, the base material layer, and the gas barrier layer were laminated in this order.

[10] Example 10

[10-1] Preparation of composition for forming hard coat layer

22.5 parts by mass of tetrafunctional acrylate (A-TMMT: pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), trifunctional acrylate (A-TMPT: trimethylolpropane triacrylate, Shin-Nakamura Chemical Co., Ltd.) Chemical Co., Ltd.) 44.9 parts by mass, bifunctional acrylate (A-400 polyethylene glycol # 400 diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 22.5 parts by mass, ultraviolet absorber (Carboprotect, BASF Co., Ltd.) F) 8.0 parts by mass, photopolymerization initiator (IRGACURE (registered trademark) 184, manufactured by BASF) 1.48 parts by mass, photopolymerization initiator (IRGACURE (registered trademark) 819, manufactured by BASF) 0.67 parts by mass, dissolved in propylene glycol monomethyl ether , and stirred and mixed to obtain composition E for hard coat layer formation.

[10-2]Production of front panel

Kawamura Sangyo Co.,Ltd. A substrate layer was prepared using a solution containing polyimide "KPI-MX300F (100)" of the present invention, Sumisorb 340 (ultraviolet ray absorber), and γ-butyrolactone as a flexible film. The amount of the ultraviolet absorber was 3 parts by mass with respect to 100 parts by mass of polyimide. The thickness of the substrate layer was 50 µm.

Composition E for forming a hard coat layer was applied to one side of the substrate layer and the composition for forming a gas barrier layer was applied to the other side by a bar coater, respectively, and dried at 80° C. for 3 minutes. The coating film was cured by irradiation with ultraviolet rays (high pressure mercury lamp: cumulative light amount of 500 mJ/cm 2 , irradiation intensity of 200 mW/cm 2 ) in a nitrogen atmosphere. In this way, a front plate composed of the hard coat layer, the substrate layer, and the gas barrier layer was obtained. The thickness of the hard coat layer was 10 μm, and the thickness of the gas barrier layer was 16 μm.

[10-3] Fabrication of laminated body

It carried out similarly to Example 1, and formed the polarizer on the hard-coat layer. In this way, a laminate was prepared in which the polarizer, the hard coat layer, the base material layer, and the gas barrier layer were laminated in this order.

[11] Example 11

A laminate was produced in the same manner as in Example 10 except that the gas barrier layer was not formed. In the layered product, a polarizer, a hard coat layer, and a substrate layer were laminated in this order.

[12] Example 12

A laminate was produced in the same manner as in Example 8 except that the polarizer layer was formed on the substrate layer. In the layered product, a polarizer, a substrate layer, and a hard coat layer (gas barrier layer) were laminated in this order.

[13] Example 13

[13-1] Preparation of a composition for forming a gas barrier layer

As a composition for forming a gas barrier layer, composition D for forming a hard coat layer was used.

[13-2]Production of front panel

Kawamura Sangyo Co.,Ltd. A substrate layer was prepared using a solution containing polyimide "KPI-MX300F (100)" of the present invention, Sumisorb 340 (ultraviolet ray absorber), and γ-butyrolactone as a flexible film. The thickness of the substrate layer was 50 µm.

On one surface of the substrate layer, the composition for forming a gas barrier layer was coated with a bar coater and cured by irradiation with ultraviolet rays to form a gas barrier layer. In addition, the thickness of the gas barrier layer was 10.0 μm. In this way, a front plate composed of the gas barrier layer and the substrate layer was obtained.

[13-3] Fabrication of laminated body

It carried out similarly to Example 1, and formed the polarizer on the base material layer. In this way, a laminate was produced in which the polarizer, the substrate layer, and the gas barrier layer were laminated in this order.

[14] Comparative Example 1

A laminate was produced in the same manner as in Example 4 except that the hard coat layer and the gas barrier layer were not formed. In the layered product, a polarizer and a substrate layer were laminated.

[15] Comparative example 2

A laminate was produced in the same manner as in Example 5 except that the hard coat layer and the gas barrier layer were not formed. In the layered product, a polarizer and a substrate layer were laminated.

For the laminates prepared in Examples 1 to 13 and Comparative Examples 1 and 2, oxygen transmission of the front plate, measurement of absorbance, heat resistance test, light resistance test, and flexibility test were performed, and the results are shown in Tables 1 and 2. indicated in Moreover, in Table 1 and Table 2, the composition in the column of gas barrier layer shows the composition which forms a gas barrier layer, and the composition in the column of hard coat layer shows the composition which forms a hard coat layer. GB represents a composition for forming a gas barrier layer, HC and A represent composition A for forming a hard coat layer, HC and B represent composition B for forming a hard coat layer, and HC and C represent composition C for forming a hard coat layer , HC and D represent composition D for forming a hard coat layer, and HC and E represent composition E for forming a hard coat layer. UVA(1) represents an ultraviolet absorber "Sumisorb 340", UVA(2) represents a compound represented by formula (I-II) in which R ^4-1 is a 2-ethylhexyl group, and UVA(3) represents an ultraviolet absorber "Carboprotect", PET represents a polyethylene terephthalate film, PEN represents a polyethylene naphthalate film, COP represents a cyclic olefin resin film, TAC represents a triacetyl cellulose film, and Z-TAC represents a phase difference in the thickness direction. The value represents a triacetyl cellulose film of about 0 nm, and PI represents polyimide "KPI-MX300F (100)". The application type in the polarizing plate column indicates the application type polarizer used in each Example and Comparative Example. Δ represents the degree of change of polarization performance Δ.

As shown in Tables 1 and 2, the laminate obtained in Examples 1 to 13, including a front plate having an oxygen permeability of 1300 cc / (m 2 24 h atm) or less, the oxygen permeability of the front plate is 1300 cc Compared to those obtained in Comparative Examples 1 and 2, including the front plate exceeding /(m 2 · 24 h · atm), even after being placed in a high temperature environment, the values of ΔPy, ΔTy and variation Δ were small. Therefore, it was found that the laminate of the present invention can effectively suppress the deterioration of the polarization performance even when exposed to a high-temperature environment and has excellent heat resistance.

1: device,
2: gas barrier layer,
3: base layer,
4: hard coat layer,
5: polarizer,
6: adhesive layer,
7: retardation film

Claims (18)

A polarizing plate and a front plate laminated on one side of the polarizing plate,
The front plate includes a base layer, and the oxygen permeability of the front plate is 1300 cc/(m 2 24 h atm) or less,
The front plate includes a hard coat layer, and the hard coat layer is disposed between the base layer and the polarizing plate and is adjacent to the base layer,
The front plate includes a gas barrier layer on the side opposite to the hard coat layer side of the substrate layer,
The oxygen permeability is based on JIS K 7126-1 (differential pressure method) and is measured using a differential pressure type gas permeability measuring device. According to claim 1,
The laminated body in which the said hard-coat layer contains a 1st ultraviolet absorber. According to claim 1 or 2,
The polarizing plate includes a polarizer, and the polarizer includes a layer in which a polymerizable liquid crystal compound is cured. According to claim 3,
The polarizing plate includes a retardation film, and the retardation film is disposed on a side opposite to the front plate side of the polarizer and includes a layer in which a polymerizable liquid crystal compound is cured. According to claim 1 or 2,
The front plate has a ratio (A 405 /A ₄₃₀ ) of absorbance at a wavelength of 405 nm (A ₄₀₅ ) to absorbance at a wavelength of ₄₃₀ nm (A ₄₃₀ ) of 3.00 or more. According to claim 1,
At least one of the substrate layer and the gas barrier layer contains a second ultraviolet absorber. According to claim 1,
The said gas barrier layer is a laminated body which is a hardened|cured material of the curable composition containing a polyfunctional (meth)acrylate monomer (A) and a cationically polymerizable monomer (B). According to claim 7,
The laminated body in which the said cationically polymerizable monomer (B) contains the cyclic ether compound (B-1) which has at least any one of 1 or more epoxy groups or 1 or more oxetanyl groups. According to claim 8,
The laminated body in which the said cyclic ether compound (B-1) contains the bis cyclic ether compound (B-1-1) which has at least any one of two or more epoxy groups or two or more oxetanyl groups. According to claim 8,
The layered product in which the cyclic ether compound (B-1) includes a radically polymerizable cyclic ether compound (B-1-2). According to claim 10,
The content of the radically polymerizable cyclic ether compound (B-1-2) is 1 to 10 parts by mass relative to 1 part by mass of the bis cyclic ether compound (B-1-1). According to claim 2,
A layered product in which the first ultraviolet absorber is a compound represented by formula (I).
[Tue 1]

(In formula (I), A represents a methylene group, a secondary amino group, an oxygen atom or a sulfur atom, R ¹ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the alkyl group has at least one methylene group In this case, at least one of the methylene groups may be substituted with an oxygen atom or a sulfur atom, R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R ⁴ is 3 to 12 carbon atoms An alkyl group of 50, or an alkyl group of 3 to 50 carbon atoms having at least one methylene group, wherein at least one of the methylene groups represents an alkyl group substituted with an oxygen atom, and a carbon atom on the alkyl group may have a substituent bonded, X ¹ represents an electron-withdrawing group, Y ¹ represents -CO-, -COO-, -OCO-, -O-, -S-, -NR ⁵ -, -NR ⁶ CO-, or -CONR ⁷ -; R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group) According to claim 1 or 2,
A laminate comprising a touch sensor. According to claim 1 or 2,
A laminate for a flexible image display device. A device comprising the laminate according to claim 1 or 2. A flexible image display device comprising the laminate according to claim 14. delete delete