Transparent laminate, image display device, and flexible device

Abstract

The present invention addresses the problem of providing a transparent laminate having high hardness and excellent bendability. A transparent laminate according to the present disclosure has a base material and a hard coat layer laminated on at least one surface of the base material, and is characterized in that: the pencil hardness of the hard coat layer surface at a load of 750 g is H or more; the transparent laminate has a minimum bendable radius of 1.5 mm or less when a cylindrical mandrel test is performed by recessing the surface of the hard coat layer of the transparent laminate, and the ratio of the indentation modulus to the indentation hardness (indentation modulus / indentation hardness) in a microhardness test of the transparent laminate is 6.0 or more.

Description

Technical Field

[0001] The present disclosure relates to a transparent laminate, an image display device, and a flexible device. Background Art

[0002] In order to improve the portability of portable information terminals such as smartphones and tablet computers, the demand for foldable devices such as foldable displays and touch panels has increased. A configuration is known in which a hard coat is used as a covering material on the outermost surface of the display of such a foldable device. In addition, the above hard coat is required to have high hardness in order to exhibit transparency and beauty, and to prevent the occurrence of damage and indentations. As an invention using such a hard coat with high hardness, for example, Patent Document 1 can be cited.

[0003] Prior Art Documents

[0004] Non-Patent Documents

[0005] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2022-081716 Summary of the Invention

[0006] Problems to be Solved by the Invention

[0007] However, if the hard coat of Patent Document 1 is made to have high hardness, the bendability (flexibility) decreases, and there is a problem that cracks are likely to occur in the hard coat or the substrate.

[0008] The present disclosure has been made to solve the above problems, and an object thereof is to provide a transparent laminate having high hardness and excellent bendability.

[0009] Technical Solution

[0010] The inventors of the present disclosure have found that, in a transparent laminate having a substrate and a hard coat laminated on at least one surface of the substrate, if the pencil hardness on the surface of the hard coat, the minimum bendable radius, and the ratio of the indentation elastic modulus to the indentation hardness in the microhardness measurement satisfy a specific range, the laminate has high hardness and excellent bendability. The present disclosure has been completed based on these findings.

[0011] That is, the above transparent laminate is a transparent laminate having a substrate and a hard coat laminated on at least one surface of the substrate, characterized in that the pencil hardness under a 750 g load on the surface of the hard coat is H or higher, the minimum bendable radius when the surface of the hard coat of the above transparent laminate is recessed to perform a cylindrical mandrel test is 1.5 mm or less, and the ratio (indentation elastic modulus / indentation hardness) of the indentation elastic modulus to the indentation hardness in the microhardness test of the above transparent laminate is 6.0 or higher.

[0012] By making the above pencil hardness H or more, the minimum bendable radius 1.5 mm or less, and the ratio of the indentation elastic modulus to the indentation hardness 6.0 or more, the surface of the hard coat is high in hardness and excellent in bendability.

[0013] Preferably, in the above transparent laminate, the haze of the above hard coat is 1.0% or less.

[0014] Preferably, in the above transparent laminate, the above hard coat is a cured product of a curable composition containing one or more curable compounds, and the above transparent laminate contains an aliphatic compound having two or more cationic polymerizable groups in the molecule as the above curable compound.

[0015] Preferably, the above transparent laminate contains polyorganosilsesquioxane as the above curable compound.

[0016] Preferably, the above transparent laminate contains two or more of the above aliphatic compounds as the above curable compound. By having the above configuration, it is easy to balance high hardness and bendability.

[0017] Preferably, the above curable composition further contains a curing catalyst.

[0018] Preferably, the above curing catalyst contains a cationic polymerization initiator.

[0019] Preferably, the above curing catalyst contains a radical polymerization initiator.

[0020] In addition, preferably, the above transparent laminate does not contain a compound equivalent to PFAS in the above hard coat.

[0021] Preferably, the above transparent laminate has a surface protective film on at least one surface.

[0022] Preferably, the above transparent laminate has the above hard coat on one surface of the above substrate and an adhesive layer on the other surface.

[0023] Preferably, the above substrate is glass having a thickness of 30 to 100 μm.

[0024] In addition, the present disclosure provides an image display device including the above transparent laminate.

[0025] Preferably, the above image display device is a flexible display.

[0026] Preferably, the above image display device is an organic electroluminescent display device.

[0027] In addition, the present disclosure provides a flexible device including the above image display device.

[0028] Advantages of the Invention

[0029] The transparent laminate of the present disclosure has high hardness and excellent bendability. Therefore, it can be applied to image display devices such as flexible displays. Detailed Description of the Invention

[0030] It should be noted that in the present disclosure, "compounds equivalent to PFAS" is a general term for perfluoroalkyl compounds and polyfluoroalkyl compounds.

[0031] [Transparent Laminate]

[0032] The transparent laminate of the present disclosure is a transparent laminate having a substrate and a hard coat laminated on at least one surface of the substrate. The pencil hardness of the surface of the hard coat under a 750 g load is H or more, and the minimum bendable radius when the hard coat side of the transparent laminate is indented to perform a cylindrical mandrel test is 1.5 mm or less. The ratio of the indentation elastic modulus to the indentation hardness (indentation elastic modulus / indentation hardness) in the microhardness test of the transparent laminate is 6.0 or more. The transparent laminate of the present disclosure having the above configuration has high hardness and excellent bendability.

[0033] The above transparent laminate may also have other layers other than the substrate and the hard coat. Examples of the other layers include a surface protective film, an adhesive layer, a primer layer for bonding the substrate and the hard coat, an antireflection layer, an antiglare layer, a fingerprint-resistant layer, an antifouling layer, a friction-resistant fingerprint layer, an antibacterial layer, a bonding layer, a polarizing layer, etc. The other layers may be formed only on one surface (single-sided) of the substrate, or may be formed on both surfaces (double-sided). In addition, when the other layers are formed on both surfaces of the substrate, the same layers may be laminated respectively, or layers having different thicknesses and compositions may be laminated respectively.

[0034] The pencil hardness of the surface of the hard coat of the above transparent laminate measured according to JIS K5600-5-4 is H or more, preferably 2H or more. By making the pencil hardness H or more, the surface hardness becomes sufficient and it is easy to exhibit abrasion resistance. It should be noted that when the hard coat is laminated on both surfaces of the above transparent laminate, it is sufficient that at least one surface satisfies the above range.

[0035] In the cylindrical mandrel test in which the above transparent laminate is bent in such a manner that the surface of the hard coat is indented according to JIS K5600-5-1, the minimum bending diameter at which no crack occurs is in the range of 1.5 mm or less. By making the above minimum bending diameter 1.5 mm or less, sufficient bendability can be exhibited. It should be noted that when the hard coat is laminated on both surfaces of the above transparent laminate, it is sufficient that at least one surface satisfies the above range, and preferably the hard coat having a pencil hardness of H or more satisfies the above minimum bending diameter.

[0036] The indentation elastic modulus in the measurement of the microhardness of the surface of the above-mentioned transparent laminate is preferably 400 to 4000 MPa, more preferably 600 to 3500 MPa, and still more preferably 800 to 3000 MPa. By making the above indentation elastic modulus 400 MPa or more, there is a tendency for excellent surface hardness. By making the above indentation elastic modulus 4000 MPa or less, elongation and bendability can be balanced while maintaining rigidity.

[0037] The indentation hardness in the measurement of the microhardness of the surface of the above-mentioned transparent laminate is preferably 50 to 500 MPa, more preferably 70 to 450 MPa, and still more preferably 90 to 400 MPa. By making the above indentation hardness 50 MPa or more, the surface hardness of the transparent laminate becomes high and it is not easy to generate dents and damages. In addition, by making the above indentation hardness 500 MPa or less, there is a tendency for excellent flexibility and bendability. It should be noted that in the case where hard coatings are laminated on both sides of the above-mentioned transparent laminate, it is sufficient that at least one surface satisfies the above range, and it is preferable that the hard coating with a pencil hardness of H or more satisfies the above indentation hardness.

[0038] The ratio (indentation elastic modulus / indentation hardness) of the above indentation elastic modulus to the above indentation hardness of the above-mentioned transparent laminate is 6.0 or more, preferably 6.5 or more, and more preferably 7.0 or more. By making the above ratio 6.0 or more, sufficient surface hardness and excellent bendability can be achieved. In addition, there is no particular limitation as the upper limit, but in order to make the surface hardness sufficient, it is preferably 80.0 or less.

[0039] The thickness of the above-mentioned transparent laminate is preferably 10 to 500 μm, more preferably 30 to 400 μm, and particularly preferably 50 to 300 μm. If the thickness of the above-mentioned transparent laminate is 10 μm or more, it is easy to make the surface hardness sufficient. In addition, if the thickness is 500 μm or less, sufficient bendability is easily exhibited.

[0040] <Substrate>

[0041] As the substrate in the transparent laminate of the present disclosure, known or conventional substrates such as plastic substrates, metal substrates, ceramic substrates, semiconductor substrates, glass substrates, paper substrates, wood substrates (wooden substrates), and substrates with a painted surface can be used. Among them, from the viewpoint of exhibiting transparency, glass substrates and plastic substrates are preferred, and glass substrates are particularly preferred. In addition, the above substrate may have a single-layer structure or a multi-layer structure, may be composed of one material, or two or more materials may be used.

[0042] Regarding the above-mentioned glass substrate, from the viewpoint of improving the strength against cracks in the case of thinning the glass and producing a panel that can withstand practical use, chemical strengthening can be carried out. From the viewpoint of producing a substrate with sufficient strength, end face treatment is preferably implemented. In addition, in order to improve abrasion resistance, smoothness, and crack resistance strength, a treatment layer or a coating film can be formed on either surface.

[0043] The thickness of the above-mentioned substrate is preferably, for example, 30 to 100 μm, more preferably 40 to 95 μm, and further preferably 50 to 90 μm. If the thickness of the above-mentioned glass substrate is 30 μm or more, sufficient strength can be easily exhibited as a substrate. In addition, if the thickness of the above-mentioned glass substrate is 100 μm or less, flexibility can be easily exhibited.

[0044] The above-mentioned transparent laminate may have a surface protective film. The above-mentioned surface protective film protects the surface of the above-mentioned hard coat, and the above-mentioned transparent laminate preferably has a surface protective film on at least one surface. In addition, in the case where the above-mentioned hard coat is formed on both surfaces of the above-mentioned substrate, etc., the above-mentioned surface protective film may also be provided on both surfaces of the above-mentioned transparent laminate.

[0045] As the above-mentioned surface protective film, a publicly known or commonly used surface protective film can be used, and there is no particular limitation. For example, a surface protective film having an adhesive layer on the surface of a plastic film can be used. As the above-mentioned plastic film, for example, those formed of plastic materials such as polyester (ethylene glycol terephthalate, ethylene glycol naphthalate, etc.), polyolefin (polyethylene, polypropylene, cyclic polyolefin, etc.), polystyrene, acrylic resin, polycarbonate, epoxy resin, fluororesin, silicone resin, diacetate resin, triacetate resin, polyarylate, polyvinyl chloride, polysulfone, polyethersulfone, polyetheretherimide, polyimide, polyamide, etc. can be cited. As the above-mentioned adhesive layer, for example, an adhesive layer formed of one or more of publicly known or commonly used adhesives such as acrylic adhesives, silicone adhesives, natural rubber adhesives, synthetic rubber adhesives, ethylene-vinyl acetate copolymer adhesives, ethylene-(meth)acrylate copolymer adhesives, styrene-isoprene block copolymer adhesives, styrene-butadiene block copolymer adhesives, etc. can be cited. In the above-mentioned adhesive layer, various additives (for example, antistatic agents, slip agents, etc.) can be contained. It should be noted that the plastic film and the adhesive layer may each have a single-layer structure or may each have a multi-layer (plural layer) structure. In addition, the thickness of the surface protective film is not particularly limited and can be appropriately selected.

[0046] As the above-mentioned surface protective film, for example, commercially available products can be obtained: the product name "SUNYTECT" series (manufactured by Sun A Kaken Co., Ltd.), the product name "E-MASK" series (manufactured by Nitto Denko Corporation), the product name "MASTACK" series (manufactured by Fujimori Kogyo Co., Ltd.), the product name "HITALEX" series (manufactured by Hitachi Chemical Co., Ltd.), the product name "ALPHAN" series (manufactured by Oji F-Tex Co., Ltd.), etc.

[0047] In addition, the above-mentioned transparent laminate may also have an adhesive layer. Preferably, the above-mentioned adhesive layer is laminated on the surface of the above-mentioned substrate opposite to the surface on which the hard coat is laminated in the above-mentioned transparent laminate. That is, when the above-mentioned transparent laminate has the above-mentioned adhesive layer, it is preferable to have the above-mentioned hard coat on one surface of the above-mentioned substrate and the above-mentioned adhesive layer on the other surface. In addition, it is more preferable that the above-mentioned transparent laminate has the above-mentioned adhesive layer on the surface of one surface.

[0048] As the adhesive constituting the above-mentioned adhesive layer, the same adhesives as those exemplified in the above-mentioned surface protective film can be used. Among them, from the viewpoints of good transparency and sufficient adhesiveness even when thin, acrylic adhesives and silicone adhesives are preferred, and acrylic adhesives are particularly preferred. It should be noted that the above-mentioned adhesives can be used alone or in combination of two or more.

[0049] The thickness of the above-mentioned adhesive layer is, for example, 0.1 to 50 μm, preferably 1 to 45 μm, more preferably 2 to 40 μm, and further preferably 5 to 35 μm.

[0050] The above-mentioned adhesive layer can be obtained by applying the above-mentioned adhesive to at least one surface of the substrate and curing it.

[0051] In addition, the above-mentioned transparent laminate may have a primer layer. Especially when the above-mentioned transparent laminate has a glass substrate, there may be problems with the adhesiveness between the substrate and the hard coat, and it is preferable to have a primer layer between the above-mentioned glass substrate and the above-mentioned hard coat.

[0052] The material of the above-mentioned primer layer is not particularly limited, and resins can be exemplified, for example. As the resin, for example, (meth)acrylic resin, polyurethane resin, (meth)acrylic polyurethane copolymer, vinyl chloride-vinyl acetate copolymer, polyester, butyral resin, chlorinated polypropylene, chlorinated polyethylene, epoxy resin, silicone resin, etc. can be exemplified. These resins can be used alone or in combination of two or more.

[0053] The thickness of the above-mentioned undercoat layer is preferably 0.1 to 30 μm, more preferably 1 to 20 μm. If the thickness of the undercoat layer is within the above range, it exhibits adhesion to the above-mentioned substrate, and when further laminating a hard coat, it is easy to improve the surface hardness of the hard coat surface.

[0054] The above-mentioned undercoat layer can be obtained by applying the above-mentioned resin to at least one surface of the substrate and curing it.

[0055] As a method for forming the above-mentioned undercoat layer, a usual coating method can be used. For example, known methods such as dip coating, roll coating, gravure coating, reverse coating, air knife coating, comma coating, die coating, screen printing method, spraying, gravure offset printing method, organic vapor deposition method, etc. can be used. As the curing treatment, for example, light irradiation using a mercury lamp, xenon lamp, carbon arc lamp, metal halide lamp, sunlight, electron beam source, laser light source, LED light source, etc. can be cited. It is preferably irradiated in a range where the cumulative irradiation amount is, for example, 300 to 10000 mJ / cm 2 . In addition, a transfer method such as adhesive material transfer, heat transfer, or UV transfer can also be used to transfer a film pre-coated on another substrate by the above-mentioned forming method to the substrate.

[0056] Preferably, after the light irradiation is completed, an annealing treatment is further performed to remove internal strain. For example, it is preferably heated at a temperature of 100 to 200 °C for about 30 minutes to 1 hour.

[0057] <Hard coat>

[0058] In the above-mentioned transparent laminate, the above-mentioned hard coat can be formed only on one surface (single-sided) of the above-mentioned substrate, and the above-mentioned hard coat can also be formed on both surfaces (double-sided) of the above-mentioned substrate. However, in the case where the above-mentioned transparent laminate has the above-mentioned adhesive layer, it is preferably formed only on one surface of the above-mentioned substrate. It should be noted that in the case of forming a hard coat on both sides of the above-mentioned substrate, as long as the physical property values of the hard coat described above and below are satisfied on at least one surface, the hard coats can be laminated with the same hard coat respectively, or layers with different thicknesses and compositions can be laminated respectively. In addition, a hard coat can be formed on one surface of the above-mentioned substrate, and the above-mentioned other layer can be formed on the other surface. From the viewpoint of suppressing crack generation, it is preferable to form the above-mentioned hard coat on at least one surface of the above-mentioned substrate and form the above-mentioned hard coat or the above-mentioned other layer on the other surface.

[0059] The above-mentioned hard coat is preferably formed from a cured product of a curable composition containing one or more curable compounds. That is, the above-mentioned curable composition preferably contains one or more curable compounds. The above-mentioned curable compounds can be used alone or in combination of two or more.

[0060] As the above-mentioned curable compound, polyorganosilsesquioxane is preferably included. By including the above-mentioned polyorganosilsesquioxane, the above-mentioned curable composition is less likely to shrink during curing, and thus a hard coat with high hardness and more excellent abrasion resistance can be produced. As the above-mentioned polyorganosilsesquioxane, free-radical polymerizable polyorganosilsesquioxane, cationic polymerizable polyorganosilsesquioxane, etc. can be cited. Among them, cationic polymerizable polyorganosilsesquioxane is preferred, and the above-mentioned cationic polymerizable polyorganosilsesquioxane is more preferably photo-cationic polymerizable polyorganosilsesquioxane.

[0061] The above-mentioned free-radical polymerizable polyorganosilsesquioxane has a free-radical polymerizable functional group in the molecule. As the above-mentioned free-radical polymerizable functional group, for example, (meth)acryloyl group, (meth)acrylamide group, vinyl group, vinylthio group, etc. can be cited.

[0062] The above-mentioned cationic polymerizable polyorganosilsesquioxane has a cationic polymerizable functional group in the molecule. As the above-mentioned cationic polymerizable functional group, for example, epoxy group, oxetanyl group, vinyl ether group, vinylphenyl group, etc. can be cited. Among them, from the viewpoint of being able to further improve the surface hardness of the hard coat, an epoxy group is preferred.

[0063] As the above-mentioned group containing an epoxy group, known or conventional groups having an ethylene oxide ring can be cited, and there is no particular limitation. From the viewpoints of the curability of the curable composition and the heat resistance of the hard coat, the group represented by the following formula (1a), the group represented by the following formula (1b), the group represented by the following formula (1c), and the group represented by the following formula (1d) are preferred, and the group represented by the following formula (1a) and the group represented by the following formula (1c) are more preferred, and the group represented by the following formula (1a) is further preferred.

[0064]

[0065] In the above formula (1a), R 1a represents a linear or branched alkylene group. As the linear or branched alkylene group, for example, methylene group, methylmethylene group, dimethylmethylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, decamethylene group, etc., linear or branched alkylene groups having 1 to 10 carbon atoms can be cited. Among them, as R 1a , from the viewpoint of the curability of the curable composition, a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms is preferred, and ethylene group, trimethylene group, propylene group are more preferred, and ethylene group and trimethylene group are further preferred.

[0066] In the above formula (1b), R 1b represents a linear or branched alkylene group, and examples thereof can be shown as the same as those of R 1aThe same group. Among them, as R 1b , from the viewpoint of the curability of the curable composition, it is preferably a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms, more preferably ethylene, trimethylene, propylene, and further preferably ethylene, trimethylene.

[0067] In the above formula (1c), R 1c represents a linear or branched alkylene group, and examples thereof include the same groups as R 1a . Among them, as R 1c , from the viewpoint of the curability of the curable composition, it is preferably a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms, more preferably ethylene, trimethylene, propylene, and further preferably ethylene, trimethylene.

[0068] In the above formula (1d), R 1d represents a linear or branched alkylene group, and examples thereof include the same groups as R 1a . Among them, as R 1d , from the viewpoint of the curability of the curable composition, it is preferably a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms, more preferably ethylene, trimethylene, propylene, and further preferably ethylene, trimethylene.

[0069] As R 1 in the formula (1), the group represented by the above formula (1a) and having R 1a being ethylene is particularly preferred [wherein, 2-(3,4-epoxycyclohexyl)ethyl].

[0070] As the above polyorganosilsesquioxane, for example, a compound having a structural unit represented by the following formula (1) can be cited.

[0071] [R 1 SiO 3 / 2 (1)

[0072] The structural unit represented by the above formula (1) is usually a silsesquioxane structural unit represented by [RSiO 3 / 2 (so-called T unit). It should be noted that R in the above formula represents a hydrogen atom or a monovalent organic group, and the same applies hereinafter. The structural unit represented by the above formula (1) is formed by hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compound. It should be noted that in this specification, a compound having the structural unit represented by the above formula (1) is sometimes referred to as "silsesquioxane (X)". R 1 in the formula (1) represents a group (monovalent group) containing the above cationic polymerizable functional group.

[0073] The silsesquioxane (X) may have only one structural unit represented by the above formula (1), or may have two or more structural units represented by the above formula (1).

[0074] Alternatively, in the silsesquioxane (X), as the silsesquioxane structural unit [RSiO 3 / 2 , in addition to having the structural unit represented by the above formula (1), it may also have a structural unit represented by the following formula (2).

[0075] [R 2 SiO 3 / 2 (2)

[0076] The structural unit represented by the above formula (2) is generally the silsesquioxane structural unit (T unit) represented by [RSiO 3 / 2 . That is, the structural unit represented by the above formula (2) is formed by the hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compound.

[0077] R in the above formula (2) 2 represents a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted alkyl group. As the above aryl group, for example, phenyl, tolyl, naphthyl, etc. can be mentioned. As the above aralkyl group, for example, benzyl, phenethyl, etc. can be mentioned. As the above cycloalkyl group, for example, cyclobutyl, cyclopentyl, cyclohexyl can be mentioned. As the above alkyl group, for example, linear or branched alkyl groups such as methyl, ethyl, propyl, n-butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, etc. can be mentioned.

[0078] As the above substituted aryl group, substituted aralkyl group, substituted cycloalkyl group, and substituted alkyl group, groups in which a hydrogen atom or a part or all of the main chain skeleton in the above aryl group, aralkyl group, cycloalkyl group, and alkyl group is substituted with at least one selected from the group consisting of an alkyl group (especially a linear or branched alkyl group having 1 to 10 carbon atoms), an ether group, an ester group, a carbonyl group, a siloxy group, a halogen atom (such as a fluorine atom), a mercapto group, an amino group, and a hydroxyl group can be mentioned.

[0079] Among them, as R 2 , it is preferably a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group, more preferably a substituted or unsubstituted aryl group, and still more preferably a phenyl group.

[0080] The ratio of each of the above silsesquioxane structural units (the structural unit represented by formula (1) and the structural unit represented by formula (2)) in the silsesquioxane (X) can be appropriately adjusted according to the composition of the raw materials (hydrolyzable trifunctional silanes) used to form these structural units.

[0081] Among them, the silsesquioxane (X) preferably contains at least R 1 a structural unit represented by the above formula (1) which is a group containing an alicyclic epoxy group, and R 2 a structural unit represented by the above formula (2) which is an aryl group that may have a substituent. In this case, there is a tendency for the surface hardness, flexibility, processability, and flame retardancy of the hard coat to be more excellent.

[0082] Alternatively, the silsesquioxane (X) may further have, in addition to the structural unit represented by the above formula (1) as a T unit and the structural unit represented by the above formula (2), at least one siloxane structural unit selected from the group consisting of a structural unit represented by [R3SiO 1 / 2 (so-called M unit), a structural unit represented by [R2SiO 2 / 2 (so-called D unit), and a structural unit represented by [SiO 4 / 2 (so-called Q unit). It should be noted that R in the above M unit and the above D unit may be the same groups as R 1 in the structural unit represented by the above formula (1) and R 2 in the structural unit represented by the above formula (2). As a silsesquioxane structural unit other than the structural unit represented by the above formula (1) and the structural unit represented by the above formula (2), for example, a structural unit represented by the following formula (3) can be cited.

[0083] [HSiO 3 / 2 (3)

[0084] The silsesquioxane (X) contains a structural unit (T3 body) represented by the following formula (I). Moreover, it may also contain a structural unit (T2 body) represented by the following formula (II).

[0085] [R a SiO 3 / 2 (I)

[0086] [R b SiO 2 / 2 (OR c )](II)

[0087] It should be noted that if the structural unit shown in the above formula (I) is described in more detail, it is represented by the following formula (I'). In addition, if the structural unit shown in the above formula (II) is described in more detail, it is represented by the following formula (II'). Among the three oxygen atoms bonded to the silicon atom shown in the structure represented by the following formula (I'), each is bonded to another silicon atom (a silicon atom not shown in formula (I')). On the other hand, the two oxygen atoms located above and below the silicon atom shown in the structure represented by the following formula (II') are each bonded to another silicon atom (a silicon atom not shown in formula (II')). That is, the above T3 body and T2 body are both structural units (T units) formed by hydrolysis and condensation reactions of corresponding hydrolyzable trifunctional silane compounds.

[0088]

[0089] R in the above formula (I) a (R in formula (I')) a is the same), and R in formula (II) b (R in formula (II')) b is the same) each represent a group containing a cationic polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a hydrogen atom. Specific examples of R a and R b can be exemplified by the same groups as R 1 in the above formula (1) and R 2 in the above formula (2). It should be noted that R a in formula (I) and R b in formula (II) are each a group derived from the group (a group other than an alkoxy group and a halogen atom) bonded to the silicon atom in the hydrolyzable trifunctional silane compound used as the raw material for the silsesquioxane (X), or, for example, when the above cationic polymerizable functional group is an epoxy group, it is a group obtained by epoxidizing the group (a group other than an alkoxy group and a halogen atom) bonded to the silicon atom in the hydrolyzable trifunctional silane compound used as the raw material for the silsesquioxane (X).

[0090] R in the above formula (II) c (R in formula (II')) c is the same) represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. As the alkyl group having 1 to 4 carbon atoms, for example, linear or branched alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, and isobutyl can be cited. Among them, methyl and ethyl are preferred, and methyl is more preferred. R in formula (II) cThe alkyl group in [compound name] generally originates from the alkyl group of the alkoxy group in the hydrolyzable silane compound used as a raw material for forming the silsesquioxane (X).

[0091] The molar ratio of the structural unit (T3 body) represented by the above formula (I) to the structural unit (T2 body) represented by the above formula (II) in the silsesquioxane (X) [structural unit represented by formula (I) / structural unit represented by formula (II)] (sometimes referred to as "T3 body / T2 body") is not particularly limited, preferably 5 or more, more preferably 5 to 20, further preferably 5 to 18, further preferably 6 to 16, further preferably 7 to 15, and particularly preferably 8 to 14. By making the above molar ratio [T3 body / T2 body] 5 or more, there is a tendency for the surface hardness of the hard coat to be further improved.

[0092] The above molar ratio [T3 body / T2 body] in the silsesquioxane (X) can be determined, for example, by 29 Si-NMR spectrum measurement. In 29 the Si-NMR spectrum, the silicon atoms in the structural unit (T3 body) represented by the above formula (I) and the silicon atoms in the structural unit (T2 body) represented by the above formula (II) show signals (peaks) at different positions (chemical shifts). Therefore, by calculating the integral ratio of these respective peaks, the above molar ratio [T3 body / T2 body] is determined. Specifically, for example, in the case where the silsesquioxane (X) has a structural unit represented by the above formula (1) and R 1 is 2-(3,4-epoxycyclohexyl)ethyl, the signal of the silicon atom in the structure (T3 body) represented by the above formula (I) appears at -64 to -70 ppm, and the signal of the silicon atom in the structure (T2 body) represented by the above formula (II) appears at -54 to -60 ppm. Therefore, in this case, the above molar ratio [T3 body / T2 body] can be determined by calculating the integral ratio of the signal (T3 body) at -64 to -70 ppm to the signal (T2 body) at -54 to -60 ppm.

[0093] The 29 Si-NMR spectrum of the silsesquioxane (X) can be measured, for example, using the following apparatus and conditions.

[0094] Measuring apparatus: Trade name "JNM-ECA500 NMR" (manufactured by JEOL Ltd.).

[0095] Solvent: Deuterated chloroform.

[0096] Number of integration times: 1800 times.

[0097] Measurement temperature: 25 °C.

[0098] The above-mentioned molar ratio [T3 body / T2 body] of the silsesquioxane (X) being 5 or more means that there is a certain amount or more of the T2 body relative to the T3 body in the silsesquioxane (X). As such a T2 body, for example, the structural unit represented by the following formula (4), the structural unit represented by the following formula (5), the structural unit represented by the following formula (6), etc. may be mentioned. R in the following formula (4) 1 and R in the following formula (5) 2 are respectively the same as R in the above formula (1) 1 and R in the above formula (2) 2 . R in the following formulas (4) to (6) c is the same as R in formula (II) c and represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0099] [R 1 SiO 2 / 2 (OR c )](4)

[0100] [R 2 SiO 2 / 2 (OR c )](5)

[0101] [HSiO 2 / 2 (OR c )](6)

[0102] The polyorganosilsesquioxane (especially the silsesquioxane (X)) may be a silsesquioxane having a cage shape (cage silsesquioxane). The cage silsesquioxane includes a complete cage silsesquioxane and an incomplete cage silsesquioxane, and among them, the incomplete cage silsesquioxane is preferred.

[0103] Generally, the complete cage silsesquioxane is a polyorganosilsesquioxane composed only of T3 bodies, and there is no T2 body in the molecule. That is, it implies that: the above-mentioned molar ratio [T3 body / T2 body] is 5 or more, and the silsesquioxane having an inherent absorption peak around 1100 cm -1 as described later has an incomplete cage silsesquioxane structure.

[0104] Whether the silsesquioxane (X) has a cage (incomplete cage) silsesquioxane structure can be confirmed by FT-IR spectrum [Reference: R.H. Raney, M. Itoh, A. Sakakibara and T. Suzuki, Chem. Rev. 95-1409 (1995)]. Specifically, in the FT-IR spectrum, there are no inherent absorption peaks around 1050 cm -1 and around 1150 cm -1 respectively, and there is an absorption peak at 1100 cm-1 When there is an inherent absorption peak in the vicinity, it is identified that the silsesquioxane (X) has a cage-type (incomplete cage-type) silsesquioxane structure. In contrast, usually in the FT-IR spectrum, when there are inherent absorption peaks in the vicinity of 1050 cm -1 and 1150 cm -1 respectively, it is identified that it has a ladder-type silsesquioxane structure. It should be noted that the FT-IR spectrum of the silsesquioxane (X) can be measured, for example, by the following apparatus and conditions.

[0105] Measuring apparatus: Trade name "FT-720" (manufactured by Horiba, Ltd.).

[0106] Measuring method: Transmission method.

[0107] Resolution: 4 cm -1 .

[0108] Measuring wavenumber range: 400 - 4000 cm -1 .

[0109] Number of integrations: 16 times.

[0110] The proportion (total amount) of the structural unit having a cationic polymerizable functional group (for example, the structural unit represented by the above formula (1), the structural unit represented by the above formula (4), etc.) in the polyorganosilsesquioxane relative to the total amount of the siloxane structural units [all siloxane structural units; the total amount of M units, D units, T units, and Q units] (100 mol%) is not particularly limited, and is preferably 50 mol% or more (for example, 50 - 100 mol%), more preferably 55 - 100 mol%, still more preferably 65 - 99.9 mol%, further preferably 80 - 99 mol%, and particularly preferably 90 - 98 mol%. If the above proportion is 50 mol% or more, the curability of the curable composition is improved, and the surface hardness of the hard coat becomes significantly higher. It should be noted that the proportion of each siloxane structural unit in the polyorganosilsesquioxane can be calculated, for example, from the composition of the raw materials, NMR spectrum measurement, etc.

[0111] The proportion of the structural unit (T3 body) represented by the above formula (I) in the silsesquioxane (X) relative to the total amount of the siloxane structural units [all siloxane structural units; the total amount of M units, D units, T units, and Q units] (100 mol%) is not particularly limited, and is preferably 50 mol% or more, more preferably 60 - 99 mol%, still more preferably 70 - 98 mol%, further preferably 80 - 95 mol%, and particularly preferably 85 - 92 mol%. It is speculated that by setting the proportion of the structural unit of the T3 body to 50 mol% or more, it is easy to form an incomplete cage shape with an appropriate molecular weight, but there is a tendency for the surface hardness of the hard coat to be further improved.

[0112] The ratio (total amount) of the structural unit represented by the above formula (2) and the structural unit represented by the above formula (5) in the silsesquioxane (X) relative to the total amount of siloxane structural units [total amount of all siloxane structural units; total amount of M unit, D unit, T unit and Q unit] (100 mol%) is not particularly limited, and is preferably 0 to 50 mol%, more preferably 0 to 40 mol%, still more preferably 0 to 30 mol%, and particularly preferably 1 to 15 mol%. By setting the above ratio to 50 mol% or less, the ratio of the structural unit having a cationic polymerizable functional group can be relatively increased, so that the curability of the curable composition is improved, and the surface hardness of the hard coat tends to become higher.

[0113] The ratio (total amount) of the structural unit represented by the above formula (I) and the structural unit represented by the above formula (II) in the silsesquioxane (X) relative to the total amount of siloxane structural units [total amount of all siloxane structural units; total amount of M unit, D unit, T unit and Q unit] (100 mol%) (especially the total ratio of T3 body and T2 body) is not particularly limited, and is preferably 60 mol% or more (for example, 60 to 100 mol%), more preferably 70 mol% or more, still more preferably 80 mol% or more, and particularly preferably 90 mol% or more. It is speculated that by setting the above ratio to 60 mol% or more, an incomplete cage shape with a moderate molecular weight is easily formed, but the surface hardness of the hard coat tends to be further improved. Particularly preferably, the ratio (total amount) of the structural unit represented by the above formula (1), the structural unit represented by the above formula (2), the structural unit represented by the above formula (4) and the structural unit represented by the above formula (5) is within the above range.

[0114] The number average molecular weight (Mn) in terms of standard polystyrene obtained by gel permeation chromatography of the silsesquioxane (X) is not particularly limited, and is preferably 1000 to 3000, more preferably 1000 to 2800, still more preferably 1100 to 2600, and particularly preferably 1500 to 2500. By setting the number average molecular weight to 1000 or more, the surface hardness of the hard coat tends to be further improved. The heat resistance and abrasion resistance of the hard coat tend to be improved. On the other hand, by setting the number average molecular weight to 3000 or less, the compatibility with other components in the curable composition is improved, and the heat resistance of the hard coat is improved.

[0115] The molecular weight dispersion (Mw / Mn) of the silsesquioxane (X) in terms of standard polystyrene conversion by gel permeation chromatography is not particularly limited, preferably 1.0 to 3.0, more preferably 1.1 to 2.0, further preferably 1.2 to 1.9, still further preferably 1.3 to 1.8, and particularly preferably 1.45 to 1.80. By setting the molecular weight dispersion to 3.0 or less, the surface hardness of the hard coat tends to become higher. On the other hand, by setting the molecular weight dispersion to 1.0 or more (especially 1.1 or more), it tends to be more likely to be in a liquid state and the operability is improved.

[0116] It should be noted that the number average molecular weight and molecular weight dispersion of the silsesquioxane (X) can be measured by the following apparatus and conditions.

[0117] Measuring apparatus: Trade name “LC-20AD” (manufactured by Shimadzu Corporation).

[0118] Chromatographic column: Shodex KF-801 × 2 columns, KF-802, and KF-803 (manufactured by Showa Denko K.K.).

[0119] Measuring temperature: 40 °C.

[0120] Eluent: THF, sample concentration 0.1 to 0.2 mass%.

[0121] Flow rate: 1 mL / minute.

[0122] Detector: UV-VIS detector (trade name “SPD-20A”, manufactured by Shimadzu Corporation).

[0123] Molecular weight: In terms of standard polystyrene conversion.

[0124] The polyorganosilsesquioxane can be produced by a known or conventional method for producing silsesquioxanes, and is not particularly limited. For example, it can be produced by hydrolyzing and condensing one or two or more hydrolyzable silane compounds.

[0125] The content ratio of the polyorganosilsesquioxane in the above curable composition is not particularly limited. Relative to the total amount of the curable compounds (100 mass%), it is preferably more than 50 mass% (for example, more than 50 mass% and 98 mass% or less), more preferably 60 to 96 mass%, further preferably 70 to 95 mass%, and particularly preferably 80 to 93 mass%. If the above content ratio is more than 50 mass%, the surface hardness of the hard coat tends to be further improved. If the above content ratio is 98 mass% or less, other components can be contained, and the effects obtained by containing them tend to be further improved. In addition, a curing catalyst can be contained, and thus the curable composition tends to be cured more effectively.

[0126] The above curable composition may contain a compound having one or more cationic polymerizable groups and one or more radical polymerizable groups in the molecule (hereinafter sometimes referred to as "Compound A"). By containing Compound A, the above curable composition can effectively increase the crosslinking density when forming a cured product, easily impart high surface hardness, excellent flexibility and flexural durability to the hard coat, and can prevent the antifouling performance from being easily reduced. It should be noted that only one kind of Compound A can be used, or two or more kinds can be used.

[0127] Examples of the "cationic polymerizable group" possessed by Compound A include an epoxy group, an oxetanyl group, a vinyl ether group, etc. From the viewpoint of suppressing the reduction of the surface hardness, flexibility and flexural durability of the hard coat, an epoxy group is preferred. It should be noted that when Compound A has two or more cationic polymerizable groups, these cationic polymerizable groups may be the same or different from each other.

[0128] Examples of the "radical polymerizable group" possessed by Compound A include a (meth)acryloyl group, a vinyl group, etc. From the viewpoints of the surface hardness and flexural durability of the hard coat, a (meth)acryloyl group is preferred. It should be noted that when Compound A has two or more radical polymerizable groups, these radical polymerizable groups may be the same or different from each other.

[0129] The number of cationic polymerizable groups in one molecule of Compound A is preferably 1 or more, and there is no particular limitation. Preferably it is 1 to 5, more preferably 1 to 3, and further preferably

[0130] 1 or 2. In addition, the number of radical polymerizable groups in one molecule of Compound A is preferably 1 or more, and there is no particular limitation. For example, it is preferably 1 to 5, more preferably 1 to 3

[0131] and further preferably 1 or 2.

[0132] The functional group equivalent of the cationic polymerizable group of Compound A is not particularly limited, and is preferably

[0133] 50 to 500, more preferably 80 to 480, and further preferably 120 to 450. If the above functional group equivalent is 50 or more, it is easy to make the flexural durability of the hard coat sufficient. If the above functional group equivalent is

[0134] 500 or less, the surface hardness of the hard coat can be made sufficient. It should be noted that the functional group equivalent of the cationic polymerizable group of Compound A can be calculated by the following formula.

[0135] [Functional group equivalent of cationic polymerizable group] = [Molecular weight of Compound A] / [Number of cationic polymerizable groups possessed by Compound A]

[0136] The functional group equivalent of the radical polymerizable group of Compound A is not particularly limited, and is preferably

[0137] 50 to 500, more preferably 80 to 480, and still more preferably 120 to 450. If the above functional group equivalent is 50 or more, it is easy to make the bending durability of the hard coat sufficient. If the above functional group equivalent is

[0138] 500 or less, the surface hardness of the hard coat can be made sufficient. It should be noted that the functional group equivalent of the radical polymerizable group of Compound A can be calculated by the following formula.

[0139] [Functional group equivalent of radical polymerizable group] = [Molecular weight of Compound A] / [Number of radical polymerizable groups possessed by Compound A]

[0140] Specific examples of Compound A include, for example: 3,4-epoxycyclohexylmethyl (meth)acrylate, glycidyl (meth)acrylate, dipropylene glycol diglycidyl ether di(meth)acrylate (a compound obtained by reacting two epoxy groups of dipropylene glycol diglycidyl ether with (meth)acrylic acid), dipropylene glycol diglycidyl ether semi(meth)acrylate (by making

[0141] (Compound obtained by reacting (meth)acrylic acid with one epoxy group of tripropylene glycol diglycidyl ether), bisphenol A epoxy di(meth)acrylate (compound obtained by reacting (meth)acrylic acid with two epoxy groups of bisphenol A diglycidyl ether), bisphenol A epoxy semi(meth)acrylate (compound obtained by reacting (meth)acrylic acid or its derivative with one epoxy group of bisphenol A diglycidyl ether), bisphenol F epoxy di(meth)acrylate, bisphenol F epoxy semi(meth)acrylate, bisphenol S epoxy di(meth)acrylate, bisphenol S epoxy semi(meth)acrylate and other compounds having an epoxy group and a (meth)acryloyl group in one molecule; (meth)acrylic acid 3-oxetanyl methyl ester, (meth)acrylic acid 3-methyl-3-oxetanyl methyl ester, (meth)acrylic acid 3-ethyl-3-oxetanyl methyl ester, (meth)acrylic acid 3-butyl-3-oxetanyl methyl ester, (meth)acrylic acid 3-hexyl-3-oxetanyl methyl ester and other compounds having an oxetanyl group and a (meth)acryloyl group in one molecule; (meth)acrylic acid 2-vinyloxyethyl ester, (meth)acrylic acid 3-vinyloxypropyl ester, (meth)acrylic acid 1-methyl-2-vinyloxyethyl ester, (meth)acrylic acid 2-vinyloxypropyl ester, (meth)acrylic acid 4-vinyloxybutyl ester, (meth)acrylic acid 1-methyl-3-vinyloxypropyl ester, (meth)acrylic acid 1-vinyloxymethylpropyl ester, (meth)acrylic acid 2-methyl-3-vinyloxypropyl ester, (meth)acrylic acid 1,1-Dimethyl-2-vinyloxyethyl ester, 3-vinyloxybutyl (meth)acrylate, 1-methyl-2-vinyloxypropyl (meth)acrylate, 2-vinyloxybutyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, 3-vinyloxymethylcyclohexylmethyl (meth)acrylate, 2-vinyloxycyclohexylmethyl (meth)acrylate, p-vinyloxymethylphenyl (meth)acrylate, m-vinyloxymethylphenyl (meth)acrylate, o-vinyloxymethylphenyl (meth)acrylate, 2-(vinyloxyethoxy)ethyl (meth)acrylate, 2-(vinyloxyisopropoxy)ethyl (meth)acrylate, 2-(vinyloxyethoxy)propyl (meth)acrylate, 2-(vinyloxyethoxy)isopropyl (meth)acrylate, 2-(vinyloxyisopropoxy)propyl (meth)acrylate, 2-(vinyloxyisopropoxy)isopropyl (meth)acrylate, 2-(vinyloxyethoxyethoxy)ethyl (meth)acrylate, 2-(vinyloxyethoxyisopropoxy)ethyl (meth)acrylate, 2-(vinyloxyisopropoxyethoxy)ethyl (meth)acrylate, 2-(vinyloxyisopropoxy)ethyl (meth)acrylate, 2-(vinyloxyethoxyethoxy)propyl (meth)acrylate, 2-(vinyloxyethoxyisopropoxy)propyl (meth)acrylate, 2-(vinyloxyisopropoxyethoxy)propyl (meth)acrylate, 2-(vinyloxyisopropoxyisopropoxy)propyl (meth)acrylate, 2-(vinyloxyethoxyethoxy)isopropyl (meth)acrylate, 2-(vinyloxyethoxyisopropoxy)isopropyl (meth)acrylate, 2-(vinyloxyisopropoxyethoxy)isopropyl (meth)acrylate, 2-(vinyloxyisopropoxyisopropoxy)isopropyl (meth)acrylate, 2-(vinyloxyethoxyethoxyethoxy)ethyl (meth)acrylate, 2-(vinyloxyethoxyethoxyethoxyethoxy)ethyl (meth)acrylate, 2-(isopropenyloxyethoxy)ethyl (meth)acrylate, 2-(isopropenyloxyethoxyethoxy)ethyl (meth)acrylate, 2-(isopropenyloxyethoxyethoxyethoxy)ethyl (meth)acrylate, 2-(isopropenyloxyethoxyethoxyethoxyethoxy)ethyl (meth)acrylate, polyethylene glycol monovinyl ether (meth)acrylate, polypropylene glycol monovinyl ether (meth)acrylate and other compounds having a vinyl ether group and a (meth)acryloyl group in one molecule, etc.,

[0142] From the viewpoints of the bending durability and surface hardness of the hard coat, as Compound A, a compound having an epoxy group as a cationically polymerizable group and a (meth)acryloyl group as a radically polymerizable group in one molecule is preferred. Specifically, (meth)acrylic acid 3,4-epoxycyclohexylmethyl ester, glycidyl (meth)acrylate, tripropylene glycol diglycidyl ether hemis (meth)acrylate, bisphenol A epoxy hemis (meth)acrylate, bisphenol F epoxy hemis (meth)acrylate, bisphenol S epoxy hemis (meth)acrylate, etc. are preferred.

[0143] Compound A can be produced by a known method. For example, it can be obtained by reacting a part of the cationically polymerizable groups of a compound having two or more cationically polymerizable groups (such as an epoxy group) in one molecule with a carboxylic acid having a radically polymerizable group (such as acrylic acid, methacrylic acid, etc.) or its derivative. In addition, as the above Compound A, commercially available products such as the trade names "LIGHTESTER G", "Epoxy Ester 200PA", "EPOXYESTER200PA-E5" (above, manufactured by Kyoeisha Chemical Co., Ltd.), and the trade name "NK OLIGO EA1010N" (manufactured by Shin-Nakamura Chemical Co., Ltd.) can also be used.

[0144] The content ratio of Compound A in the above curable composition is not particularly limited. It is preferably 0.05 to 8% by mass, more preferably 0.1 to 5% by mass, and further preferably 0.2 to 3% by mass relative to the total amount (100% by mass) of the curable compounds. If the above content ratio is within the above range, the sebum adhesion resistance of the surface of the hard coat is more excellent.

[0145] The content (mixing amount) of Compound A in the above curable composition is not particularly limited. As a solid component, it is preferably 1 to 100 parts by mass, more preferably 1.5 to 75 parts by mass, and further preferably 2 to 50 parts by mass relative to 100 parts by mass of the above polyorganosilsesquioxane. By setting the content of Compound A to 1 part by mass or more, there is a tendency for the bending property and bending durability of the hard coat to be further improved. On the other hand, by setting the content of Compound A to 100 parts by mass or less, there is a tendency for the surface hardness of the hard coat to be maintained.

[0146] In addition, the above curable composition preferably contains an aliphatic compound having two or more cationically polymerizable groups in the molecule (hereinafter sometimes referred to as Compound B), and more preferably contains two or more kinds of Compound B. By containing Compound B, the flexibility of the hard coat can be imparted, and the bending and bending durability can be easily exhibited. In particular, by containing two or more kinds of Compound B, the surface hardness can be maintained, and higher bending properties can be exhibited. It should be noted that Compound B is a compound that does not belong to the above polyorganosilsesquioxane and Compound A.

[0147] As the above-mentioned cationic polymerizable group, the same groups as those exemplified in Compound A can be mentioned. For example, an epoxy group, an oxetanyl group, a vinyl ether group, etc. can be mentioned. From the viewpoint of exhibiting the surface hardness, flexibility, and flexural durability of the above-mentioned hard coat, an epoxy group is preferred, and from the viewpoint of reactivity, a glycidyl group is more preferred. It should be noted that the two or more cationic polymerizable groups possessed by Compound B may be the same or different from each other.

[0148] The number of cationic polymerizable groups possessed by Compound B in one molecule is two or more, and there is no particular limitation. For example, it is preferably 2 to 5, more preferably 2 to 3, and further preferably 2.

[0149] The "aliphatic compound" in Compound B refers to an aliphatic compound that does not have a cyclic structure other than the above-mentioned cationic polymerizable group. As Compound B, for example, a glycidyl ether of a dihydric or higher alcohol without a cyclic structure; a glycidyl ester of a dihydric or higher carboxylic acid [such as adipic acid, sebacic acid, maleic acid, itaconic acid, etc.] can be mentioned. As the above-mentioned dihydric or higher alcohol without a cyclic structure, for example, dihydric alcohols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol; polyhydric alcohols with 3 or more hydroxyl groups such as glycerin, diglycerin, erythritol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, etc. can be mentioned. In addition, the dihydric or higher alcohol may be a polyether polyol, a polyester polyol, a polycarbonate polyol, a polyolefin polyol, etc.

[0150] As Compound B, a compound having two cationic polymerizable functional groups at both ends of the above-mentioned aliphatic compound is preferred. Specifically, a compound represented by the following formula (A) is preferred.

[0151] [Chemical formula 7]

[0152] E 1 —O—M—O—E 2 (A)

[0153] In the above formula (A), M represents a linear or branched alkylene group having 2 to 10 carbon atoms or an ethylene glycol group having 5 to 15 repeating units. Examples of the linear or branched alkylene group having 2 to 10 carbon atoms include linear or branched alkylene groups having 2 to 10 carbon atoms such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, and decamethylene. Among them, as M, from the viewpoints of improving the surface hardness, flexibility, and flexural durability of the hard coat film and preventing the antifouling performance from being easily reduced, a linear or branched alkylene group having 3 to 8 carbon atoms is preferred, a linear alkylene group having 5 to 7 carbon atoms is more preferred, and a linear alkylene group having 6 carbon atoms (hexamethylene) is further preferred. In addition, examples of the ethylene glycol group having 5 to 15 repeating units include hexaethylene glycol group, nonaethylene glycol group, and decaethylene glycol group. In order to maintain the surface hardness and further improve the flexibility, the nonaethylene glycol group is preferred. It should be noted that in the case of containing two or more compounds B, it is preferred to contain both a compound having a linear or branched alkylene group having 2 to 10 carbon atoms as M and a compound having an ethylene glycol group having 5 to 15 repeating units.

[0154] In the above formula (A), E 1 and E 2 are the same or different and represent cationically polymerizable functional groups. From the viewpoints of reactivity, improving the surface hardness, flexibility, and flexural durability of the hard coat, and preventing the antifouling performance from being easily reduced, a group represented by the following formula (E) is preferred.

[0155]

[0156] In formula (E), R A represents a linear or branched alkylene group having 1 to 6 carbon atoms. Examples of the linear or branched alkylene group having 1 to 6 carbon atoms include: methylene, methylmethylene, dimethylmethylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, decamethylene, etc. Among them, as R A , from the viewpoints of reactivity, improving the surface hardness, flexibility, and flexural durability of the hard coat, and preventing the antifouling performance from being easily reduced, a linear alkylene group having 1 to 4 carbon atoms is preferred, more preferably methylene or ethylene, and further

[0157] preferably methylene. R B is a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, preferably

[0158] a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

[0159] The functional group equivalent of the cationically polymerizable group of compound B is not particularly limited, and is preferably

[0160] 50 to 500, more preferably 80 to 480, and still more preferably 120 to 450. When the amount of the above functional group is

[0161] 50 or more, the bending durability of the hard coat is likely to be sufficient. When the epoxy equivalent of the above functional group is

[0162] 500 or less, the surface hardness of the hard coat can be sufficient. In addition, in the case of containing two or more kinds of

[0163] Compound B, the epoxy equivalent of at least one Compound B is preferably 50 to 200, more preferably

[0164] 80 to 180, and still more preferably 100 to 160. In addition, the functional group of the other Compound B

[0165] equivalent is preferably more than 200 to 500, more preferably 220 to 450, and still more preferably 240 to 400.

[0166] By combining Compound B containing a functional group equivalent within the above range, the surface hardness can be maintained,

[0167] and higher flexibility can be exhibited. It should be noted that the functional group equivalent of the cation-polymerizable

[0168] group of Compound B can be calculated by the following formula.

[0169] [Functional group equivalent of cation-polymerizable group] = [Molecular weight of Compound B] / [Number of cation-polymerizable groups possessed by Compound B]

[0170] It should be noted that hereinafter, in this specification, Compound B with a functional group equivalent of 50 to 200

[0171] may sometimes be referred to as "Compound B with a short chain length", and Compound B with a functional group equivalent of more than 200 to 500

[0172] may sometimes be referred to as "Compound B with a long chain length".

[0173] Specific examples of Compound B include, for example: ethylene glycol diglycidyl ether,

[0174] 1,3-propanediol diglycidyl ether, 2-methyl-1,3-propanediol diglycidyl ether, 2-butyl-2-ethyl-

[0175] 1,3-propanediol diglycidyl ether, 1,4-butanediol diglycidyl ether (tetramethylene glycol diglycidyl ether),

[0176] neopentyl glycol diglycidyl ether, 3-methyl-2,4-pentanediol diglycidyl ether,

[0177] 2,4-pentanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether (pentamethylene glycol diglycidyl ether

[0178] glyceryl ether), 3-methyl-1,5-pentanediol diglycidyl ether, 2-methyl-2,4-pentanediol diglycidyl ether

[0179] Glyceryl ether, 2,4-diethyl-1,5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether

[0180] (hexamethylene glycol diglycidyl ether), 1,7-heptanediol diglycidyl ether, 3,5-heptanediol

[0181] Diglycidyl ether, 1,8-octanediol diglycidyl ether, 2-methyl-1,8-octanediol diglycidyl ether

[0182] ether, alkylene glycol diglycidyl ethers (alkanediol diglycidyl ethers) such as 1,9-nonanediol diglycidyl ether, or (poly)alkylene glycol diglycidyl ethers such as diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl ether, and nonaethylene glycol diglycidyl ether. Among them, as compound B, it is preferred to contain glycol diglycidyl ether and (poly)alkylene glycol diglycidyl ether, more preferably to contain glycol diglycidyl ether as a compound B with a short chain length and (poly)alkylene glycol diglycidyl ether as a compound B with a long chain length, and particularly preferably to contain nonaethylene glycol diglycidyl ether and 1,6-hexanediol diglycidyl ether in combination.

[0183] Commercially available products of compound B include: trade names "Epolight 40E", "Epolight 100E", "Epolight 200E", "Epolight 400E", "Epolight 1600", "Epolight 1600N" (manufactured by Kyoeisha Chemical Co., Ltd.), and trade name "YH-300" (manufactured by Nippon Steel Chemicals Co., Ltd.).

[0184] The content of compound B in the curable composition is not particularly limited, but is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, and even more preferably 5 to 13% by mass relative to the total amount of the curable compound (100% by mass). When the content is within the above range, the bendability of the transparent laminate becomes more appropriate.

[0185] The content of Compound B is not particularly limited. As a solid component, relative to 100 parts by mass of the above polyorganosilsesquioxane, it is preferably 1 to 20 parts by mass, more preferably 3 to 17 parts by mass, and still more preferably 5 to 15 parts by mass. If the above content is within the above range, the flexibility of the transparent laminate becomes more appropriate.

[0186] In addition, in the case of containing Compound B with a short chain length and Compound B with a long chain length respectively, the content of Compound B with a long chain length is preferably 35 to 95% by mass, more preferably 50 to 90% by mass, and still more preferably 65 to 87% by mass relative to the total amount of Compound B (100% by mass). In Compound B, if the content of Compound B with a long chain length is 35% by mass or more, the flexibility is easily exhibited. In addition, if the content of Compound B with a long chain length is 95% by mass or less, the surface hardness can be sufficiently improved.

[0187] Preferably, the above curable composition contains a curing catalyst. The above curing catalyst is a compound capable of initiating or promoting the polymerization reaction of curable compounds such as the above polyorganosilsesquioxane, Compound A, and Compound B. The above curing catalyst can be used alone or in combination of two or more.

[0188] As the above curing catalyst, it is selected according to the type of curable functional group possessed by the above curable compound. Among them, a cationic polymerization initiator and / or a radical polymerization initiator are preferred. The above cationic polymerization initiator is a compound that generates cationic species by heat or active energy ray irradiation and initiates the curing reaction of curable compounds.

[0189] As the above cationic polymerization initiator, a photo cationic polymerization initiator (photoacid generator) and a thermal cationic polymerization initiator (thermal acid generator) can be cited.

[0190] As the above photo cationic polymerization initiator, a known or conventional photo cationic polymerization initiator can be used. For example, sulfonium salts (salts formed by sulfonium ions and anions), iodonium salts (salts formed by iodonium ions and anions), selenonium salts (salts formed by selenonium ions and anions), ammonium salts (salts formed by ammonium ions and anions), phosphonium salts (salts formed by phosphonium ions and anions), salts formed by transition metal complex ions and anions, etc. can be cited.

[0191] Examples of the above-mentioned sulfonium salts include: triarylsulfonium salts such as triphenylsulfonium salt, tri-p-tolylsulfonium salt, tri-o-tolylsulfonium salt, tris(4-methoxyphenyl)sulfonium salt, 1-naphthyldiphenylsulfonium salt, 2-naphthyldiphenylsulfonium salt, tris(4-fluorophenyl)sulfonium salt, tri-1-naphthylsulfonium salt, tri-2-naphthylsulfonium salt, tris(4-hydroxyphenyl)sulfonium salt, diphenyl[4-(phenylthio)phenyl]sulfonium salt, 4-(p-tolylthio)phenyl di-(p-phenyl)sulfonium salt; diarylsulfonium salts such as diphenylbenzoylmethylsulfonium salt, diphenyl 4-nitrobenzoylmethylsulfonium salt, diphenylbenzylsulfonium salt, diphenylmethylsulfonium salt; monoarylsulfonium salts such as phenylmethylbenzylsulfonium salt, 4-hydroxyphenylmethylbenzylsulfonium salt, 4-methoxyphenylmethylbenzylsulfonium salt; trialkylsulfonium salts such as dimethylbenzoylmethylsulfonium salt, benzoylmethyltetrahydrothiophenium salt, dimethylbenzylsulfonium salt, etc.

[0192] Examples of the above-mentioned diphenyl[4-(phenylthio)phenyl]sulfonium salt include: diphenyl[4-(phenylthio)phenyl]sulfonium tetrakis(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate, etc. In addition, commercially available products such as the trade name "CPI-100P" (manufactured by San-Apro Ltd., 50% propylene carbonate solution of diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate) can also be used.

[0193] Examples of the above-mentioned iodonium salts include the trade name "RHODORSIL PHOTOINITIATOR 2074" (manufactured by Rhodia Japan Ltd., tetrakis(pentafluorophenyl)borate = [(1-methylethyl)phenyl](methylphenyl)iodonium), the trade name "WPI-124" (manufactured by Wako Pure Chemical Industries, Ltd.), diphenyliodonium salt, di-p-tolyliodonium salt, bis(4-dodecylphenyl)iodonium salt, bis(4-methoxyphenyl)iodonium salt, etc.

[0194] Examples of the above-mentioned selenonium salts include: triarylselenonium salts such as triphenylselenonium salt, tri-p-tolylselenonium salt, tri-o-tolylselenonium salt, tris(4-methoxyphenyl)selenonium salt, 1-naphthyldiphenylselenium salt; diarylselenonium salts such as diphenylbenzoylmethylselenonium salt, diphenylbenzylselenonium salt, diphenylmethylselenonium salt; monoarylselenonium salts such as phenylmethylbenzylselenonium salt; trialkylselenonium salts such as dimethylbenzoylmethylselenium salt, etc.

[0195] As the above-mentioned ammonium salts, for example, the following can be cited: tetraalkylammonium salts such as tetramethylammonium salt, ethyltrimethylammonium salt, diethyldimethylammonium salt, triethylmethylammonium salt, tetraethylammonium salt, trimethyl-n-propylammonium salt, trimethyl-n-butylammonium salt; pyrrolonium salts such as N,N-dimethylpyrrolonium salt, N-ethyl-N-methylpyrrolonium salt; imidazolinium salts such as N,N'-dimethylimidazolinium salt, N,N'-diethylimidazolinium salt; tetrahydropyrimidinium salts such as N,N'-dimethyltetrahydropyrimidinium salt, N,N'-diethyltetrahydropyrimidinium salt; morpholinium salts such as N,N-dimethylmorpholinium salt, N,N-diethylmorpholinium salt; piperidinium salts such as N,N-dimethylpiperidinium salt, N,N-diethylpiperidinium salt; pyridinium salts such as N-methylpyridinium salt, N-ethylpyridinium salt; imidazolium salts such as N,N'-dimethylimidazolium salt; quinolinium salts such as N-methylquinolinium salt; isoquinolinium salts such as N-methylisoquinolinium salt; thiazolium salts such as benzylbenzothiazolium salt; acridinium salts such as benzylacridinium salt, etc.

[0196] As the above-mentioned phosphonium salts, for example, the following can be cited: tetraarylphosphonium salts such as tetraphenylphosphonium salt, tetrakis(p-tolyl)phosphonium salt, tetrakis(2-methoxyphenyl)phosphonium salt; triarylphosphonium salts such as triphenylbenzylphosphonium salt; tetraalkylphosphonium salts such as triethylbenzylphosphonium salt, tributylbenzylphosphonium salt, tetraethylphosphonium salt, tetrabutylphosphonium salt, triethylbenzoylmethylphosphonium salt, etc.

[0197] As the salts of the above-mentioned transition metal complex ions, for example, the following can be cited: salts of chromium complex cations such as (η 5 -cyclopentadienyl)(η 6 -toluene)Cr + and (η 5 -cyclopentadienyl)(η 6 -xylene)Cr + ; salts of iron complex cations such as (η 5 -cyclopentadienyl)(η 6 -toluene)Fe + and (η 5 -cyclopentadienyl)(η 6 -xylene)Fe + etc.

[0198] As the anions constituting the above-mentioned salts, for example, the following can be cited: PF6 - 、BF4 - 、(C6F5)4B - 、(C6F5)4Ga -, sulfonate anions (trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion, methanesulfonate anion, benzenesulfonate anion, p-toluenesulfonate anion, etc.), perhalate ions, halosulfonate ions, sulfate ions, carbonate ions, aluminate ions, carboxylate ions, arylborate ions, thiocyanate ions, nitrate ions, etc.

[0199] As the above-mentioned thermal cationic polymerization initiator, for example, the following can be cited: arylsulfonium salts, aryl iodonium salts, allene-ion complexes, quaternary ammonium salts, aluminum chelates, boron trifluoride amine complexes, etc. In addition, as the anion constituting the above-mentioned salt, the same anions as those in the photo cationic polymerization initiator can be cited.

[0200] As the above-mentioned arylsulfonium salts, for example, pentafluorophenyl borate, hexafluorophosphate, etc. can be cited. In the curable composition of the present disclosure, for example, commercially available products such as "SP-66", "SP-77" (manufactured by ADEKA Corporation); "San-Aid SI-150L", "San-Aid SI-110", "San-Aid SI-360", "San-Aid SI-300", "San-Aid SI-B4", "San-Aid SI-B5", "San-Aid SI-B3", "San-Aid SI-B3A", "San-Aid SI-B7", "San-Aid SI-B2A" (manufactured by Sanshin Chemical Industry Co., Ltd.) can be used. As the above-mentioned aluminum chelates, for example, ethyl acetoacetate aluminum diisopropyl, tris(ethylacetoacetato)aluminum, etc. can be cited. In addition, as the above-mentioned boron trifluoride amine complexes, for example, boron trifluoride monoethylamine complex, boron trifluoride imidazole complex, boron trifluoride piperidine complex, etc. can be cited.

[0201] The above-mentioned radical polymerization initiator is a compound that generates radicals by heat or active energy ray irradiation and initiates the curing reaction of the curable compound.

[0202] As the above-mentioned radical polymerization initiator, photo radical polymerization initiators and thermal radical polymerization initiators can be cited. As the above-mentioned photo radical polymerization initiators, for example, the following can be cited: alkyl phenyl ketone-based photo radical polymerization initiators, acylphosphine oxide-based photo radical polymerization initiators, oxime ester-based photo radical polymerization initiators, α-hydroxy ketone-based photo radical polymerization initiators, etc.

[0203] As the above-mentioned alkyl phenyl ketone-based photo radical polymerization initiators, for example, the following can be cited: 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-[4-(4-morpholinyl)phenyl]-1-butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, benzophenone, methylbenzophenone, o-benzoylbenzoic acid, benzoyl ethyl ether, 2,2-diethoxyacetophenone, 2,4-diethylthioxanthone, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl-(2,4,6-trimethylbenzoyl)phenyl phosphonate, 4,4'-bis(diethylamino)benzophenone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, oligomers of 2-hydroxy-1-(4-isopropenylphenyl)-2-methylpropan-1-one, etc.

[0204] As the above-mentioned acylphosphine oxide-based photo radical polymerization initiators, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, etc. can be cited.

[0205] As the above-mentioned oxime ester-based photo radical polymerization initiators, for example, 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxy), 1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone O-acetyl oxime, etc. can be cited.

[0206] As the above-mentioned α-hydroxy ketone-based photo radical polymerization initiators, for example, the following can be cited: benzoin, benzoin methyl ether, benzoin butyl ether, 1-hydroxycyclohexyl phenyl ketone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl phenyl ketone, etc.

[0207] The content (blending amount) of the above-mentioned curing catalyst in the above-mentioned curable composition is not particularly limited, and is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, and further preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the total amount of the curable compound. If the content of the curing catalyst is 0.01 part by mass or more, the curing reaction can be carried out effectively and sufficiently, and there is a tendency for the surface hardness of the hard coat to be further improved. On the other hand, if the content of the curing catalyst is 10 parts by mass or less, there is a tendency for the storage stability of the curable composition to be improved and the coloring of the cured product to be suppressed.

[0208] The content (mixing amount) of the cationic polymerization initiator in the above curable composition is not particularly limited. Relative to 100 parts by mass of the total amount of the curable compound, it is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, further preferably 0.15 to 3 parts by mass, and particularly preferably 0.2 to 2 parts by mass. If the above content is 0.05 parts by mass or more, the curing reaction can be effectively and sufficiently carried out, and there is a tendency for the surface hardness of the cured product to be further improved. If the above content is 10 parts by mass or less, there is a tendency for the storage stability of the curable composition to be improved and the coloring of the cured product to be suppressed.

[0209] The content (mixing amount) of the radical polymerization initiator in the above curable composition is not particularly limited. Relative to 100 parts by mass of the total amount of the curable compound, it is preferably 0.1 to 5 parts by mass, more preferably 0.3 to 3 parts by mass, further preferably 0.5 to 2 parts by mass. If the above content is 0.1 parts by mass or more, the curing reaction can be effectively and sufficiently carried out, and there is a tendency for the surface hardness of the cured product to be further improved. If the above content is 5 parts by mass or less, there is a tendency for the storage stability of the curable composition to be improved and the coloring of the cured product to be suppressed.

[0210] The above curable composition preferably contains a radical-curable polyorganosiloxane as a leveling agent. By using the above radical-curable polyorganosiloxane, the smoothness of the hard coat surface is improved, the sebum resistance is excellent, and fingerprints are not easily attached to the hard coat surface. In addition, the above active energy ray-curable polyorganosiloxane preferably does not belong to a compound equivalent to PFAS. In this case, while not belonging to a compound equivalent to PFAS, the above effects are exhibited. Since the above radical-curable polyorganosiloxane has radical curability, it also corresponds to the above curable compound. The above radical-curable polyorganosiloxane may be used alone or in combination of two or more.

[0211] The above radical-curable polyorganosiloxane has a radical polymerizable functional group in the molecule. As the above radical-curable functional group, a photo-radical polymerizable functional group can be cited.

[0212] As the above photo-radical polymerizable functional group, for example, (meth)acryloyl, (meth)acrylamide group, vinyl, vinylthio group, etc. can be cited. Among them, (meth)acryloyl is preferred.

[0213] As the polyorganosiloxane in the above radical-curable polyorganosiloxane, from the viewpoint of further exerting the effect as a leveling agent, linear polyorganosiloxane is preferred.

[0214] The content of the above-mentioned free radical curable polyorganosiloxane is not particularly limited. As the solid component, it is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and still more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the above-mentioned polyorganosilsesquioxane.

[0215] Preferably, the above-mentioned curable composition contains an antioxidant. By the above-mentioned curable composition containing an antioxidant, there is a tendency that the storage stability of the hard coat is further improved. As the above-mentioned antioxidant, only one kind can be used, or two or more kinds can be used.

[0216] As the antioxidant, known or conventional antioxidants can be used, and there is no particular limitation. For example, phenolic antioxidants, hindered amine antioxidants, phosphorus antioxidants, sulfur antioxidants, etc. can be mentioned.

[0217] As the above-mentioned phenolic antioxidant, for example, monophenols such as 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-tert-butyl-p-ethylphenol, stearyl-β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, etc.; bisphenols such as 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 3,9-bis[1,1-dimethyl-2-{β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl] 2,4,8,10-tetraoxaspiro[5.5]undecane, etc.; polymeric phenols such as 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tetra[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-tert-butylphenyl)butyric acid]ethylene glycol ester, 1,3,5-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)-s-triazine-2,4,6-(1H,3H,5H)trione, tocopherol, etc.

[0218] As the above-mentioned hindered amine antioxidant, for example, bis(1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl] malonate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, etc. can be mentioned.

[0219] Examples of the above-mentioned phosphorus-based antioxidants include: phosphite esters such as triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, cyclopentanetetraylbis(octadecyl) phosphite, cyclopentanetetraylbis(2,4-di-tert-butylphenyl) phosphite, cyclopentanetetraylbis(2,4-di-tert-butyl-4-methylphenyl) phosphite, and bis[2-tert-butyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl] hydrogen phosphite; oxaphosphaphenanthrene oxides such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 10-(3,5-di-tert-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, etc.

[0220] Examples of the above-mentioned sulfur-based antioxidants include: dodecyl mercaptan, dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, etc.

[0221] When the above curable composition contains an antioxidant, the content of the antioxidant is not particularly limited. Relative to the total amount (100 parts by mass) of the curable compound, it is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 1 part by mass. If the content of the antioxidant is 0.05 part by mass or more, sufficient stability can be achieved. In addition, if the content of the antioxidant is 5 parts by mass or less, coloring of the hard coat can be suppressed.

[0222] When the above curable composition contains an antioxidant, the content of the antioxidant is not particularly limited. Relative to 100 parts by mass of the polyorganosilsesquioxane, it is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass. If the content of the antioxidant is 0.05 part by mass or more, sufficient stability can be achieved. In addition, if the content of the antioxidant is 5 parts by mass or less, coloring of the hard coat can be suppressed.

[0223] The above curable composition may further contain a solvent. As the solvent, there is no particular limitation as long as it can dissolve the above polyorganosilsesquioxane and additives used as needed and does not hinder polymerization. The above solvent may be used alone or in combination of two or more.

[0224] Preferably, the above solvent is a solvent that can impart fluidity suitable for coating on a hard coat and can be easily removed by heating at a temperature capable of suppressing polymerization, and preferably a solvent having a boiling point (under one atmosphere) of 170 °C or lower (for example, aromatic solvents such as toluene, xylene, and mesitylene, esters such as butyl acetate, ketones such as methyl isobutyl ketone and cyclohexanone, ethers such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, etc.).

[0225] From the viewpoint of excellent coatability, preferably, the above solvent is used in the range of, for example, preferably 5 to 100% by mass, more preferably 10 to 80% by mass, and particularly preferably 20 to 70% by mass based on the non-volatile components contained in the curable composition. However, the addition amount should be selected and adjusted to the optimal addition amount that can achieve an appropriate film thickness viscosity, and is not limited to the above range. That is, if the amount of the solvent used is excessive, the viscosity of the curable composition decreases, and there is a tendency that it is difficult to form a coating film with an appropriate film thickness. On the other hand, if the amount of the solvent used is too small, the viscosity of the curable composition becomes too high, and there is a tendency that it is difficult to coat the substrate uniformly.

[0226] The above curable composition may further contain the following conventional additives as other components: precipitated silica, wet silica, fumed silica, calcined silica, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate, carbon black, silicon carbide, silicon nitride, boron nitride and other inorganic fillers, and inorganic fillers obtained by treating these fillers with organosilicon compounds such as organohalosilanes, organoalkoxysilanes, and organosilazanes; organic resin fine powders such as silicone resins, epoxy resins, and fluororesins; fillers such as conductive metal powders of silver, copper, etc., curing aids, stabilizers (light stabilizers, heat stabilizers, heavy metal passivators, etc.), ultraviolet absorbers (triazine-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, oxybenzophenone-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers), flame retardants (phosphorus-based flame retardants, halogen-based flame retardants, inorganic-based flame retardants, etc.), flame retardant aids, reinforcing materials (other fillers, etc.), nucleating agents, coupling agents (silane coupling agents, etc.), lubricants, waxes, plasticizers, mold release agents, impact resistance improvers, hue improvers, clarifying agents, rheology modifiers (flowability improvers, etc.), processability improvers, colorants (dyes, pigments, etc.), antistatic agents, dispersants, surface modifiers (slip agents, etc.), matting agents, defoaming agents, foam suppressants, degassing agents, antibacterial agents, preservatives, viscosity modifiers, tackifiers, photosensitizers, foaming agents, etc. The above other components may be used alone or in combination of two or more. The content of the above other components is not particularly limited, and is preferably 100 parts by mass or less, more preferably 30 parts by mass or less (for example, 0.01 to 30 parts by mass), and still more preferably 10 parts by mass or less (for example, 0.1 to 10 parts by mass) relative to 100 parts by mass of the total amount of the curable compound.

[0227] In addition, the above curable composition preferably does not contain compounds equivalent to PFAS. By having the above configuration, without using PFAS, it is possible to obtain a product compliant with PFAS restrictions.

[0228] The above curable composition is not particularly limited and can be prepared by stirring / mixing the above components at room temperature or while heating as needed. It should be noted that the above curable composition can be used as a one-component composition in which the components are pre-mixed and used directly, or can be used as a multi-component (for example, two-component) composition in which two or more components stored separately are mixed at a specified ratio before use.

[0229] The above-mentioned curable composition is not particularly limited, and is preferably a liquid at normal temperature (about 25°C). More specifically, regarding the above-mentioned curable composition, the viscosity of the liquid diluted to 20% with a solvent [in particular, a curable composition solution with a proportion of 20% by mass of methyl isobutyl ketone] at 25°C is preferably 300 to 20,000 mPa·s, more preferably 500 to 10,000 mPa·s, and further preferably 1,000 to 8,000 mPa·s. By setting the above viscosity to 300 mPa·s or more, the cured product (coating film) tends to be further improved. On the other hand, by setting the above viscosity to 20,000 mPa·s or less, the preparation and treatment of the curable composition become easy, and in addition, there is a tendency that air bubbles are not easily left in the cured product (coating film). It should be noted that the viscosity of the above-mentioned curable composition is measured using a viscometer (trade name "MCR301", manufactured by Anton Paar) under the conditions of a swing angle of 5%, a frequency of 0.1 to 100 (1 / s), and a temperature of 25°C.

[0230] As a method for manufacturing the above-mentioned hard coat, it can be manufactured according to a publicly known or conventional method for manufacturing a hard coat, and the manufacturing method is not particularly limited. For example, it can be manufactured by coating the above-mentioned curable composition on at least one surface of the above-mentioned substrate (the surface of the undercoat when the undercoat is formed), and removing the solvent by drying as needed, and then curing the above-mentioned curable composition (curable composition layer). The coating method of the curable composition and the conditions during curing are not particularly limited, and can be appropriately selected from the following conditions.

[0231] As a method for coating and curing the above-mentioned hard coat, a usual coating method can be used. Specifically, the same methods as the coating method of the above-mentioned undercoat can be cited. It should be noted that when ultraviolet rays are irradiated during the curing of the above-mentioned hard coat, for example, the cumulative irradiation amount is preferably about 1 to 5000 mJ / cm 2 or so.

[0232] As specific curing conditions, there is no particular limitation. For example, the above-mentioned curable composition can be first heat-treated (pre-baked) at preferably 60°C or higher, more preferably 120°C or higher, and further preferably 150°C or higher for preferably 10 seconds or more, more preferably 30 seconds or more, and further preferably 60 seconds or more. Then, ultraviolet rays are irradiated (irradiation conditions (irradiation amount): preferably 300 mJ / cm 2 or more; irradiation intensity: 100 mW / cm 2Thereafter, heat treatment (aging) is preferably carried out at 120°C or higher, preferably for 0.5 hours or more, to cure it. However, the curing conditions are not limited to this range, and the pre-baking temperature, time, aging temperature, and time can be appropriately selected according to the solvent used. In addition, the ultraviolet irradiation conditions can also be appropriately selected according to the curing agent used.

[0233] As described above, the above curable composition can form a hard coat having high surface hardness and toughness through coating and curing. The transparency laminate including the hard coat thus produced is excellent in bendability and bend durability, and at the same time, the surface hardness of the hard coat can be improved.

[0234] In order to further improve the recoatability of the above hard coat, surface treatments such as corona discharge treatment, plasma discharge treatment, ozone exposure treatment, and excimer treatment for surface modification by corona discharge irradiation can be performed on the surface of the above hard coat. Among them, corona discharge treatment is more preferable in terms of being able to easily improve the recoatability.

[0235] Corona discharge treatment is a treatment for processing the surface of the hard coat by generating an uneven electric field around a sharp electrode (needle electrode) and generating continuous discharge. Plasma discharge treatment is a treatment for processing the surface of the hard coat by discharging in the atmosphere to generate activated positive and negative charged particles. Ozone exposure treatment is, for example, a treatment for processing the surface of the hard coat by generating ozone by ultraviolet irradiation using a low-pressure mercury lamp or the like in the presence of oxygen. Excimer treatment is a treatment for processing the surface of the hard coat by ultraviolet irradiation or laser irradiation using an excimer lamp in a vacuum state.

[0236] The haze of the above hard coat is preferably 1% or less, more preferably 0.7% or less, and still more preferably 0.5% or less. It should be noted that the lower limit of the haze is, for example, 0.1%. By setting the haze to 1% or less, there is a tendency to be suitable for applications requiring high transparency.

[0237] The thickness of the above hard coat is preferably 5 to 100 μm, more preferably 10 to 70 μm. If the thickness of the hard coat is 5 μm or more, sufficient surface hardness can be exhibited. In addition, if the thickness of the hard coat is 100 μm or less, bendability is easily exhibited. In addition, when the above hard coat is formed on both sides of the above substrate, the thickness of at least one hard coat is preferably 5 μm or more, more preferably 10 μm or more. In addition, from the viewpoint of exhibiting bendability, the thicknesses of the two hard coats are each preferably 50 μm or less, more preferably 45 μm or less.

[0238] [Image display device]

[0239] As one embodiment of the present disclosure, an image display device including the above-described transparent laminate can be cited. In the image display device, the above-described transparent laminate is disposed, for example, such that the above-described hard coat forms the surface on the visible side. The above-described image display device is not particularly limited, and examples thereof include display devices such as an organic electroluminescence display device, an inorganic electroluminescence display device, and a liquid crystal display device. Since the surface of the above-described hard coat has sufficient surface hardness, the surface is not easily damaged and has excellent touch properties. In addition, since the above-described image display device has excellent flexibility and bending durability, it can also be used as a flexible display that can be wound or the like. Moreover, since it has sufficient surface hardness, flexibility, and bending durability, it can also be suitably used as a flexible device including the above-described image display device.

[0240] Each aspect disclosed in this specification can also be combined with any other feature disclosed in this specification. In addition, each configuration and the combination of each configuration in each embodiment are examples, and additional, omission, and other changes of the configuration can be appropriately made without departing from the gist of the present disclosure. The present disclosure is not limited by the embodiments but is limited only by the claims.

[0241] Examples

[0242] Hereinafter, one embodiment of the present disclosure will be described in more detail based on examples.

[0243] Production Example 1

[0244] (Production of polyorganosilsesquioxane)

[0245] Into a 1000-ml flask (reaction vessel) equipped with a thermometer, a stirring device, a reflux condenser, and a nitrogen inlet tube, 277.2 mmol (68.30 g) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3.0 mmol (0.56 g) of phenyltrimethoxysilane, and 275.4 g of acetone were charged under a nitrogen stream, and the temperature was raised to 50°C. To the mixture thus obtained, 7.74 g of a 5% aqueous potassium carbonate solution (2.8 mmol as potassium carbonate) was added over 5 minutes, and then 2800.0 mmol (50.40 g) of water was added over 20 minutes. It should be noted that no significant temperature rise occurred during the addition. Thereafter, the temperature was maintained at 50°C, and a polycondensation reaction was carried out for 5 hours under a nitrogen stream.

[0246] Thereafter, while cooling the reaction solution, 137.70 g of methyl isobutyl ketone and 100.60 g of 5% brine were added. The solution was transferred to a 1 L separatory funnel, and 137.70 g of methyl isobutyl ketone was added again for washing with water. After liquid separation, the aqueous layer was drawn off and washed with water until the lower layer became neutral. After separating the upper layer, the solvent was distilled off from the upper layer under the conditions of 1 mmHg and 50 °C to obtain 75.18 g of a colorless, transparent and liquid product (epoxy group-containing low molecular weight polyorganosilsesquioxane: silsesquioxane) containing 23% by mass of methyl isobutyl ketone.

[0247] It should be noted that the product was analyzed, and as a result, the number average molecular weight was 2235 and the molecular weight dispersity was 1.54. The ratio of T2 body to T3 body [T3 body / T2 body] calculated from the 29 Si-NMR spectrum of the above product was 11.9. The obtained epoxy group-containing low molecular weight polyorganosilsesquioxane was 1 confirmed by 29 H-NMR and

[0248] Si-NMR. 29 It should be noted that the molecular weight of the product was measured using a pump: Shimadzu LC-20AD, a detector: ShodexRI-504, columns: Shodex GPC KF-602, KF-603, a guard column: ShodexGPC KF-G, a solvent: THF, and measurement conditions: 40 °C. In addition, the ratio of T2 body to T3 body [T3 body / T2 body] in the product was measured by

[0249] (Preparation of hard coat agent)

[0250] Each material was mixed in the sesquioxane in such a way as to achieve the composition ratios shown in Table 1 to prepare a hard coat agent. It should be noted that the content ratios shown in Tables 1 to 7 are the blending ratios of each component, and the sesquioxane (active ingredient 77% by mass) and RS-57 (active ingredient 20% by mass)

[0251] are values for solutions, and the other components are values for active ingredients.

[0252] [Table 1]

[0253] Table 1

[0254]

[0255] Example 1

[0256] Using a wire-wound rod #5, coat the product name "CELV B0955" (manufactured by Daicel Corporation) onto chemically strengthened UTG (manufactured by Nippon Electric Glass Co., Ltd., thickness 90 μm) to a thickness of 5 μm as a primer. Then, using a high-pressure mercury lamp, irradiate ultraviolet rays at an illuminance of 300 mJ / cm 2 for curing. Next, respectively use a wire-wound rod #30 to apply the above-mentioned hard coat agent onto the above-mentioned primer to a cured thickness of 25 μm, and then place it in an oven at 80 °C for 1 minute and in an oven at 120 °C for 2 minutes. Then, use a high-pressure mercury lamp to irradiate ultraviolet rays at an illuminance of 300 mJ / cm 2 to form a hard coat. Then, place it in an oven at 120 °C for 60 minutes to produce the transparent laminate of Example 1.

[0257] Example 2

[0258] Using the hard coat agent with the composition ratio shown in Table 2, otherwise, produce the transparent laminate of Example 2 in the same manner as Example 1.

[0259] [Table 2]

[0260] Table 2

[0261]

[0262] Example 3

[0263] Using the hard coat liquid with the composition ratio shown in Table 3, otherwise, produce the transparent laminate of Example 3 in the same manner as Example 1.

[0264] [Table 3]

[0265] Table 3

[0266]

[0267] Example 4

[0268] Using the hard coat agent with the composition ratio shown in Table 4, otherwise, produce the transparent laminate of Example 4 in the same manner as Example 1.

[0269] [Table 4]

[0270] Table 4

[0271]

[0272] Example 5

[0273] Using the hard coat agent with the composition ratio shown in Table 5, otherwise, produce the transparent laminate of Example 5 in the same manner as Example 1.

[0274] [Table 5]

[0275] Table 5

[0276]

[0277] Comparative Example 1

[0278] A hard coat agent having the composition ratio shown in Table 6 was used, and in other respects, a transparent laminate of Comparative Example 1 was produced in the same manner as in Example 1.

[0279] [Table 6]

[0280] Table 6

[0281]

[0282]

[0283] Comparative Example 2

[0284] A hard coat agent having the composition ratio shown in Table 7 was used, and in other respects, a transparent laminate of Comparative Example 2 was produced in the same manner as in Example 1.

[0285] [Table 7]

[0286] Table 7

[0287]

[0288] Reference Example 1

[0289] The above-mentioned UTG monomer was used as Reference Example 1 for evaluation.

[0290] Each component used in Tables 1 to 7 will be described in detail below.

[0291] 200PA-E5: Trade name “EPOXYESTER 200PA-E5”, manufactured by Kyoeisha Chemical Co., Ltd. (a compound having one or more cationic polymerizable functional groups and one or more radical polymerizable functional groups in one molecule).

[0292] Epolight 1600N: Trade name “Epolight 1600N”, manufactured by Kyoeisha Chemical Co., Ltd. (an aliphatic compound having two or more cationic polymerizable groups), functional group equivalent of 1,6-hexanediol diglycidyl ether: 140 to 160, compound B with a short chain length.

[0293] Epolight 400E: The product name is "Epolight 400E", manufactured by Kyoeisha Chemical Co., Ltd. (an aliphatic compound having two or more cationic polymerizable groups in the molecule), the functional group equivalent containing nonaethylene glycol diglycidyl ether: 264 - 290, and compound B with a long chain.

[0294] Omnirad127: The product name is "Omnirad127", manufactured by IGM Resins B.V. (a radical polymerization initiator).

[0295] The salt of triarylsulfonium and tetrakis(pentafluorophenyl)gallium: A cationic polymerization initiator.

[0296] ADEKA STAB AO - 02: The product name is "ADEKA STAB AO - 02", manufactured by ADEKA Corporation (an antioxidant).

[0297] RS - 57: The product name is "RS - 57", a radical - curable polyorganosiloxane without a compound equivalent to PFAS, manufactured by DIC Corporation (a leveling agent).

[0298] MIBK: Methyl isobutyl ketone (a solvent).

[0299] MEK: Methyl ethyl ketone (a solvent).

[0300] [Evaluation]

[0301] The following evaluations were performed on the transparent laminates produced in the examples and comparative examples and the glass substrates in the reference examples, and the results are shown in Table 8.

[0302] (1) Micro - hardness measurement

[0303] For the hard - coat surfaces of the transparent laminates produced in the examples and comparative examples, using a nano - indentation instrument (product name "ENT - 2100", manufactured by ELIONIX Corporation) with a Berkovich indenter, 10 points were measured with a maximum load of 500 μN, and the average values of the indentation elastic modulus and indentation hardness were measured. In addition, the ratio of the indentation elastic modulus to the indentation hardness (indentation elastic modulus / indentation hardness) was calculated based on the average values of the above - mentioned indentation elastic modulus and indentation hardness.

[0304] (2) Pencil hardness

[0305] For the transparent laminates produced in the examples and comparative examples, the pencil hardness of the hard - coat surface was evaluated according to JIS K5600 - 5 - 4

[0306] (750 g load).

[0307] (3) Flexibility

[0308] For the transparent laminates produced in the Examples and Comparative Examples and the glass substrates in the Reference Examples, using a cylindrical mandrel bending tester (trade name "Bending Tester (Cylindrical Mandrel Method)", manufactured by TP Giken Co., Ltd.), the bendability was measured by the cylindrical mandrel method according to JIS K5600-5-1 (1999) with the hard coat on the inner side.

[0309] [Table 8]

[0310] Table 8

[0311]

[0312]

[0313] The pencil hardness of the transparent laminate of the Example is H or more, the minimum bendable radius when the hard coat side is recessed in the cylindrical mandrel test is 1.5 mm or less, and the ratio of the indentation elastic modulus to the indentation hardness in the microhardness measurement is 6.0 or more. Thus, a transparent laminate having high hardness and excellent bendability can be produced. On the other hand, it was confirmed that when the ratio of the indentation elastic modulus to the indentation hardness in the microhardness measurement is less than 6.0, the flexibility is poor (Comparative Example 1), or the surface hardness is insufficient (Comparative Example 2).

[0314] Hereinafter, modifications of the invention of the present disclosure will be described.

[0315] [Supplementary Note 1]

[0316] A transparent laminate having a substrate and a hard coat laminated on at least one surface of the substrate, wherein the pencil hardness of the surface of the hard coat under a 750 g load is H or more, the minimum bendable radius when the surface of the hard coat of the transparent laminate is recessed in a cylindrical mandrel test is 1.5 mm or less, and the ratio (indentation elastic modulus / indentation hardness) of the indentation elastic modulus to the indentation hardness in the microhardness test of the transparent laminate is 6.0 or more.

[0317] [Supplementary Note 2]

[0318] The transparent laminate according to Supplementary Note 1, wherein the haze of the hard coat is 1.0% or less.

[0319] [Supplementary Note 3]

[0320] The transparent laminate according to Supplementary Note 1 or 2, wherein the hard coat is a cured product of a curable composition containing one or more curable compounds, and the transparent laminate contains an aliphatic compound having two or more cationic polymerizable groups in the molecule as the curable compound.

[0321] [Supplementary Note 4]

[0322] The transparent laminate according to Note 3, wherein a polyorganosilsesquioxane is included as the curable compound.

[0323] [Note 5]

[0324] The transparent laminate according to Note 3 or 4, wherein two or more of the aliphatic compounds are included as the curable compound.

[0325] [Note 6]

[0326] The transparent laminate according to any one of Notes 3 to 5, wherein the curable composition further includes a curing catalyst.

[0327] [Note 7]

[0328] The transparent laminate according to Note 6, wherein the curing catalyst includes a cationic polymerization initiator.

[0329] [Note 8]

[0330] The transparent laminate according to Note 6 or 7, wherein the curing catalyst includes a radical polymerization initiator.

[0331] [Note 9]

[0332] The transparent laminate according to any one of Notes 1 to 8, wherein the hard coat does not contain a compound equivalent to PFAS.

[0333] [Note 10]

[0334] The transparent laminate according to any one of Notes 1 to 9, wherein a surface protective film is provided on at least one surface.

[0335] [Note 11]

[0336] The transparent laminate according to any one of Notes 1 to 10, wherein the hard coat is provided on one surface of the substrate and the adhesive layer is provided on the other surface.

[0337] [Note 12]

[0338] The transparent laminate according to any one of Notes 1 to 11, wherein the substrate is glass having a thickness of 30 to 100 μm.

[0339] [Note 13]

[0340] An image display device including the transparent laminate according to any one of Notes 1 to 12.

[0341] [Note 14]

[0342] The image display device according to Note 13, wherein the image display device is a flexible display.

[0343] [Note 15]

[0344] The image display device according to Note 13 or 14, wherein the image display device is an organic electroluminescent display device.

[0345] [Note 16]

[0346] A flexible device comprising the image display device according to any one of Notes 13 to 15.

Claims

1. A transparent laminate having a substrate and a hard coat laminated on at least one surface of the substrate, The pencil hardness of the surface of the hard coat under a 750 g load is H or higher, When performing a cylindrical mandrel test by denting the surface of the hard coat of the transparent laminate, the minimum bendable radius is 1.5 mm or less, In the microhardness test of the transparent laminate, the ratio of the indentation elastic modulus to the indentation hardness, i.e., indentation elastic modulus / indentation hardness, is 6.0 or higher.

2. The transparent laminate according to claim 1, wherein The haze of the hard coat is 1.0% or less.

3. The transparent laminate according to claim 1 or 2, wherein The hard coat is a cured product of a curable composition containing one or more curable compounds, The transparent laminate contains an aliphatic compound having two or more cationic polymerizable groups in the molecule as the curable compound.

4. The transparent laminate according to claim 3, wherein Contains polyorganosilsesquioxane as the curable compound.

5. The transparent laminate according to claim 3, wherein Contains two or more of the above aliphatic compounds as the curable compound.

6. The transparent laminate according to claim 3, wherein The curable composition further contains a curing catalyst.

7. The transparent laminate according to claim 6, wherein The curing catalyst contains a cationic polymerization initiator.

8. The transparent laminate according to claim 6, wherein The curing catalyst contains a radical polymerization initiator.

9. The transparent laminate according to claim 1 or 2, wherein The hard coat does not contain a compound equivalent to PFAS.

10. The transparent laminate according to claim 1 or 2, wherein Has a surface protective film on at least one surface.

11. The transparent laminate according to claim 1 or 2, wherein The hard coat is provided on one surface of the substrate, and an adhesive layer is provided on the other surface.

12. The transparent laminate according to claim 1 or 2, wherein The substrate is glass with a thickness of 30 to 100 μm.

13. An image display device comprising the transparent laminate according to claim 1 or 2.

14. The image display device according to claim 13, wherein The image display device is a flexible display.

15. The image display device according to claim 13, wherein The image display device is an organic electroluminescent display device.

16. A flexible device comprising the image display device according to claim 13.

Images