Laminate and image display device

Abstract

The purpose of the present invention is to provide a laminate having excellent surface hardness, impact resistance, and bending resistance. The laminate according to the present disclosure has a glass substrate and a hard coat layer laminated on at least one surface of the glass substrate, the thickness of the glass substrate is 1-100 m, the press-in hardness when the hard coat layer is used as the outermost surface is 850 N / mm2 or more, cracks are not generated when a pen is dropped from a height of 30 mm, and the thickness of the hard coat layer is 1-100 m. The minimum bending diameter of the hard coat layer is 10 mm [phi] or less when the hard coat layer is bent so that cracks do not occur.

Description

Technical Field

[0001] The present disclosure relates to a laminate and an image display device. This application claims priority from Japanese Patent Application No. 2023-010550, filed on January 26, 2023, the contents of which are incorporated herein by reference. Background Art

[0002] Glass used for displays of televisions, personal computers, smartphones, and the like is known to have a structure in which a hard coat layer is laminated on the surface for the purpose of preventing scratches and indentations while emphasizing transparency and aesthetics.

[0003] Furthermore, in the case of ultra-thin glass (UTG) used for flexible applications, since it is easily broken by impact, there is known an invention in which impact resistance is imparted to a hard coat layer (for example, Patent Document 1).

[0004] Prior art literature

[0005] Non-patent literature

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2022-44010 Summary of the Invention

[0007] Problems to be solved by the invention

[0008] However, conventional inventions including Patent Document 1 have a problem in that if the surface hardness of the hard coat layer is increased in order to exhibit impact resistance, the bending resistance is deteriorated.

[0009] Furthermore, when a soft impact-absorbing layer is provided to enhance impact resistance, there are problems such as insufficient surface hardness, which easily leads to scratches and indentations; and problems such as impaired contact properties, making it difficult to achieve a high level of balance among surface hardness, bending resistance, and impact resistance.

[0010] The present disclosure has been made to solve the above-mentioned technical problems, and an object thereof is to provide a laminate having excellent surface hardness, impact resistance, and bending resistance.

[0011] Solutions for solving problems

[0012] The inventors of the present disclosure have discovered that a laminate comprising a glass substrate and a hard coating layer laminated on at least one surface of the glass substrate, wherein the thickness of the glass substrate, its indentation hardness, and the minimum bending diameter at which cracks are not generated when the hard coating layer is bent inward are adjusted within certain ranges, can achieve excellent surface hardness, impact resistance, and bending resistance when a pen is dropped from a height of 30 mm. The present disclosure was completed based on these findings.

[0013] That is, the present disclosure provides a laminate comprising a glass substrate and a hard coating layer laminated on at least one surface of the glass substrate, wherein the thickness of the glass substrate is 1 to 100 μm, and the indentation hardness of the hard coating layer as the outermost surface is 850 N / mm. 2 The above-mentioned conditions ensure that the pen does not crack when dropped from a height of 30 mm, and the minimum bending diameter at which the pen does not crack when bent with the hard coating facing inward is 10 mmΦ or less.

[0014] The present disclosure can achieve excellent surface hardness, impact resistance, and bending resistance by having the above-mentioned configuration.

[0015] Preferably, the haze value of the laminate is 1% or less. By having the above-mentioned structure, the laminate has excellent transparency and can be applied to display devices.

[0016] Furthermore, it is preferred that the total light transmittance of the laminated body is 85% or more. By having the above-mentioned structure, the laminated body has excellent transparency and can be applied to display devices.

[0017] Preferably, the thickness of the hard coating layer is 25 μm or more. By having the above-mentioned structure, the laminated body can easily exhibit impact resistance and suppress the generation of cracks.

[0018] Preferably, the hard coat layer is a cured product of a curable composition containing one or more curable compounds, and at least one of the curable compounds is a polyorganosilsesquioxane.

[0019] Preferably, the minimum bending diameter at which the glass substrate does not crack when bent is 10 mmφ or less. With the above configuration, the laminate easily exhibits bending resistance.

[0020] Furthermore, the present disclosure provides a display device including the above-mentioned laminated body.

[0021] Effects of the Invention

[0022] The laminated body disclosed herein has excellent surface hardness, impact resistance, and bending resistance, and is therefore suitable for use in image display devices such as display equipment. DETAILED DESCRIPTION

[0023] In this specification, "(meth)acryloyl" refers to acryloyl and / or methacryloyl. "(meth)acrylate" refers to acrylate and / or methacrylate.

[0024] [Laminated body]

[0025] The laminated body disclosed herein comprises a glass substrate and a hard coating layer laminated on at least one surface of the glass substrate, wherein the thickness of the glass substrate is 1 to 100 μm and the indentation hardness of the hard coating layer as the outermost surface is 850 N / mm.2 As described above, the pen does not crack when dropped from a height of 30 mm, and the minimum bending diameter at which no crack occurs when bent with the hard coating layer facing inward is 10 mmφ or less.

[0026] The laminate may also include other layers in addition to the glass substrate and the hard coating layer. Examples of these other layers include a primer layer and an antireflection layer for bonding the glass substrate and the hard coating layer. These other layers may be formed on only one surface (single-sided) or on both surfaces (double-sided). Furthermore, when these other layers are formed on both sides of the glass substrate, they may be identical layers or layers of different thicknesses or compositions.

[0027] The minimum bending diameter at which cracks do not form when the laminate is bent with the hard coating layer facing inward, as measured using the cylindrical mandrel method according to JIS K5600-5-1, is 10 mmΦ or less, preferably 8 mmΦ or less, and more preferably 6 µmΦ or less. A minimum bending diameter of 10 mmΦ or less allows for excellent bending resistance. It should be noted that when hard coating layers of different thicknesses are formed on both sides of the laminate, measurements are made with the thicker hard coating layer facing inward.

[0028] The laminated body was formed with the hard coating layer on the outermost surface. The average value of the indentation load (indentation hardness) measured by adjusting the indentation load to 50 μN toward the hard coating layer was 850 N / mm. 2 Above, preferably 1000N / mm 2 More than 1200 N / mm 2 In addition, the upper limit is not particularly limited, but from the perspective of exerting bending resistance, it is preferably 5000 N / mm 2 Below, more preferably 3000N / mm 2 Below, more preferably 2000N / mm 2 Below. The hardness is 850N / mm by pressing 2 The above-mentioned surface hardness is sufficient, and the touch properties when used as a touch panel are excellent. It should be noted that when hard coatings are formed on both sides of the laminate, the indentation hardness is measured with the thicker hard coating as the outermost surface.

[0029] Furthermore, the laminated body exhibited no cracking in the impact resistance test (pencil drop test) described in the Examples below. Furthermore, preferably, the laminated body exhibited no cracking in the pen drop test even when a hard coating layer was formed on only one surface, while the other surface lacked a hard coating layer or the aforementioned other layers. It should be noted that when hard coating layers were formed on both surfaces of the laminated body, the impact resistance test was conducted using the thicker of the hard coating layers as the outermost surface.

[0030] The haze value of the laminate is preferably 1.0% or less, more preferably 0.8% or less, further preferably 0.6% or less, and particularly preferably 0.5% or less. A haze value of 1.0% or less makes it easier to ensure transparency.

[0031] The total light transmittance of the laminate is preferably 85% or higher, more preferably 88% or higher, and particularly preferably 91% or higher. A total light transmittance of 85% or higher makes it easier to ensure transparency.

[0032] The thickness of the laminate is preferably 26 to 250 µm, more preferably 30 to 200 µm, and particularly preferably 35 to 150 µm. A thickness of 26 µm or greater enhances impact resistance and suppresses cracking. Furthermore, a thickness of 250 µm or less enhances bending resistance.

[0033] <Glass substrate>

[0034] From the perspective of exhibiting bending resistance, the glass substrate has a minimum crack-free bending diameter, as measured by the cylindrical mandrel method according to JIS K5600-5-1, of preferably 10 mmΦ or less, more preferably 8 mmΦ or less, and particularly preferably 6 mmΦ or less. When the glass substrate has a crack-free minimum bending diameter of 10 mmΦ or less, the laminate can readily exhibit its bending resistance. Furthermore, from the perspective of exhibiting bending resistance, the glass substrate alone preferably has a crack-free minimum bending diameter smaller than the crack-free minimum bending diameter of the laminate.

[0035] The glass substrate can be chemically strengthened to improve strength against cracking when thinning the glass and to produce a durable panel. To achieve sufficient strength, it is preferably end-face treated. This treatment can be a single layer or multiple layers. Furthermore, to improve wear resistance, smoothness, and crack resistance, a treatment layer or coating can be formed on any surface.

[0036] The thickness of the glass substrate is preferably 1 to 100 µm, more preferably 5 to 80 µm, and particularly preferably 10 to 60 µm. A glass substrate thickness of 1 µm or greater facilitates sufficient strength as a substrate. Furthermore, a glass substrate thickness of 100 µm or less facilitates bending resistance.

[0037] <Hard Coating>

[0038] The laminate can be produced by forming the hard coating layer on the glass substrate. It should be noted that, even if the hard coating layer is formed on only one surface (single surface) of the glass substrate in the laminate, it preferably suppresses the generation of cracks in the laminate and has sufficient surface hardness. Furthermore, the hard coating layer may be formed on both surfaces (double surfaces) of the glass substrate. It should be noted that when the hard coating layer is formed on both surfaces of the glass substrate, the hard coating layers may be laminated with the same layer or with layers of different thickness and composition. Furthermore, the hard coating layer may be formed on one surface of the glass substrate and the other layer may be formed on the other surface. From the perspective of suppressing the generation of cracks, it is preferred that the hard coating layer be formed on at least one surface of the glass substrate and the hard coating layer or the other layer be formed on the other surface.

[0039] The hard coat layer is preferably a hard coat layer containing a curable resin. Examples of the curable resin include curable polyorganosilsesquioxane resins and curable acrylic resins. From the perspective of increasing surface hardness, a curable polyorganosilsesquioxane resin is preferred. Furthermore, the curable resin is preferably a cured product of a curable composition containing a curable compound. Specifically, the curable compound used to form the hard coat layer preferably contains a polyorganosilsesquioxane.

[0040] The polyorganosilsesquioxane preferably includes a polyorganosilsesquioxane having a structural unit represented by the following formula (1) (hereinafter sometimes referred to as the "polyorganosilsesquioxane of the present disclosure"). Specifically, the curable composition used to form the hard coat layer (hereinafter sometimes referred to as the "hard coat agent") preferably contains a polyorganosilsesquioxane having a structural unit represented by the following formula (1). As described later, the hard coat agent may also contain other components such as a curing agent and an antioxidant.

[0041] [Chemical Formula 1]

[0042]

[0043] [In formula (1), R 1 represents a group containing an active energy ray-curable functional group]

[0044] The polyorganosilsesquioxane disclosed herein is characterized by having a structural unit represented by the aforementioned formula (1). Furthermore, the polyorganosilsesquioxane disclosed herein preferably has a structural unit represented by the following formula (I) (sometimes referred to as a "T3 form") and a structural unit represented by the following formula (II) (sometimes referred to as a "T2 form"). Furthermore, the polyorganosilsesquioxane disclosed herein preferably has a structural unit represented by the following formula (2).

[0045] [Chemical Formula 2]

[0046]

[0047] [Chemical Formula 3]

[0048]

[0049] The structural unit shown in the above formula (1) is usually [RSiO 3 / 2 ] represents a silsesquioxane structural unit (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 the hydrolysis and condensation reaction of a corresponding hydrolyzable trifunctional silane compound (specifically, for example, a compound represented by formula (a) described below).

[0050] R in formula (1) 1 "" represents a group (monovalent group) containing an active energy ray-curable functional group. Specifically, the polyorganosilsesquioxane disclosed herein is a photocationically curable compound (photocationically polymerizable compound) or a photoradical curable compound (photoradical polymerizable compound) having at least an active energy ray-curable functional group in the molecule.

[0051] The "photocationically polymerizable functional group" in the group containing an active energy ray-curable functional group is not particularly limited as long as it is photocationically polymerizable. Examples thereof include epoxy groups, oxetane groups, vinyl ether groups, and vinylphenyl groups. The "photoradical polymerizable functional group" in the group containing an active energy ray-curable functional group is not particularly limited as long as it is photoradical polymerizable. Examples thereof include (meth)acryloyloxy groups, (meth)acrylamide groups, vinyl groups, and vinylthio groups. From the perspective of achieving a surface hardness (e.g., H or higher) of the cured product (coating film), epoxy groups and (meth)acryloyloxy groups are preferred, with epoxy groups being particularly preferred.

[0052] Examples of the group containing the epoxy group include known or commonly used groups having an oxirane ring, and are not particularly limited. From the viewpoint of the curability of the hard coat agent, the scratch resistance of the cured product (coating film), and the toughness, preferably, the group is represented by the following formula (1a), the group is represented by the following formula (1b), the group is represented by the following formula (1c), and the group is represented by the following formula (1d). More preferably, the group is represented by the following formula (1a) and the group is represented by the following formula (1c). Even more preferably, the group is represented by the following formula (1a).

[0053] [Chemical Formula 4]

[0054]

[0055] [Chemical Formula 5]

[0056]

[0057] [Chemical Formula 6]

[0058]

[0059] [Chemical Formula 7]

[0060]

[0061] In the above formula (1a), R 1a represents a linear or branched alkylene group. Examples of the linear or branched alkylene group include a linear or branched alkylene group having 1 to 10 carbon atoms, such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, and decamethylene. 1a From the viewpoint of the scratch resistance and toughness of the cured product (coating film), preferably, it is a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms, more preferably, it is an ethylene group, a trimethylene group, or a propylene group, and still more preferably, it is an ethylene group or a trimethylene group.

[0062] In the above formula (1b), R 1b represents a linear or branched alkylene group, and examples thereof include 1a The same group. 1b From the viewpoint of the scratch resistance and toughness of the cured product (coating film), preferably, it is a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms, more preferably, it is an ethylene group, a trimethylene group, or a propylene group, and still more preferably, it is an ethylene group or a trimethylene group.

[0063] In the above formula (1c), R 1c represents a linear or branched alkylene group, and examples thereof include 1aThe same group. 1c From the viewpoint of the scratch resistance and toughness of the cured product (coating film), preferably, it is a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms, more preferably, it is an ethylene group, a trimethylene group, or a propylene group, and still more preferably, it is an ethylene group or a trimethylene group.

[0064] In the above formula (1d), R 1d represents a linear or branched alkylene group, and examples thereof include 1a The same group. 1d From the viewpoint of the scratch resistance and toughness of the cured product (coating film), preferably, it is a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms, more preferably, it is an ethylene group, a trimethylene group, or a propylene group, and still more preferably, it is an ethylene group or a trimethylene group.

[0065] As R in formula (1) 1 From the viewpoint of the scratch resistance and toughness of the cured product (coating film), the above-mentioned formula (1a) and R 1a An ethylene group [among which, 2-(3',4'-epoxycyclohexyl)ethyl].

[0066] Examples of the oxetane group-containing group include, but are not particularly limited to, known or commonly used groups having an oxetane ring. Examples include oxetane itself and groups in which an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms) has a hydrogen atom (usually one or more, preferably one hydrogen atom) substituted with an oxetane group. From the perspective of the curability of the hard coat agent and the scratch resistance and toughness of the cured product (coating film), preferred groups include 3-oxetane, oxetane-3-ylmethyl, 3-ethyloxetane-3-ylmethyl, 2-(oxetane-3-yl)ethyl, 2-(3-ethyloxetane-3-yl)ethyl, 3-(oxetane-3-ylmethoxy)propyl, and 3-(3-ethyloxetane-3-ylmethoxy)propyl.

[0067] Examples of the group containing a vinyl ether group include, but are not particularly limited to, known or commonly used groups containing a vinyl ether group. Examples include a vinyl ether group itself and a group in which a hydrogen atom (usually one or more, preferably one hydrogen atom) of an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms) is substituted with a vinyl ether group. From the perspective of the curability of the hard coat agent and the scratch resistance and toughness of the cured product (coating film), preferred groups include vinyloxymethyl, 2-(vinyloxy)ethyl, and 3-(vinyloxy)propyl.

[0068] Examples of the vinylphenyl group-containing group include known or commonly used groups having a vinylphenyl group, without particular limitation. Examples include vinylphenyl itself and groups in which a hydrogen atom (usually one or more, preferably one hydrogen atom) of an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms) is substituted with a vinylphenyl group. From the perspective of the curability of the hard coat agent and the scratch resistance and toughness of the cured product (coating film), 4-vinylphenyl, 3-vinylphenyl, and 2-vinylphenyl are preferred.

[0069] Examples of the group containing a (meth)acryloyloxy group include, but are not particularly limited to, known or commonly used groups having a (meth)acryloyloxy group. Examples include a (meth)acryloyloxy group itself, and a group in which a hydrogen atom (usually one or more, preferably one hydrogen atom) of an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms) is substituted with a (meth)acryloyloxy group. From the perspective of curability of the hard coat agent (coating film), and the scratch resistance and toughness of the cured product (coating film), preferred groups include a 2-((meth)acryloyloxy)ethyl group and a 3-((meth)acryloyloxy)propyl group.

[0070] Examples of the group containing a (meth)acrylamide group include, but are not particularly limited to, known or commonly used groups containing a (meth)acrylamide group. Examples include a (meth)acrylamide group itself, and a group in which a hydrogen atom (usually one or more, preferably one hydrogen atom) of an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms) is substituted with a (meth)acrylamide group. From the perspective of the curability of the hard coat agent, the scratch resistance of the cured product (coating film), and the toughness, preferred groups include 2-((meth)acrylamide)ethyl and 3-((meth)acrylamide)propyl.

[0071] Examples of the vinyl group-containing group include known or commonly used groups having a vinyl group, without particular limitation. Examples include vinyl groups themselves and groups in which a hydrogen atom (usually one or more, preferably one hydrogen atom) of an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms) is substituted with a vinyl group. From the perspective of the curability of the hard coat agent and the scratch resistance and toughness of the cured product (coating film), vinyl groups, vinylmethyl groups, 2-vinylethyl groups, and 3-vinylpropyl groups are preferred.

[0072] Examples of the vinylthio group-containing group include, but are not particularly limited to, known or commonly used groups containing a vinylthio group. Examples include vinylthio groups themselves and groups in which a hydrogen atom (usually one or more, preferably one hydrogen atom) of an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms) is substituted with a vinylthio group. Preferred groups include vinylthiomethyl, 2-(vinylthio)ethyl, and 3-(vinylthio)propyl from the viewpoint of the curability of the hard coat agent and the scratch resistance and toughness of the cured product (coating film).

[0073] As R in formula (1) 1 From the viewpoint of the scratch resistance and toughness of the cured product (coating film), an epoxy group or a (meth)acryloyloxy group is preferred, and a group represented by the above formula (1a) and R 1a The ethylene group [among which, 2-(3',4'-epoxycyclohexyl)ethyl], 3-(acryloyloxy)propyl, and 3-(methacryloyloxy)propyl.

[0074] The polyorganosilsesquioxane disclosed herein 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).

[0075] The polyorganosilsesquioxane of the present disclosure may have, in addition to the structural unit represented by the above formula (1), a structural unit represented by the following formula (2) as a silsesquioxane structural unit [RSiO 3 / 2 ].

[0076] [Chemical Formula 8]

[0077]

[0078] The structural unit shown in the above formula (2) is usually [RSiO 3 / 2 ] is a silsesquioxane structural unit (T unit) represented by formula (2). That is, the structural unit represented by formula (2) is formed by the hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compound (specifically, for example, a compound represented by formula (b) described later).

[0079] 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, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group. Examples of the aryl group include phenyl, tolyl, and naphthyl. Examples of the aralkyl group include benzyl and phenethyl. Examples of the cycloalkyl group include cyclobutyl, cyclopentyl, and cyclohexyl. Examples of the alkyl group include linear or branched alkyl groups such as methyl, ethyl, propyl, n-butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, and isopentyl. Examples of the alkenyl group include linear or branched alkenyl groups such as vinyl, allyl, and isopropenyl.

[0080] Examples of the substituted aryl group, substituted aralkyl group, substituted cycloalkyl group, substituted alkyl group, and substituted alkenyl group include groups in which a portion or all of the hydrogen atoms or main chain skeletons of the aforementioned aryl group, aralkyl group, cycloalkyl group, alkyl group, and alkenyl group are substituted with at least one selected from the group consisting of an ether group, an ester group, a carbonyl group, a siloxane group, a halogen atom (such as a fluorine atom), an acryloyl group, a methacryloyl group, a mercapto group, an amino group, and a hydroxyl group.

[0081] Among them, as R 2 , preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, more preferably a substituted or unsubstituted aryl group, and further preferably a phenyl group.

[0082] The ratio of the above-mentioned silsesquioxane structural units (structural unit represented by formula (1) and structural unit represented by formula (2)) in the polyorganosilsesquioxane of the present disclosure can be appropriately adjusted according to the composition of the raw material (hydrolyzable trifunctional silane) used to form these structural units.

[0083] The polyorganosilsesquioxane of the present disclosure may further have at least one selected from the group consisting of the following siloxane structural units: silsesquioxane structural units other than the structural units represented by the above formula (1) and the structural units represented by the above formula (2); 3 / 2 ]、[R3SiO 1 / 2 ] (so-called M unit), [R2SiO 2 / 2 ] (so-called D unit) and [SiO 4 / 2 ] (so-called Q unit). It should be noted that examples of silsesquioxane structural units other than the structural unit represented by the above-mentioned formula (1) and the structural unit represented by the formula (2) include the structural unit represented by the following formula (3).

[0084] [Chemical Formula 9]

[0085]

[0086] When the polyorganosilsesquioxane of the present disclosure comprises a structural unit (T3 form) represented by formula (I) and a structural unit (T2 form) represented by formula (II), the ratio [T3 form / T2 form] is not particularly limited and can be appropriately selected from a range of 5 or greater (e.g., 5 or greater and 500 or less). The lower limit of the ratio [T3 form / T2 form] is preferably 20, more preferably 21, more preferably 23, and even more preferably 25. A ratio [T3 form / T2 form] of 5 or greater tends to improve the surface hardness, scratch resistance, and toughness of the cured product (coating film). On the other hand, the upper limit of the ratio [T3 form / T2 form] is preferably 500, more preferably 100, more preferably 50, and even more preferably 40. A ratio [T3 form / T2 form] of 500 or less improves compatibility with other components in the hard coat agent and suppresses viscosity, thereby facilitating handling and enabling easy application as a hard coat agent.

[0087] It should be noted that, if the structural unit represented by formula (I) is described in more detail, it is represented by the following formula (I'). Furthermore, if the structural unit represented by formula (II) is described in more detail, it is represented by the following formula (II'). The three oxygen atoms bonded to the silicon atom shown in the structure represented by formula (I') are each 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 formula (II') are each bonded to another silicon atom (a silicon atom not shown in formula (II')). In other words, both the T3 and T2 forms are structural units (T units) formed by the hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compounds.

[0088] [Chemical Formula 10]

[0089]

[0090] [Chemical Formula 11]

[0091]

[0092] R in the above formula (I) a (R in formula (I') a Likewise) and R in formula (II) b (R in formula (II') b Similarly) each represents a group containing an active energy ray-curable 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, a substituted or unsubstituted alkenyl group, or a hydrogen atom. aand R b As a specific example, R in the above formula (1) can be shown. 1 , R in the above formula (2) 2 It should be noted that R in formula (I) a and R in formula (II) b Each of the groups bonded to a silicon atom (groups other than an alkoxy group and a halogen atom; for example, R in formulas (a) to (c) described below) is derived from a hydrolyzable trifunctional silane compound used as a raw material of the polyorganosilsesquioxane of the present disclosure. 1 、R 2 , hydrogen atoms, etc.).

[0093] R in the above formula (II) c (R in formula (II') c Similarly) represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a linear or branched alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. R in formula (II) c The alkyl group in the alkyl group is usually derived from an alkoxy group (e.g., X described below) in a hydrolyzable silane compound used as a raw material for forming the polyorganosilsesquioxane of the present disclosure. 1 ~X 3 alkyl groups (e.g., alkoxy groups, etc.).

[0094] The above ratio [T3 form / T2 form] in the polyorganosilsesquioxane disclosed herein can be obtained, for example, by 29 It can be determined by Si-NMR spectrum measurement. 29 In the Si-NMR spectrum, the silicon atoms in the structural unit (T3 form) represented by the above formula (I) and the silicon atoms in the structural unit (T2 form) 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 ratio [T3 form / T2 form] can be obtained. Specifically, for example, in the polyorganosilsesquioxane of the present disclosure having the above formula (1) and R 1 In the case of a 2-(3',4'-epoxycyclohexyl)ethyl structural unit, the signal of the silicon atom in the structure represented by formula (I) (T3 form) appears at -64 to -70 ppm, and the signal of the silicon atom in the structure represented by formula (II) (T2 form) appears at -54 to -60 ppm. Therefore, in this case, the ratio [T3 form / T2 form] can be calculated by calculating the integrated ratio of the signal at -64 to -70 ppm (T3 form) to the signal at -54 to -60 ppm (T2 form). 1In the case of a group containing an active energy ray-curable functional group other than 2-(3′,4′-epoxycyclohexyl)ethyl, [T3 form / T2 form] can be determined in the same manner.

[0095] The polyorganosilsesquioxane disclosed herein 29 Si-NMR spectrum can be measured, for example, using the following apparatus and conditions.

[0096] Measuring apparatus: Trade name “JNM-ECA500NMR” (manufactured by JEOL Ltd.).

[0097] Solvent: deuterated chloroform.

[0098] Cumulative number of times: 1800 times.

[0099] Measurement temperature: 25℃.

[0100] When the ratio [T3 form / T2 form] of the polyorganosilsesquioxane disclosed herein is within the above range (e.g., 5 or more and 500 or less), it means that a certain amount of T2 form exists relative to the T3 form in the polyorganosilsesquioxane disclosed herein. Examples of such T2 form include the structural unit represented by the following formula (4), the structural unit represented by the following formula (5), and the structural unit represented by the following formula (6). In the following formula (4), R 1 and R in the following formula (5) 2 Respectively with R in the above formula (1) 1 and R in the above formula (2) 2 The same. R in the following formulas (4) to (6) c With R in formula (II) c Likewise, it represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0101] [Chemical Formula 12]

[0102]

[0103] [Chemical Formula 13]

[0104]

[0105] [Chemical Formula 14]

[0106]

[0107] The polyorganosilsesquioxane disclosed herein may have any of a cage type, an incomplete cage type, a ladder type, and a random type silsesquioxane structure, or may have a combination of two or more of these silsesquioxane structures.

[0108] When the polyorganosilsesquioxane of the present disclosure has a structural unit represented by formula (4), the ratio (total amount) of the structural unit represented by formula (1) and the structural unit represented by formula (4) relative to the total amount of siloxane structural units [total siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%) is not particularly limited, but is preferably 55 to 100 mol%, more preferably 65 to 100 mol%, and even more preferably 80 to 99 mol%. By setting the ratio to 55 mol% or greater, the curability of the hard coat agent is improved, and the scratch resistance and toughness of the cured product (coating film) are significantly improved. It should be noted that the ratio of each siloxane structural unit in the polyorganosilsesquioxane of the present disclosure can be calculated, for example, from the composition of the raw materials, NMR spectrum measurement, and the like.

[0109] The ratio (total amount) of the structural unit represented by the above formula (2) and the structural unit represented by the above formula (5) relative to the total amount of siloxane structural units (total siloxane structural units; total amount of M units, D units, T units, and Q units) (100 mol %) in the polyorganosilsesquioxane disclosed herein is not particularly limited, but is preferably 0 to 70 mol %, more preferably 0 to 60 mol %, further preferably 0 to 40 mol %, and particularly preferably 1 to 15 mol %. By setting the above ratio to 70 mol % or less, the ratio of the structural unit represented by the above formula (1) and the structural unit represented by the above formula (4) can be relatively increased, thereby tending to improve the curability of the hard coating agent and to increase the scratch resistance and toughness of the cured product (coating film).

[0110] The ratio (total amount) of the structural unit represented by formula (1), the structural unit represented by formula (2), the structural unit represented by formula (4), and the structural unit represented by formula (5) relative to the total amount of siloxane structural units (total siloxane structural units; total amount of M units, D units, T units, and Q units) in the polyorganosilsesquioxane of the present disclosure (100 mol %) is not particularly limited, but is preferably 60 to 100 mol %, more preferably 70 to 100 mol %, and even more preferably 80 to 100 mol %. When the ratio is 60 mol % or more, the scratch resistance and toughness of the cured product (coating film) tend to be higher.

[0111] The number average molecular weight (Mn) of the polyorganosilsesquioxane disclosed herein, as measured by gel permeation chromatography and in terms of standard polystyrene, is not particularly limited and can be appropriately selected from the range of 1,000 to 50,000, for example. The lower limit of the number average molecular weight is preferably 1,500, more preferably 1,800, and even more preferably 2,000. By setting the number average molecular weight to 1,000 or greater, the scratch resistance and toughness of the cured product (coating film) tend to be further improved. On the other hand, the upper limit of the number average molecular weight is preferably 50,000, more preferably 10,000, and even more preferably 8,000. By setting the number average molecular weight to 50,000 or less (e.g., 3,000 or less), compatibility with other components in the hard coat agent is improved, and the scratch resistance and toughness of the cured product (coating film) tend to be further improved.

[0112] The molecular weight dispersion (Mw / Mn) of the polyorganosilsesquioxane disclosed herein, as measured by gel permeation chromatography and in terms of standard polystyrene, is not particularly limited and can be appropriately selected from the range of 1.0 to 4.0. The lower limit of the molecular weight dispersion is preferably 1.0, more preferably 1.1, and even more preferably 1.2. By setting the molecular weight dispersion to 1.1 or greater, the hard coat agent tends to be more liquid, improving workability. On the other hand, the upper limit of the molecular weight dispersion is preferably 4.0, more preferably 3.0, and even more preferably 2.5. By setting the molecular weight dispersion to 4.0 or less, the scratch resistance and toughness of the cured product (coating film) tend to be higher.

[0113] It should be noted that the number average molecular weight and molecular weight dispersion of the polyorganosilsesquioxane disclosed herein can be measured using the following apparatus and conditions.

[0114] Measuring apparatus: Trade name “LC-20AD” (manufactured by Shimadzu Corporation).

[0115] Chromatographic columns: Shodex KF-801 × 2, KF-802, and KF-803 (manufactured by Showa Denko K.K.).

[0116] Measurement temperature: 40℃.

[0117] Eluent: THF, sample concentration: 0.1-0.2% by mass.

[0118] Flow rate: 1 mL / min.

[0119] Detector: UV-VIS detector (trade name “SPD-20A”, manufactured by Shimadzu Corporation).

[0120] Molecular weight: converted to standard polystyrene.

[0121] The temperature (T) at which the polyorganosilsesquioxane of the present invention loses 5% of its weight in air atmosphere isd5 ) is not particularly limited, but is preferably 330°C or higher (e.g., 330-450°C), more preferably 340°C or higher, and even more preferably 350°C or higher. A 5% weight loss temperature of 330°C or higher tends to further improve the scratch resistance and toughness of the cured product (coating film). In particular, by ensuring that the polyorganosilsesquioxane of the present disclosure has a ratio [T3 form / T2 form] of 5 to 500, a number average molecular weight of 1,000 to 50,000, and a molecular weight dispersion of 1.0 to 4.0, the 5% weight loss temperature can be controlled to 330°C or higher. The 5% weight loss temperature is the temperature at which 5% of the pre-heating weight is reduced when heated at a constant heating rate and serves as an indicator of heat resistance. This 5% weight loss temperature can be measured by TGA (thermogravimetric analysis) in an air atmosphere at a heating rate of 5°C / minute.

[0122] The polyorganosilsesquioxane disclosed herein can be produced by a known or customary method for producing polysiloxanes, without particular limitation. For example, it can be produced by hydrolyzing and condensing one or two or more hydrolyzable silane compounds. However, as the hydrolyzable silane compound, a hydrolyzable trifunctional silane compound (a compound represented by the following formula (a)) is required to form the structural unit represented by the above-mentioned formula (1).

[0123] More specifically, for example, the polyorganosilsesquioxane of the present disclosure can be produced by a method of hydrolyzing and condensing a compound represented by the following formula (a), and optionally a compound represented by the following formula (b), and a compound represented by the following formula (c). The compound represented by the following formula (a) is a hydrolyzable silane compound used to form the silsesquioxane structural unit (T unit) in the polyorganosilsesquioxane of the present disclosure.

[0124] [Chemical Formula 15]

[0125]

[0126] [Chemical Formula 16]

[0127]

[0128] [Chemical Formula 17]

[0129]

[0130] The compound represented by the above formula (a) is a compound that forms the structural unit represented by the formula (1) in the polyorganosilsesquioxane of the present disclosure. 1 Compared with R in the above formula (1) 1The same as , represents a group containing an active energy ray-curable functional group. That is, as R in formula (a) 1 , preferably a group represented by the above formula (1a), a group represented by the above formula (1b), a group represented by the above formula (1c), or a group represented by the above formula (1d), more preferably a group represented by the above formula (1a), or a group represented by the above formula (1c), further preferably a group represented by the above formula (1a), and particularly preferably a group represented by the above formula (1a) and R 1a is an ethylene group [in which 2-(3',4'-epoxycyclohexyl)ethyl] . In addition, as described above, as R in formula (a) 1 , 3-(acryloyloxy)propyl and 3-(methacryloyloxy)propyl are also preferred.

[0131] X in the above formula (a) 1 represents an alkoxy group or a halogen atom. 1 Examples of the alkoxy group in the group include alkoxy groups having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, and isobutoxy. 1 The halogen atom in X includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. 1 , preferably alkoxy, more preferably methoxy, ethoxy. 1 They can be the same or different.

[0132] The compound represented by the above formula (b) is a compound that forms the structural unit represented by the formula (2) in the polyorganosilsesquioxane of the present disclosure. 2 Compared with R in the above formula (2) 2 The same as R in formula (b) represents 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 substituted or unsubstituted alkenyl group. 2 , preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, more preferably a substituted or unsubstituted aryl group, and further preferably a phenyl group.

[0133] X in the above formula (b) 2 represents an alkoxy group or a halogen atom. 2 Specific examples of X include 1 Here, as an example, 2 , preferably alkoxy, more preferably methoxy, ethoxy. 2 They can be the same or different.

[0134] The compound represented by the above formula (c) is a compound that forms the structural unit represented by the formula (3) in the polyorganosilsesquioxane of the present disclosure. 3 represents an alkoxy group or a halogen atom. 3 Specific examples of X include 1 Here, as an example, 3 , preferably alkoxy, more preferably methoxy, ethoxy. 3 They can be the same or different.

[0135] As the hydrolyzable silane compound, a hydrolyzable silane compound other than the compounds represented by formulas (a) to (c) above may be used in combination. Examples thereof include hydrolyzable trifunctional silane compounds other than the compounds represented by formulas (a) to (c) above, hydrolyzable monofunctional silane compounds that form M units, hydrolyzable difunctional silane compounds that form D units, and hydrolyzable tetrafunctional silane compounds that form Q units.

[0136] The amount and composition of the hydrolyzable silane compound can be adjusted appropriately depending on the desired structure of the polyorganosilsesquioxane of the present disclosure. For example, the amount of the compound represented by formula (a) is not particularly limited, but is preferably 55 to 100 mol %, more preferably 65 to 100 mol %, and even more preferably 80 to 99 mol %, relative to the total amount of the hydrolyzable silane compound used (100 mol %).

[0137] The amount of the compound represented by formula (b) used is not particularly limited, but is preferably 0 to 70 mol %, more preferably 0 to 60 mol %, further preferably 0 to 40 mol %, and particularly preferably 1 to 15 mol %, relative to the total amount of the hydrolyzable silane compound used (100 mol %).

[0138] The ratio (total ratio) of the compound represented by formula (a) and the compound represented by formula (b) relative to the total amount (100 mol %) of the hydrolyzable silane compound used is not particularly limited, but is preferably 60 to 100 mol %, more preferably 70 to 100 mol %, and even more preferably 80 to 100 mol %.

[0139] When two or more hydrolyzable silane compounds are used in combination, the hydrolysis and condensation reactions of these hydrolyzable silane compounds may be performed simultaneously or sequentially. When the reactions are performed sequentially, the order of the reactions is not particularly limited.

[0140] The hydrolysis and condensation reactions of the hydrolyzable silane compound can be carried out in a single step or in two or more steps. For example, to efficiently produce the polyorganosilsesquioxane of the present disclosure having a [T3 form / T2 form] ratio of less than 20 and / or a number average molecular weight of less than 2500 (hereinafter sometimes referred to as a "low-molecular-weight polyorganosilsesquioxane"), it is preferred to carry out the hydrolysis and condensation reactions in a single step. Furthermore, to efficiently produce the polyorganosilsesquioxane of the present disclosure having a [T3 form / T2 form] ratio of 20 or greater and / or a number average molecular weight of 2500 or greater (hereinafter sometimes referred to as a "high-molecular-weight polyorganosilsesquioxane"), it is preferred to carry out the hydrolysis and condensation reactions in two or more steps (preferably two steps). Specifically, the low-molecular-weight polyorganosilsesquioxane is used as a starting material and subjected to the hydrolysis and condensation reactions in one or more steps. Hereinafter, a scheme is described in which a low molecular weight polyorganosilsesquioxane is obtained by performing a hydrolysis and condensation reaction of a hydrolyzable silane compound in a single step, and a high molecular weight polyorganosilsesquioxane is obtained by further performing a hydrolysis and condensation reaction on the low molecular weight polyorganosilsesquioxane. However, the method for producing polyorganosilsesquioxane of the present disclosure is not limited thereto.

[0141] When the hydrolysis and condensation reaction of the present disclosure is carried out in two stages, it is preferred that, in the first stage of the hydrolysis and condensation reaction, a low molecular weight polyorganosilsesquioxane having a ratio [T3 form / T2 form] of 5 or more and less than 20 and a number average molecular weight of 1000 or more and less than 2500 is obtained, and in the second stage, the low molecular weight polyorganosilsesquioxane is further subjected to a hydrolysis and condensation reaction to obtain a high molecular weight polyorganosilsesquioxane having a ratio [T3 form / T2 form] of 20 or more and 500 or less and a number average molecular weight of 2500 or more and 50,000 or less is obtained.

[0142] The hydrolysis and condensation reaction in the first stage can be carried out in the presence of a solvent or in the absence of a solvent. It is preferably carried out in the presence of a solvent. Examples of the above-mentioned solvent include: aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran, and dioxane; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, isopropyl acetate, and butyl acetate; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; nitriles such as acetonitrile, propionitrile, and benzonitrile; alcohols such as methanol, ethanol, isopropanol, and butanol. Among the above-mentioned solvents, ketones and ethers are preferred. It should be noted that the solvents may be used alone or in combination of two or more.

[0143] The amount of the solvent used in the first-stage hydrolysis and condensation reaction is not particularly limited and can be adjusted appropriately depending on the desired reaction time and the like within a range of 0 to 2000 parts by mass relative to 100 parts by mass of the total amount of the hydrolyzable silane compound.

[0144] The hydrolysis and condensation reaction of the first stage is preferably carried out in the presence of a catalyst and water. The catalyst may be an acid catalyst or a base catalyst, but in order to suppress the decomposition of active energy ray-curable functional groups such as epoxy groups, base catalysts are preferred. Examples of the acid catalyst include: inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid; phosphate esters; carboxylic acids such as acetic acid, formic acid, and trifluoroacetic acid; sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid; solid acids such as activated clay; Lewis acids such as ferric chloride, etc. Examples of the base catalyst include: hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; hydroxides of alkaline earth metals such as magnesium hydroxide, calcium hydroxide, and barium hydroxide; carbonates of alkali metals such as lithium carbonate, sodium carbonate, potassium carbonate, and cesium carbonate; carbonates of alkaline earth metals such as magnesium carbonate; bicarbonates of alkali metals such as lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, and cesium bicarbonate; organic acid salts of alkali metals such as lithium acetate, sodium acetate, potassium acetate, and cesium acetate (for example, acetic acid) salts); organic acid salts of alkaline earth metals such as magnesium acetate (e.g., acetates); alkali metal alkoxides such as lithium methoxide, sodium methoxide, sodium ethoxide, sodium isopropoxide, potassium ethoxide, and potassium tert-butoxide; alkali metal phenolates such as sodium phenoxide; amines (such as tertiary amines) such as triethylamine, N-methylpiperidine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and 1,5-diazabicyclo[4.3.0]non-5-ene; and nitrogen-containing aromatic heterocyclic compounds such as pyridine, 2,2'-bipyridine, and 1,10-phenanthroline. It should be noted that the catalyst may be used alone or in combination of two or more. Furthermore, the catalyst may be used dissolved or dispersed in water, a solvent, or the like.

[0145] The amount of the catalyst used in the first-stage hydrolysis and condensation reaction is not particularly limited and can be appropriately adjusted within the range of 0.002 to 0.200 mol per 1 mol of the total amount of the hydrolyzable silane compound.

[0146] The amount of water used in the first-stage hydrolysis and condensation reaction is not particularly limited and can be appropriately adjusted within the range of 0.5 to 20 mol relative to 1 mol of the total amount of the hydrolyzable silane compound.

[0147] The method for adding the water in the first-stage hydrolysis and condensation reaction is not particularly limited. The total amount of water used (total amount used) may be added all at once or in portions. When added in portions, the addition may be continuous or intermittent.

[0148] As for the reaction conditions for the first-stage hydrolysis and condensation reaction, it is particularly important to select reaction conditions such that the ratio [T3 form / T2 form] of the low molecular weight polyorganosilsesquioxane is 5 or greater and less than 20. The reaction temperature for the first-stage hydrolysis and condensation reaction is not particularly limited, but is preferably 40-100°C, more preferably 45-80°C. By controlling the reaction temperature within this range, the ratio [T3 form / T2 form] tends to be more efficiently controlled to 5 or greater and less than 20. Furthermore, the reaction time for the first-stage hydrolysis and condensation reaction is not particularly limited, but is preferably 0.1-10 hours, more preferably 1.5-8 hours. Furthermore, the first-stage hydrolysis and condensation reaction can be carried out under normal pressure, under increased pressure, or under reduced pressure. The atmosphere for the first-stage hydrolysis and condensation reaction is not particularly limited and can be, for example, an inert gas atmosphere such as nitrogen or argon, or in the presence of oxygen such as air, with an inert gas atmosphere being preferred.

[0149] The first-stage hydrolysis and condensation reaction can produce a low-molecular-weight polyorganosilsesquioxane. After the first-stage hydrolysis and condensation reaction, the catalyst is preferably neutralized to suppress decomposition of active energy-ray-curable functional groups, such as epoxy ring-opening. Furthermore, the low-molecular-weight polyorganosilsesquioxane can be isolated and purified by separation methods such as water washing, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or combinations thereof.

[0150] The low molecular weight polyorganosilsesquioxane obtained by the hydrolysis and condensation reaction in the first stage can be subjected to a second stage of hydrolysis and condensation reaction to produce a high molecular weight polyorganosilsesquioxane. The second stage of hydrolysis and condensation reaction can be carried out in the presence of a solvent or in the absence of a solvent. When the second stage of hydrolysis and condensation reaction is carried out in the presence of a solvent, the solvents listed in the first stage of hydrolysis and condensation reaction can be used. As the solvent for the second stage of hydrolysis and condensation reaction, the low molecular weight polyorganosilsesquioxane containing the reaction solvent, extraction solvent, etc. of the first stage of hydrolysis and condensation reaction can be used as it is, or a substance obtained by distilling off a portion of these solvents can be used. It should be noted that the solvents can be used alone or in combination of two or more.

[0151] When a solvent is used in the second-stage hydrolysis and condensation reaction, the amount used is not particularly limited and can be adjusted appropriately according to the desired reaction time, etc., within a range of 0 to 2000 parts by mass based on 100 parts by mass of the low-molecular-weight polyorganosilsesquioxane.

[0152] The hydrolysis and condensation reaction of the second stage is preferably carried out in the presence of a catalyst and water. The above-mentioned catalyst can use the catalysts listed in the hydrolysis and condensation reaction of the first stage. In order to suppress the decomposition of active energy ray-curable functional groups such as epoxy groups, it is preferably an alkali catalyst, more preferably an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, cesium hydroxide; Alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate. It should be noted that the catalyst can be used alone or in combination of two or more. In addition, the catalyst can also be used in a state where it is dissolved or dispersed in water, a solvent, etc.

[0153] The amount of the catalyst used in the second-stage hydrolysis and condensation reaction is not particularly limited and can be appropriately adjusted within the range of preferably 0.01 to 10,000 ppm, more preferably 0.1 to 1,000 ppm, relative to the low molecular weight polyorganosilsesquioxane (1,000,000 ppm).

[0154] The amount of water used in the second-stage hydrolysis and condensation reaction is not particularly limited and can be appropriately adjusted within a range of preferably 10 to 100,000 ppm, more preferably 100 to 20,000 ppm, relative to the low molecular weight polyorganosilsesquioxane (1,000,000 ppm). If the amount of water used exceeds 100,000 ppm, it may be difficult to control the ratio (T3 form / T2 form) and number average molecular weight of the high molecular weight polyorganosilsesquioxane within the specified range.

[0155] The method for adding the water in the second-stage hydrolysis and condensation reaction is not particularly limited. The total amount of water used (total amount used) may be added all at once or in portions. When added in portions, the addition may be continuous or intermittent.

[0156] As for the reaction conditions for the second-stage hydrolysis and condensation reaction, it is particularly important to select reaction conditions such that the ratio [T3 form / T2 form] in the high molecular weight polyorganosilsesquioxane is 20 to 500, and the number average molecular weight is 2,500 to 50,000. The reaction temperature for the second-stage hydrolysis and condensation reaction varies depending on the catalyst used and is not particularly limited, but is preferably 5 to 200°C, more preferably 30 to 100°C. By controlling the reaction temperature within the above range, there is a tendency to more efficiently control the ratio [T3 form / T2 form] and number average molecular weight within the desired range. In addition, the reaction time for the second-stage hydrolysis and condensation reaction is not particularly limited, but is preferably 0.5 to 1,000 hours, more preferably 1 to 500 hours. Furthermore, by carrying out the hydrolysis and condensation reactions within the above-mentioned reaction temperature range while sampling at appropriate times and monitoring the above-mentioned ratio [T3 form / T2 form] and number average molecular weight while carrying out the reaction, a high molecular weight polyorganosilsesquioxane having the desired ratio [T3 form / T2 form] and number average molecular weight can also be obtained.

[0157] The hydrolysis and condensation reaction in the second stage can be carried out under normal pressure, or under increased pressure or reduced pressure. It should be noted that the atmosphere during the hydrolysis and condensation reaction in the second stage is not particularly limited, and can be, for example, an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere; or an air atmosphere or the like in the presence of oxygen, preferably an inert gas atmosphere.

[0158] The high molecular weight polyorganosilsesquioxane can be obtained through the hydrolysis and condensation reaction in the second stage. After the hydrolysis and condensation reaction in the second stage is completed, the catalyst is preferably neutralized to suppress the decomposition of active energy radiation-curable functional groups such as epoxy ring opening. Furthermore, the high molecular weight polyorganosilsesquioxane can be isolated and purified by separation methods such as water washing, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or combinations thereof.

[0159] Since the polyorganosilsesquioxane of the present disclosure has the above-mentioned structure, a cured product (coating film) having excellent scratch resistance and toughness can be formed by applying and curing a hard coating agent containing the polyorganosilsesquioxane as an essential component.

[0160] In the hard coating agent, the polyorganosilsesquioxane disclosed in the present invention may be used alone or in combination of two or more.

[0161] The content (amount blended) of the polyorganosilsesquioxane disclosed herein in the hard coat agent is not particularly limited, but is preferably 70% to less than 100% by mass, more preferably 80 to 99.8% by mass, and even more preferably 90 to 99.5% by mass, relative to the total amount of the hard coat agent excluding the solvent (100% by mass). By setting the content of the polyorganosilsesquioxane disclosed herein to 70% by mass or greater, the scratch resistance and toughness of the cured product (coating film) tend to be further improved. On the other hand, by setting the content of the polyorganosilsesquioxane disclosed herein to less than 100% by mass, the hard coat agent can be incorporated with a curing agent, which tends to result in more efficient curing of the hard coat agent.

[0162] The ratio of the polyorganosilsesquioxane disclosed herein relative to the total amount (100% by mass) of the photocationically curable compound or photoradical curable compound contained in the hard coat agent is not particularly limited, but is preferably 70 to 100% by mass, more preferably 75 to 98% by mass, and even more preferably 80 to 95% by mass. By setting the content of the photocationically curable compound or photoradical curable compound to 70% by mass or greater, the abrasion resistance and toughness of the cured product (coating film) tend to be further improved.

[0163] The hard coat agent preferably further contains a curing agent to promote the curing reaction by irradiation with active energy rays. In particular, a photocationic polymerization initiator or a photoradical polymerization initiator is particularly preferred in order to further shorten the curing time until the coating becomes tack-free.

[0164] As the photocationic polymerization agent, the same ones as those disclosed for the photocurable composition can be used.

[0165] The photoradical polymerization initiator is a compound that can initiate or accelerate the photoradical polymerization reaction of a photoradical curable compound such as the polyorganosilsesquioxane disclosed herein.

[0166] Examples of the photoradical polymerization initiator include benzophenone, benzylacetophenone, benzyl dimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone, diphenyl disulfide, methyl o-benzoylbenzoate, ethyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2-methyl-1-[4-(methyl)phenyl]-2-morpholinopropanone-1, 1-hydroxycyclohexylphenyl ketone, 2-dimethylamino-2-(4-morpholino)benzoyl-1-phenylpropane, and 2-amino-2-benzoyl-2-propane. These include aminobenzene derivatives such as 1-phenylalkane compounds, tetrakis(tert-butylperoxycarbonyl)benzophenone, benzil, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, and 4,4'-bisdiethylaminobenzophenone; imidazole compounds such as 2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole; halomethylated triazine compounds such as 2,6-bis(trichloromethyl)-4-(4-methoxynaphthalen-1-yl)-1,3,5-triazine; and halomethylated oxadiazole compounds such as 2-trichloromethyl-5-(2-benzofuran-2-yl-vinyl)-1,3,4-oxadiazole. A photosensitizer may also be added as needed.

[0167] In addition, in the hard coating agent, the curing agent may be used alone or in combination of two or more.

[0168] The content (amount blended) of the curing agent in the hard coat agent is not particularly limited, but is preferably 0.01 to 10.0 parts by mass, more preferably 0.05 to 5.0 parts by mass, and even more preferably 0.1 to 3.0 parts by mass, relative to the total amount (100 parts by mass) of the polyorganosilsesquioxane disclosed herein and other active energy ray-curable compounds described below. A curing agent content of 0.01 parts by mass or greater allows for efficient and sufficient curing reactions, tending to further improve the scratch resistance and toughness of the cured product (coating film). On the other hand, a curing agent content of 5.0 parts by mass or less tends to further improve the shelf life of the hard coat agent and suppress coloration of the cured product (coating film).

[0169] The hard coat agent may further contain an active energy ray-curable compound other than the polyorganosilsesquioxane disclosed herein (sometimes referred to as "other active energy ray-curable compounds"). Examples of the other active energy ray-curable compounds include photocationic curable compounds other than the polyorganosilsesquioxane disclosed herein (sometimes referred to as "other photocationic curable compounds") and / or photoradical curable compounds other than the polyorganosilsesquioxane disclosed herein (sometimes referred to as "other photoradical curable compounds").

[0170] As other photocationically curable compounds, known or commonly used photocationically curable compounds can be used without particular limitation. Examples thereof include epoxy compounds other than the polyorganosilsesquioxane disclosed herein, oxetane compounds, and vinyl ether compounds. It should be noted that in the hard coat agent, the other photocationically curable compounds may be used alone or in combination of two or more.

[0171] Examples of the epoxy compound and the oxetane compound include the same compounds as those described for the photocurable composition.

[0172] As the vinyl ether compound, known or commonly used compounds having one or more vinyl ether groups in the molecule can be used without particular limitation. Examples thereof include 2-hydroxyethyl vinyl ether (ethylene glycol monovinyl ether), 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxyisobutyl vinyl ether, 2-hydroxyisobutyl vinyl ether, 1-methyl-3-hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl vinyl ether, 1-hydroxymethylpropyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, 1,6-hexanediol monovinyl ether, and the like. Vinyl ether, 1,6-hexanediol divinyl ether, 1,8-octanediol divinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, 1,4-cyclohexanedimethanol divinyl ether, 1,3-cyclohexanedimethanol divinyl ether, 1,3-cyclohexanedimethanol divinyl ether, 1,2-cyclohexanedimethanol divinyl ether, 1,2-cyclohexanedimethanol divinyl ether, p-xylene glycol monovinyl ether, p-xylene glycol divinyl ether, m-xylene glycol divinyl ether, m-xylene glycol divinyl ether, o-xylene glycol monovinyl ether, o-xylene glycol divinyl ether, ethylene glycol divinyl ether, diethylene glycol monovinyl ether, diethylene glycol Alcohol divinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether, tetraethylene glycol monovinyl ether, tetraethylene glycol divinyl ether, pentaethylene glycol monovinyl ether, pentaethylene glycol divinyl ether, oligoethylene glycol monovinyl ether, oligoethylene glycol divinyl ether, polyethylene glycol monovinyl ether, polyethylene glycol divinyl ether, dipropylene glycol monovinyl ether, dipropylene glycol divinyl ether, tripropylene glycol monovinyl ether, tripropylene glycol divinyl ether, tetrapropylene glycol monovinyl ether, tetrapropylene glycol divinyl ether, pentapropylene glycol monovinyl ether, pentapropylene glycol divinyl ether, oligopropylene glycol monovinyl ether, oligopropylene glycol divinyl ether, polypropylene glycol monovinyl ether, Polypropylene glycol divinyl ether, isosorbide divinyl ether, oxa-norbornene divinyl ether, phenyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octyl vinyl ether, cyclohexyl vinyl ether, hydroquinone divinyl ether, 1,4-butanediol divinyl ether, cyclohexanedimethanol divinyl ether, trimethylolpropane divinyl ether, trimethylolpropane trivinyl ether, bisphenol A divinyl ether, bisphenol F divinyl ether, hydroxyoxa-norbornene methanol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, etc.

[0173] In the above-mentioned hard coating agent, it is preferable to use an epoxy compound as another photocationically curable compound together with the polyorganosilsesquioxane disclosed herein.

[0174] As other photo-radical-curable compounds, known or customary photo-radical-curable compounds can be used without particular limitation. Examples include compounds other than the polyorganosilsesquioxane disclosed herein that have one or more photo-radical-polymerizable groups, such as (meth)acryloyl groups, (meth)acryloyloxy groups, (meth)acrylamido groups, vinyl ether groups, vinylaryl groups, and vinyloxycarbonyl groups, per molecule. It should be noted that in the hard coat agent, the other photo-radical-curable compounds may be used alone or in combination of two or more.

[0175] Examples of the compound having one or more (meth)acryloyl groups in one molecule include 1-butene-3-one, 1-pentene-3-one, 1-hexene-3-one, 4-phenyl-1-butene-3-one, 5-phenyl-1-pentene-3-one, and derivatives thereof.

[0176] Examples of the compound having one or more (meth)acryloyloxy groups in one molecule include monomers or oligomers having one or more (meth)acryloyloxy groups in one molecule.

[0177] Examples of monomers having one or more (meth)acryloyloxy groups in one molecule include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, n-lauryl (meth)acrylate, n-stearyl (meth)acrylate, n-butoxyethyl (meth)acrylate, butoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, and methoxypolyethylene glycol. (Meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, acrylic acid, methacrylic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxyethyl-2-hydroxy Propyl phthalate, glycidyl (meth)acrylate, 2-(meth)acryloyloxyethyl acid phosphate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, decane di(meth)acrylate, glycerol di(meth)acrylate, 2-(meth)acrylate Hydroxy-3-(meth)acryloyloxypropyl, dimethyloltricyclodecane di(meth)acrylate, trifluoroethyl(meth)acrylate, perfluorooctylethyl(meth)acrylate, isoamyl(meth)acrylate, isomyristyl(meth)acrylate, γ-(meth)acryloyloxypropyltrimethoxysilane, 2-(meth)acryloyloxyethyl isocyanate, 1,1-bis(acryloyloxy)ethyl isocyanate, 2-(2-(meth)acryloyloxyethyloxy)ethyl isocyanate, 3-(meth)acryloyloxypropyltriethoxysilane, and derivatives thereof.

[0178] Examples of the oligomer having one or more (meth)acryloyloxy groups in one molecule include urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyether (meth)acrylate oligomers, and polyester (meth)acrylate oligomers.

[0179] Examples of urethane (meth)acrylate oligomers include polycarbonate urethane (meth)acrylates, polyester urethane (meth)acrylates, polyether urethane (meth)acrylates, and caprolactone urethane (meth)acrylates. Urethane (meth)acrylate oligomers can be obtained by reacting an isocyanate compound obtained by reacting a polyol with a diisocyanate with a hydroxyl group-containing (meth)acrylate monomer. Examples of these polyols include polycarbonate diols, polyester polyols, polyether polyols, and polycaprolactone polyols.

[0180] Epoxy (meth)acrylate oligomers are obtained, for example, by an esterification reaction of an oxirane ring of a low-molecular-weight bisphenol epoxy resin or a novolac epoxy resin with acrylic acid.

[0181] The polyether (meth)acrylate oligomer is obtained by obtaining a polyether oligomer having hydroxyl groups at both terminals through a dehydration condensation reaction of a polyol, and then esterifying the hydroxyl groups at both terminals with acrylic acid.

[0182] A polyester (meth)acrylate oligomer is obtained, for example, by condensing a polycarboxylic acid and a polyol to obtain a polyester oligomer having hydroxyl groups at both terminals, and then esterifying the hydroxyl groups at both terminals with acrylic acid.

[0183] The weight average molecular weight of the oligomer having one or more (meth)acryloyloxy groups in one molecule is preferably 100,000 or less, particularly preferably 500 to 50,000.

[0184] Examples of the compound having one or more (meth)acryloylamino groups in one molecule include 4-(meth)acryloylmorpholine, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, N-n-butoxymethyl(meth)acrylamide, N-hexyl(meth)acrylamide, N-octyl(meth)acrylamide, and derivatives thereof.

[0185] Examples of the compound having one or more vinyl ether groups in one molecule include 3,3-bis(vinyloxymethyl)oxetane, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxyisobutyl vinyl ether, 2-hydroxyisobutyl vinyl ether, 1-methyl-3-hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl vinyl ether, 1-hydroxymethylpropyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, 1,6-hexanediol monovinyl ether, 1,4 - Cyclohexanedimethanol monovinyl ether, 1,3-cyclohexanedimethanol monovinyl ether, 1,2-cyclohexanedimethanol monovinyl ether, p-xylene glycol monovinyl ether, m-xylene glycol monovinyl ether, o-xylene glycol monovinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, pentaethylene glycol monovinyl ether, oligoethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, dipropylene glycol monovinyl ether, tripropylene glycol monovinyl ether, tetrapropylene glycol monovinyl ether, pentapropylene glycol monovinyl ether, oligopropylene glycol monovinyl ether, polypropylene glycol monovinyl ether, and derivatives thereof.

[0186] Examples of the compound having one or more vinyl aromatic groups in one molecule include styrene, divinylbenzene, methoxystyrene, ethoxystyrene, hydroxystyrene, vinylnaphthalene, vinylanthracene, 4-vinylphenyl acetate, (4-vinylphenyl)dihydroxyborane, N-(4-vinylphenyl)maleimide, and derivatives thereof.

[0187] Examples of the compound having one or more vinyloxycarbonyl groups in one molecule include isopropenyl formate, isopropenyl acetate, isopropenyl propionate, isopropenyl butyrate, isopropenyl isobutyrate, isopropenyl hexanoate, isopropenyl valerate, isopropenyl isovalerate, isopropenyl lactate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate, vinyl octanoate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl cyclohexanecarboxylate, vinyl pivalate, vinyl octanoate, vinyl monochloroacetate, divinyl adipate, vinyl acrylate, vinyl methacrylate, vinyl crotonate, vinyl sorbate, vinyl benzoate, vinyl cinnamate, and derivatives thereof.

[0188] In addition, in the said hard coating agent, other active energy ray-curable compounds may be used individually by 1 type, or may use 2 or more types together.

[0189] When the hard coat agent contains other active-energy-ray-curable compounds, their content (amount added) is not particularly limited. However, it is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, and even more preferably 7 to 30% by mass, relative to the total amount of the polyorganosilsesquioxane of the present disclosure and other active-energy-ray-curable compounds (100% by mass of the total amount of active-energy-ray-curable compounds). By setting the content of other active-energy-ray-curable compounds to 50% by mass or less, the abrasion resistance and toughness of the cured product (coating film) tend to be further improved. On the other hand, by setting the content of other active-energy-ray-curable compounds to 3% or more, desirable properties (such as rapid curing of the hard coat agent and viscosity adjustment) may be imparted to the hard coat agent and the cured product (coating film).

[0190] When the hard coat agent contains a vinyl ether compound (particularly a vinyl ether compound having one or more hydroxyl groups in its molecule), its content (amount added) is not particularly limited, but is preferably 0.01 to 10% by mass, more preferably 0.05 to 9% by mass, and even more preferably 1 to 8% by mass, relative to the total amount of the polyorganosilsesquioxane and other active energy ray-curable compounds disclosed herein (100% by mass of the total amount of active energy ray-curable compounds). Controlling the vinyl ether compound content within this range tends to further improve the surface hardness of the cured product (coating film), enabling the production of a cured product (coating film) with significantly higher surface hardness even with reduced exposure to active energy rays (e.g., ultraviolet rays). In particular, controlling the content of the vinyl ether compound having one or more hydroxyl groups in its molecule within this range tends to result in a particularly high surface hardness of the cured product (coating film).

[0191] The hard coating agent preferably contains an antioxidant. When the hard coating agent contains an antioxidant, the cured product (coating film) tends to be further improved.

[0192] As the antioxidant, known or commonly used antioxidants can be used without particular limitation, and examples thereof include phenolic antioxidants (phenolic compounds), hindered amine antioxidants (hindered amine compounds), phosphorus antioxidants (phosphorus compounds), and sulfur antioxidants (sulfur compounds).

[0193] Examples of the phenolic antioxidant include monophenols such as 2,6-di-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-tert-butyl-p-ethylphenol, and stearyl-β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate; 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'-butylenebis(3-methyl-6-tert-butylphenol), 3,9-bis[1,1-dimethyl-2-{β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl 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, tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-tert-butylphenyl)butyrate]ethylene glycol ester, 1,3,5-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)-s-triazine-2,4,6-(1H,3H,5H)trione, tocopherol and other high molecular weight phenols.

[0194] Examples of the hindered amine antioxidant include bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl-1,2,2,6,6-pentamethyl-4-piperidinyl sebacate, and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine.

[0195] Examples of the phosphorus-based antioxidant include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, diisodecyl pentaerythritol phosphite, tris(2,4-di-tert-butylphenyl) phosphite, cycloneopentanylate tetraylbis(octadecyl)phosphite, cycloneopentanylate tetraylbis(2,4-di-tert-butylphenyl)phosphite, cycloneopentanylate tetraylbis(2,4-di-tert-butylphenyl)phosphite, and cycloneopentanylate tetraylbis(octadecyl)phosphite. Phosphites such as 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;

[0196] Examples of the sulfur-based antioxidant include dodecanethiol, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, and distearyl-3,3'-thiodipropionate.

[0197] Among them, as antioxidants, phenolic antioxidants, phosphorus antioxidants, and sulfur antioxidants are preferred, and phenolic antioxidants are particularly preferred. It should be noted that in the hard coating agent, the antioxidants may be used alone or in combination of two or more.

[0198] When the hard coat agent contains an antioxidant, its content (amount added) is not particularly limited, but is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, relative to the total amount (100 parts by mass) of the active energy ray-curable compound contained in the hard coat agent. If the antioxidant content is less than 0.05 parts by mass, the cured product (coating film) may be insufficient. On the other hand, if the antioxidant content exceeds 5 parts by mass, the cured product (coating film) may be easily colored.

[0199] The hard coat agent preferably comprises a compound having one or more thermally polymerizable functional groups and one or more photopolymerizable functional groups within a single molecule (hereinafter sometimes referred to as "Compound A"). By including the polyorganosilsesquioxane disclosed herein and Compound A in the hard coat agent, the crosslinking density of the resulting cured product can be effectively increased, thereby easily imparting high surface hardness to the cured product (coating film).

[0200] The "thermally polymerizable functional group" possessed by compound A is not particularly limited as long as it is a functional group that imparts polymerizability to compound A by heat. Examples thereof include a hydroxyl group, an epoxy group, an oxetane group, and a vinyl ether group. From the perspective of the surface hardness of the coating film disclosed herein, a hydroxyl group and an epoxy group are preferred. It should be noted that when compound A has two or more thermally polymerizable functional groups, these thermally polymerizable functional groups may be the same or different.

[0201] The "photopolymerizable functional group" possessed by Compound A is not particularly limited as long as it is a functional group that imparts polymerizability to Compound A by light (e.g., ultraviolet light). Examples thereof include (meth)acryloyl groups and vinyl groups. From the perspective of the surface hardness of the coating film disclosed herein, a (meth)acryloyl group is preferred. It should be noted that when Compound A possesses two or more photopolymerizable functional groups, these photopolymerizable functional groups may be the same or different.

[0202] The number of thermally polymerizable functional groups possessed by Compound A in one molecule is not particularly limited, as long as it is one or more. For example, it is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2. Furthermore, the number of photopolymerizable functional groups possessed by Compound A in one molecule is not particularly limited, as long as it is one or more. For example, it is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2.

[0203] The functional group equivalent weight of the thermally polymerizable functional group of Compound A is not particularly limited, but is preferably 50 to 500, more preferably 80 to 480, and even more preferably 120 to 450. If the functional group equivalent weight is less than 50, the cured product (coating film) may be insufficient. On the other hand, if the functional group equivalent weight exceeds 500, the surface hardness of the cured product (coating film) may decrease. The functional group equivalent weight of the thermally polymerizable functional group of Compound A can be calculated using the following formula.

[0204] [Functional group equivalent weight of thermally polymerizable functional group] = [Molecular weight of compound A] / [Number of thermally polymerizable functional groups in compound A]

[0205] The functional group equivalent weight of the photopolymerizable functional group of Compound A is not particularly limited, but is preferably 50 to 500, more preferably 80 to 480, and even more preferably 120 to 450. If the functional group equivalent weight is less than 50, the cured product (coating film) may be insufficient. On the other hand, if the functional group equivalent weight exceeds 500, the surface hardness of the cured product (coating film) may decrease. The functional group equivalent weight of the photopolymerizable functional group of Compound A can be calculated using the following formula.

[0206] [Functional group equivalent weight of photopolymerizable functional group] = [Molecular weight of compound A] / [Number of photopolymerizable functional groups in compound A]

[0207] Specific examples of compound A include 3,4-epoxycyclohexylmethyl (meth)acrylate, glycidyl (meth)acrylate, tripropylene glycol diglycidyl ether di(meth)acrylate (a compound obtained by reacting (meth)acrylic acid with two epoxy groups of tripropylene glycol diglycidyl ether), tripropylene glycol diglycidyl ether half (meth)acrylate (a compound obtained by reacting (meth)acrylic acid with one epoxy group of tripropylene glycol diglycidyl ether), bisphenol A epoxy di(meth)acrylate (a compound obtained by reacting (meth)acrylic acid with two epoxy groups of bisphenol A diglycidyl ether), bisphenol A epoxy half (meth)acrylate (a compound obtained by reacting (meth)acrylic acid or a derivative thereof with one epoxy group of bisphenol A diglycidyl ether), bisphenol F epoxy di(meth)acrylate, bisphenol F epoxy half (meth)acrylate, bisphenol S epoxy di(meth)acrylate, and bisphenol S epoxy half (meth)acrylate. Compounds having an epoxy group and / or a hydroxyl group and a (meth)acryloyl group in one molecule, such as esters; compounds having an oxetanyl group and a (meth)acryloyl group in one molecule, such as 3-oxetanylmethyl (meth)acrylate, 3-methyl-3-oxetanylmethyl (meth)acrylate, 3-ethyl-3-oxetanylmethyl (meth)acrylate, 3-butyl-3-oxetanylmethyl (meth)acrylate, and 3-hexyl-3-oxetanylmethyl (meth)acrylate; 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate, 4-vinyloxybutyl (meth)acrylate, 1-methyl-3-vinyloxypropyl (meth)acrylate, 1-vinyloxymethylpropyl (meth)acrylate, 2-methyl-3-vinyloxypropyl (meth)acrylate, 1,1-Dimethyl-2-vinyloxyethyl (meth)acrylate, 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-vinyloxymethylphenylmethyl (meth)acrylate, m-vinyloxymethylphenylmethyl (meth)acrylate, o-vinyloxymethylphenylmethyl (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-(Vinyloxyisopropoxyethoxy)ethyl (meth)acrylate, 2-(Vinyloxyisopropoxyethoxy)ethyl (meth)acrylate, 2-(Vinyloxyisopropoxyethoxy)ethyl (meth)acrylate, (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-(vinyloxyisopropoxyethoxy)isopropyl (meth)acrylate, Compounds having a vinyl ether group and a (meth)acryloyl group in one molecule, such as 2-(vinyloxyethoxyethoxyethoxy)ethyl acrylate, 2-(vinyloxyethoxyethoxyethoxy)ethyl (meth)acrylate, 2-(isopropenyloxyethoxy)ethyl (meth)acrylate, 2-(isopropenyloxyethoxyethoxy)ethyl (meth)acrylate, 2-(isopropenyloxyethoxyethoxyethoxy)ethyl (meth)acrylate, 2-(isopropenyloxyethoxyethoxyethoxy)ethyl (meth)acrylate, polyethylene glycol monovinyl (meth)acrylate, and polypropylene glycol monovinyl (meth)acrylate.

[0208] From the viewpoint of the surface hardness of the cured product (coating film), compound A is preferably a compound having an epoxy group and / or a hydroxyl group as a thermally polymerizable functional group and a (meth)acryloyl group as a photopolymerizable functional group in one molecule. Specifically, 3,4-epoxycyclohexylmethyl (meth)acrylate, glycidyl (meth)acrylate, tripropylene glycol diglycidyl ether semi-(meth)acrylate, bisphenol A epoxy semi-(meth)acrylate, bisphenol F epoxy semi-(meth)acrylate, bisphenol S epoxy semi-(meth)acrylate, and the like are preferred.

[0209] It should be noted that in the hard coat agent, compound A may be used alone or in combination of two or more. Compound A can be produced by known methods, for example, by reacting a portion of the thermally polymerizable functional groups of a compound having two or more thermally polymerizable functional groups (e.g., epoxy groups or hydroxyl groups) within a molecule with a carboxylic acid having a photopolymerizable functional group (e.g., acrylic acid, methacrylic acid, etc.) or a derivative thereof.

[0210] The content (amount blended) of Compound A in the hard coat agent is not particularly limited. However, based on solid content, it is preferably 1.0 to 100 parts by mass, more preferably 1.3 to 75 parts by mass, and even more preferably 1.5 to 50 parts by mass, per 100 parts by mass of the total amount of the polyorganosilsesquioxane and other active energy ray-curable compounds disclosed herein (the total amount of active energy ray-curable compounds). A content of 1 part by mass or greater tends to further improve the quality of the cured product (coating film). On the other hand, a content of 100 parts by mass or less tends to maintain the surface hardness of the cured product (coating film).

[0211] The hard coat agent preferably contains a fluorinated photopolymerizable compound. A fluorinated photopolymerizable compound is a compound (monomer, oligomer, or polymer) containing a fluorinated group, such as a fluorinated aliphatic hydrocarbon backbone, and a photopolymerizable functional group within the molecule. By including the polyorganosilsesquioxane disclosed herein, compound A, and a fluorinated photopolymerizable compound in the hard coat agent, the following properties are achieved: The crosslink density of the coating film surface when the cured product is formed is effectively increased, the surface smoothness and other appearance of the cured product (coating film) are enhanced, and the surface hardness, scratch resistance, and antifouling properties are improved. The effects of the fluorinated photopolymerizable compound are particularly pronounced when incorporated into the hard coat agent along with compound A.

[0212] Examples of the photopolymerizable functional group possessed by the fluorinated photopolymerizable compound include the same functional groups as those possessed by the aforementioned "photopolymerizable functional group" of Compound A. From the perspective of the scratch resistance and antifouling properties of the coating film disclosed herein, a (meth)acryloyl group is preferred. It should be noted that when the fluorinated photopolymerizable compound possesses two or more photopolymerizable functional groups, these photopolymerizable functional groups may be the same or different.

[0213] The number of photopolymerizable functional groups contained in one molecule of the fluorine-containing photopolymerizable compound is not particularly limited as long as it is one or more, but is preferably 1 to 5, and more preferably 1 to 3.

[0214] The "fluorine-containing group" possessed by the above-mentioned fluorine-containing photopolymerizable compound is not particularly limited as long as it has a fluorine atom, and examples thereof include groups having a fluorinated aliphatic hydrocarbon skeleton. Examples of the fluorinated aliphatic hydrocarbon skeleton include fluorinated methane, fluorinated ethane, fluorinated propane, fluorinated isopropyl, fluorinated butyl, fluorinated isobutyl, fluorinated tert-butyl, fluorinated pentane, fluorinated hexane and the like. 1-10 Alkanes, etc.

[0215] These fluorinated aliphatic hydrocarbon skeletons may have at least a portion of hydrogen atoms substituted with fluorine atoms, but from the perspective of improving the scratch resistance, slip properties, and antifouling properties of the coating film, perfluorinated aliphatic hydrocarbon skeletons in which all hydrogen atoms are substituted with fluorine atoms are preferred.

[0216] Furthermore, the fluoroaliphatic hydrocarbon skeleton can also form a polyfluoroalkylene ether skeleton as a repeating unit connected via an ether bond. The fluoroaliphatic hydrocarbon group as a repeating unit can be selected from fluoromethylene, fluoroethylene, fluoropropylene, fluoroisopropylene and other fluoroC 1-4 At least one of the group consisting of an alkylene group. The number of repetitions (polymerization degree) of the polyfluoroalkylene ether unit is, for example, 10 to 3000, preferably 30 to 1000, and more preferably 50 to 500.

[0217] In addition to the above-mentioned "photopolymerizable functional group" and "fluorine-containing group", the above-mentioned fluorine-containing photopolymerizable compound may also have a silicone-containing group. When the fluorine-containing photopolymerizable compound further has a silicone-containing group, there is a tendency that the affinity with the polyorganosilsesquioxane disclosed in the present invention is improved, and the surface hardness, scratch resistance, and antifouling properties of the cured product (coating film) are further improved. The silicone-containing group is a group having a polyorganosiloxane skeleton, and any polyorganosiloxane formed by M units, D units, T units, and Q units may be used. Generally, polyorganosiloxane formed by D units is preferably used. As the organic group of the polyorganosiloxane, C 1-4Alkyl group, aryl group, generally methyl group, phenyl group (particularly methyl group). The number of repetitions (polymerization degree) of the siloxane unit is, for example, 2 to 3000, preferably 3 to 2000, and more preferably 5 to 1000.

[0218] These fluorine-containing photopolymerizable compounds may be used alone or in combination of two or more.

[0219] The content (amount blended) of the fluorinated photopolymerizable compound in the hard coat agent is not particularly limited, but is, based on solid content, for example, 0.01 to 15 parts by mass, preferably 0.02 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, and even more preferably 0.04 to 3 parts by mass, per 100 parts by mass of the total amount of the polyorganosilsesquioxane disclosed herein and other active energy ray-curable compounds (total amount of active energy ray-curable compounds). When the content of the fluorinated photopolymerizable compound is 0.01 parts by mass or greater, the scratch resistance and antifouling properties of the cured product (coating film) tend to be further improved.

[0220] The hard coating agent preferably contains a surface conditioner. As the surface conditioner, a known or commonly used compound added for the purpose of defoaming, leveling, or anti-foaming can be used.

[0221] As the defoaming agent, leveling agent, and anti-foaming agent, for example, aqueous or non-aqueous compounds containing as main components polymers such as butadiene, acrylic acid, and olefin, or containing as main components selected from silicone-based main components such as silicone and fluorinated silicone can be used.

[0222] The content (amount blended) of the surface conditioner in the hard coat agent is not particularly limited. Based on solid content, the content is, for example, 0.01 to 15 parts by mass, preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.2 to 3 parts by mass, relative to 100 parts by mass of the total amount of the polyorganosilsesquioxane disclosed herein and other active energy ray-curable compounds (total amount of active energy ray-curable compounds). A surface conditioner content of 0.01 parts by mass or greater tends to further improve the leveling properties of the cured product (coating film).

[0223] The hard coating agent may preferably further contain a solvent. The solvent is not particularly limited as long as it can dissolve the polyorganosilsesquioxane disclosed herein and additives used as needed and does not inhibit polymerization.

[0224] The solvent preferably has fluidity suitable for coating on the hard coat layer and can be easily removed by heating at a temperature that can inhibit the progress of polymerization. It is preferred to use one or more solvents having a boiling point (at 1 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).

[0225] To achieve excellent coating properties, the solvent is preferably used in an amount where the concentration of the non-volatile components in the hard coat agent is, for example, approximately 5 to 100% by mass, preferably 10 to 80% by mass, and particularly preferably 20 to 70% by mass. However, the amount added should be optimized to achieve a viscosity that achieves an appropriate film thickness and is not limited to the above range. In other words, if the amount of solvent used is excessive, the viscosity of the hard coat agent tends to be low, making it difficult to form a coating film of appropriate thickness. On the other hand, if the amount of solvent used is too low, the viscosity of the hard coat agent tends to be too high, making it difficult to evenly apply the hard coat agent to the glass substitute substrate.

[0226] The hard coating agent may further contain the following conventional additives as other optional components: inorganic fillers such as precipitated silica, wet silica, fumed silica, calcined silica, titanium oxide, aluminum oxide, glass, quartz, silicic acid, iron oxide, zinc oxide, calcium carbonate, carbon black, silicon carbide, silicon nitride, and boron nitride; inorganic fillers obtained by treating these fillers with organic silicon compounds such as organohalogenated silanes, organoalkoxysilanes, and organosilazanes; fine powders of organic resins such as silicone resins, epoxy resins, and fluororesins; fillers such as conductive metal powders such as silver and copper; curing aids; stabilizers (light stabilizers, heat stabilizers, heavy metal deactivators, etc.); ultraviolet absorbers (triazine-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers); The present invention also includes the following additives: UV absorbers (such as benzophenone-based UV absorbers, oxybenzophenone-based UV absorbers, salicylate-based UV absorbers, cyanoacrylate-based UV absorbers), flame retardants (phosphorus-based flame retardants, halogen-based flame retardants, inorganic flame retardants, etc.), flame retardant adjuvants, reinforcing materials (other fillers, etc.), nucleating agents, coupling agents (silane coupling agents, etc.), lubricants, waxes, plasticizers, release agents, impact modifiers, hue modifiers, transparentizing agents, rheology modifiers (flowability modifiers, etc.), processability modifiers, colorants (dyes, pigments, etc.), antistatic agents, dispersants, surface modifiers (slip agents, etc.), matting agents, defoaming agents, antifoaming agents, deaerators, antimicrobial agents, preservatives, viscosity modifiers, tackifiers, photosensitizers, foaming agents, etc. These additives may be used alone or in combination of two or more.

[0227] The hard coating agent is not particularly limited and can be prepared by stirring / mixing the aforementioned components at room temperature or, if necessary, by heating. The hard coating agent can be used as a single-liquid composition in which the components are premixed, or as a multi-liquid (e.g., two-liquid) composition in which two or more components, stored separately, are mixed at a predetermined ratio before use.

[0228] The hard coat agent is not particularly limited, but is preferably a liquid at room temperature (approximately 25°C). More specifically, the viscosity of the hard coat agent at 25°C as a liquid diluted to 20% solvent (particularly, a hard coat agent solution containing 20% by mass of methyl isobutyl ketone) is preferably 300 to 20,000 mPa·s, more preferably 500 to 10,000 mPa·s, and even more preferably 1,000 to 8,000 mPa·s. A viscosity of 300 mPa·s or higher tends to improve the quality of the cured product (coating film). On the other hand, a viscosity of 20,000 mPa·s or lower tends to facilitate preparation and handling of the hard coat agent and reduce the likelihood of bubbles remaining in the cured product (coating film). The viscosity of the hard coating agent was measured using a viscometer (trade name "MCR301", manufactured by Anton-Paar) at a swing angle of 5%, a frequency of 0.1 to 100 (1 / s), and a temperature of 25°C.

[0229] As a coating and curing method for the above-mentioned hard coating layer, a common coating method can be used. For example, well-known methods such as dipping, roller coating, gravure coating, reverse coating, air knife coating, comma coating, die coating, screen printing, spray coating, gravure offset printing, and organic vapor deposition can be used. As a curing method, for example, light irradiation using a mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, sunlight, an electron beam source, a laser light source, and an LED light source can be listed. It should be noted that when ultraviolet rays are irradiated during the curing of the above-mentioned hard coating layer, for example, the cumulative irradiation amount is preferably 1 to 5000 mJ / cm 2 about.

[0230] Specific curing conditions are not particularly limited. For example, the hard coating agent is first heat-treated (pre-baked) at preferably 60° C. or higher, more preferably 120° C. or higher, and even more preferably 150° C. or higher for preferably 10 seconds or longer, more preferably 30 seconds or longer, and even more preferably 60 seconds or longer, and then irradiated with ultraviolet rays (irradiation conditions (irradiation dose): preferably 300 mJ / cm 2 Above; irradiation intensity: 100mW / cm 2The pre-baking temperature and time, as well as the aging temperature and time, can be appropriately selected depending on the solvent used. Furthermore, the ultraviolet irradiation conditions can also be appropriately selected depending on the curing agent used.

[0231] As described above, the hard coating agent can form a hard coating layer having high scratch resistance, surface hardness, and toughness by coating and curing. The laminate thus produced has excellent adhesion and can increase the surface hardness of the hard coating layer.

[0232] The thickness of the hard coating layer is preferably 25 μm or more, more preferably 30 μm or more. When the thickness of the hard coating layer is 25 μm or more, impact resistance can be easily exerted and cracks caused by the pen drop test can be prevented. As an upper limit, there is no particular limitation, but it is preferably 70 μm or less, more preferably 60 μm or less. When the thickness of the hard coating layer is 70 μm or less, bending resistance can be easily exerted. In addition, when the hard coating layer is formed on both sides of the glass substrate, the thickness of at least one hard coating layer is preferably 25 μm or more, more preferably 30 μm or more. In addition, from the viewpoint of exerting bending resistance, the thicknesses of the two hard coating layers are preferably 70 μm or less, more preferably 60 μm or less.

[0233] [Display device]

[0234] As one embodiment of the present disclosure, a display device having the above-mentioned laminate can be listed. In the above-mentioned marking device, the above-mentioned laminate is configured, for example, so that the above-mentioned hard coating constitutes the surface of the visible side. The above-mentioned display device is not particularly limited, and examples thereof include organic EL display devices, inorganic EL display devices, liquid crystal display devices and other display devices. Since the surface of the above-mentioned hard coating layer has sufficient indentation hardness, the surface of the above-mentioned display device is not easily damaged and has excellent touchability. In addition, the above-mentioned display device can also be used as a flexible display that can be bent or rolled.

[0235] Each solution disclosed in this specification may be combined with any other feature disclosed in this specification. Furthermore, the various configurations and combinations thereof in the various embodiments are merely examples, and additions, omissions, substitutions, and other modifications to the configurations may be made as appropriate without departing from the spirit of this disclosure. This disclosure is not limited to the embodiments but only to the technical solutions.

[0236] Example

[0237] Hereinafter, one embodiment of the present disclosure will be described in more detail based on examples.

[0238] Production Example 1

[0239] (Manufacturing of polyorganosilsesquioxane)

[0240] A 1000 ml flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet was charged with 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 under a nitrogen stream. The temperature was then raised to 50°C. To the resulting mixture, 7.74 g (2.8 mmol as potassium carbonate) of a 5% aqueous solution was added over 5 minutes, followed by 2800.0 mmol (50.40 g) of water over 20 minutes. It should be noted that no significant temperature increase occurred during the additions. A polycondensation reaction was then carried out under a nitrogen stream, maintained at 50°C, for 5 hours.

[0241] While the reaction solution was cooling, 137.70 g of methyl isobutyl ketone and 100.60 g of 5% saline were added. The solution was transferred to a 1 L separatory funnel, and 137.70 g of methyl isobutyl ketone was added again, followed by water washing. After separation, the aqueous layer was withdrawn and washed with water until the lower layer became neutral. After the upper layer was separated, the solvent was distilled off from the upper layer at 1 mmHg and 50°C, yielding 75.18 g of a colorless, transparent liquid product (epoxy-containing low-molecular-weight polyorganosilsesquioxane: SQ1) containing 23% by mass of methyl isobutyl ketone.

[0242] It should be noted that the product was analyzed and the results showed that the number average molecular weight was 2235 and the molecular weight dispersion was 1.54. 29 The ratio of T2-to-T3-isomer [T3-isomer / T2-isomer] calculated from Si-NMR spectrum was 11.9. 1 H-NMR, 29 Confirmed by Si-NMR.

[0243] The molecular weight of the product was measured using a Shimadzu LC-20AD pump, a Shodex RI-504 detector, Shodex GPC KF-602 and KF-603 columns, a Shodex GPC KF-G guard column, THF as solvent, and measurement conditions at 40°C. Furthermore, the ratio of the T2-to-T3-isomer in the product [T3-to-T2-isomer] was measured using a JEOLECA500 (500 MHz) 29 Si-NMR spectrum measurement was performed.

[0244] (Preparation of Hard Coat)

[0245] The respective materials were mixed with the epoxy-containing low-molecular-weight polyorganosilsesquioxane (SQ1) at the constituent ratios shown in Table 1 to prepare a hard coating agent.

[0246] [Table 1]

[0247]

[0248] The components used in Table 1 are described in detail below.

[0249] 200PA-E5: Trade name “Epoxy Ester 200PA-E5”, manufactured by Kyoeisha Chemical Co., Ltd. (a compound having one or more thermally polymerizable functional groups and one or more photopolymerizable functional groups in one molecule).

[0250] Epolight 1600: Trade name “Epolight 1600”, manufactured by Kyoeisha Chemical Co., Ltd. (other photocationically curable compound).

[0251] Omnirad 127: Trade name “Omnirad 127”, manufactured by IGM Resins BV (photoradical polymerization initiator).

[0252] CPI-310FG: Trade name “CPI-310FG”, manufactured by San-Apro Co., Ltd. (photocationic polymerization initiator).

[0253] ADK STAB AO-02: Trade name “ADK STAB AO-02”, manufactured by ADEKA Corporation (antioxidant).

[0254] KY1203: Trade name “KY1203”, a compound having a radical polymerizable group and fluorine, manufactured by Shin-Etsu Chemical Co., Ltd. (surface conditioner).

[0255] FTERGENT 602A: Trade name "FTERGENT 602A," a fluorine-based surfactant having a free-radically polymerizable group and a branched fluorinated aliphatic hydrocarbon group, manufactured by Neos Corporation (leveling agent).

[0256] MIBK: Methyl isobutyl ketone (solvent).

[0257] MEK: Methyl Ethyl Ketone (solvent).

[0258] Examples 1-3, Comparative Examples 1-2

[0259] The hard coating agent was applied using wire rods #12, #24, #34, #44, and #60, respectively, to a thickness of 10µm, 20µm, 30µm, 40µm, and 55µm after curing on UTG (manufactured by SCHOTT, thickness 70µm, minimum bending diameter without cracking 4mmΦ). The hard coating agent was then placed in an oven at 80°C for 1 minute and then in an oven at 120°C for 2 minutes. Subsequently, a high-pressure mercury lamp was used to apply the hard coating agent at 300mJ / cm 2 The hard coating layer was formed by irradiating the film with ultraviolet light at an illumination of 1000 nm. Thereafter, the film was placed in an oven at 120° C. for 60 minutes to produce the laminates of Examples 1 to 3 and Comparative Examples 1 and 2.

[0260] Comparative Example 3

[0261] As Comparative Example 3, a sample in which a hard coating layer was not formed on the above-mentioned UTG was used.

[0262] [Table 2]

[0263]

[0264] Comparative Example 4

[0265] Instead of the hard coating agent, a hard coating liquid was prepared by mixing urethane acrylate (trade name "H-575", manufactured by Negami Industry Co., Ltd.), a radical polymerization initiator (trade name "Omnirad 184", manufactured by IGM Resins BV), and toluene as a solvent at the composition ratios listed in Table 2. The hard coating liquid was applied using a wire rod #44 to a thickness of 30µm after curing. The hard coating liquid was then placed in an oven at 120°C for 3 minutes. The hard coating liquid was then heated using a high-pressure mercury lamp at 500mJ / cm 2 The laminate of Comparative Example 4 was produced by irradiating with ultraviolet rays at an illumination of .

[0266] [evaluate]

[0267] The following evaluations were performed on the laminates produced in Examples and Comparative Examples, and the results are shown in Table 3.

[0268] (1) Bending resistance

[0269] The laminates of Examples 1 to 3 and Comparative Examples 1 to 4 were tested for bending resistance as follows using a cylindrical mandrel bending tester (trade name: "Bending Tester (Cylindrical Mandrel Method)", manufactured by TP Giken Co., Ltd.) using the cylindrical mandrel method in accordance with JIS K5600-5-1 (the tester was equipped with 12 replaceable mandrels having diameters of 2 mmΦ, 3 mmΦ, 4 mmΦ, 5 mmΦ, 6 mmΦ, 8 mmΦ, 10 mmΦ, 12 mmΦ, 16 mmΦ, 20 mmΦ, 25 mmΦ, and 32 mmΦ).

[0270] In a bending test using a cylindrical mandrel method, test pieces (15 mm x 150 mm) cut from the laminate were bent with the hard coating facing inward. The minimum bending diameter (mmΦ) at which cracks did not occur was determined. In this bending test, the laminate, as the test object, was bent 180° around a mandrel (a core rod of a specified diameter) with the hard coating facing inward relative to the glass substrate.

[0271] (2) Indentation hardness

[0272] The following test was conducted using an indentation hardness tester (trade name "ELONIX Inc. ENT-1100a", manufactured by ELIONIX). The laminates produced in Examples 1-3 and Comparative Examples 1-4 were cut into a size of approximately 4 mm x 4 mm, suitable for placement on a test bench. With the hard-coated surface facing the outermost surface, an instant adhesive (trade name "Aron Alpha Quick-Acting Multi-Purpose", manufactured by Toagosei Co., Ltd.) was applied and secured to the test stand. The indentation load was adjusted to 50 µN, and the average of the results from ten measurements was calculated as the indentation hardness (N / mm). 2 ).

[0273] (3) Impact resistance (pen drop test)

[0274] The laminates produced in Examples 1-3 and Comparative Examples 1-4 were placed on a 4 mm thick soda glass sheet, with the hard coating layer on the upper surface. A pen tip was dropped vertically onto the sample surface from the opposite side of the laminate to the soda glass, at a distance of 30 mm from the pen tip. Samples that developed cracks on the surface were deemed unacceptable, while those that did not were deemed acceptable. The pen used was a BIC ballpoint pen model E-ORMJ20EGBLK (13.7 mm in size, 5.7 g in weight, 1.0 mm in diameter).

[0275] (4) Haze

[0276] The haze value (%) of each laminate of Examples 1 to 3 and Comparative Examples 1 to 4 was measured using a haze meter (trade name "NDH-5000W", manufactured by Nippon Denshoku Industries, Ltd.) This measurement was performed in accordance with JIS K7136.

[0277] (5) Total light transmittance

[0278] The total light transmittance (%) of each laminate of Examples 1 to 3 and Comparative Examples 1 to 4 was measured using a total light transmittance measuring apparatus (trade name "NDH-5000W", manufactured by Nippon Denshoku Industries, Ltd.) This measurement was performed in accordance with JIS K7105.

[0279] [Table 3]

[0280]

[0281] It was confirmed that the minimum bending diameter without cracking in the mandrel test of the laminated bodies of Examples 1 to 3 was 10 mmΦ or less, and the indentation strength was 850 N / mm 2 As described above, the laminated bodies did not crack in the pen drop test and were excellent in impact resistance, surface hardness, and bending resistance. On the other hand, the laminated bodies of Comparative Examples 1 to 3 cracked in the pen drop test and had poor impact resistance. The laminated body of Comparative Example 4 had an indentation hardness of less than 850 N / mm. 2 , cracks occurred in the pen drop test, and the impact resistance and surface hardness were poor.

[0282] Modifications of the disclosed invention will be described below.

[0283] [Note 1]

[0284] A laminate comprising a glass substrate and a hard coating layer laminated on at least one surface of the glass substrate, wherein the thickness of the glass substrate is 1 to 100 μm and the indentation hardness of the hard coating layer as the outermost surface is 850 N / mm 2 As described above, the pen does not crack when dropped from a height of 30 mm, and the minimum bending diameter without cracking when bent with the hard coating layer facing inward is 10 mmφ or less.

[0285] [Note 2]

[0286] The laminate according to Supplementary Note 1, wherein the laminate has a haze value of 1% or less.

[0287] [Note 3]

[0288] The laminate according to Supplementary Note 1 or 2, wherein the total light transmittance of the laminate is 85% or more.

[0289] [Note 4]

[0290] The laminate according to any one of Supplementary Notes 1 to 3, wherein the hard coat layer has a thickness of 25 µm or more.

[0291] [Note 5]

[0292] The laminate according to any one of Appendixes 1 to 4, wherein the hard coat layer is a cured product of a curable composition containing one or more curable compounds, and at least one of the curable compounds is a polyorganosilsesquioxane.

[0293] [Note 6]

[0294] The laminate according to any one of Supplementary Notes 1 to 5, wherein a minimum bending diameter at which cracks are not generated when the glass substrate is bent is 10 mmφ or less.

[0295] [Note 7]

[0296] An image display device comprising the laminate according to any one of Supplementary Notes 1 to 6.

Claims

1. A laminate comprising a glass substrate and a hard coating layer laminated on at least one surface of the glass substrate, The thickness of the glass substrate is 1 to 100 μm. The indentation hardness when the hard coating layer is the outermost surface is 850 N / mm 2 above, The pen will not crack when dropped from a height of 30mm. The minimum bending diameter at which cracks are not generated when the hard coating layer is bent with the hard coating layer facing inward is 10 mmφ or less.

2. The laminate according to claim 1, wherein The haze value of the laminate is 1% or less.

3. The laminate according to claim 1 or 2, wherein The total light transmittance of the laminate is 85% or higher.

4. The laminate according to claim 1 or 2, wherein The thickness of the hard coating layer is greater than 25 μm.

5. The laminate according to claim 1 or 2, wherein The hard coat layer is a cured product of a curable composition containing one or more curable compounds, and at least one of the curable compounds is a polyorganosilsesquioxane.

6. The laminate according to claim 1 or 2, wherein The minimum bending diameter at which the glass substrate does not crack when bent is 10 mmφ or less. 7 . An image display device comprising the laminate according to claim 1 .

Images