Method for producing hard-coat-layer-attached laminate, and hard-coat-layer-attached laminate

Abstract

The present invention relates to a method for producing a laminate with a hard coat layer, the method comprising, in this order, a primer coating step for coating a primer containing a silane coupling agent on a substrate; a drying step for drying the primer to form an undercoat layer; a hard coating agent application step in which a hard coating agent containing a silsesquioxane derivative is applied to the undercoat layer; and a curing step of curing the hard coating agent to form a hard coating layer. And a laminate with a hard coat layer, the laminate having, in this order, a base material; an undercoat layer containing a cured product of a silane coupling agent; and a hard coating layer containing a cured product of a hard coating agent containing a silsesquioxane derivative.

Description

Technical Field

[0001] The present disclosure relates to a method for manufacturing a laminate with a hard coat and a laminate with a hard coat. Background Art

[0002] In order to impart functionality to substrates such as glass substrates and resin substrates, a hard coat is sometimes formed using a hard coat agent. Polyfunctional acrylates are widely used in hard coat agents.

[0003] For example, in Patent Document 1, in a method for manufacturing a base for an optical recording medium by providing a cured resin guide groove and a preformat signal on a glass substrate using a 2P method, it is characterized in that, before providing the cured resin guide groove and the preformat signal on the glass substrate, the surface of the glass substrate is subjected to UV / O₃ cleaning and / or plasma cleaning, and then a silane coupling agent treatment is carried out.

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: Japanese Patent Laid-Open No. 10-030068 Summary of the Invention

[0007] Problems to be Solved by the Invention

[0008] Conventionally, the hard coat preferably provided on a substrate has a high hardness. In particular, in recent years, the hardness requirement for the hard coat has been further increased. In particular, it is required to further increase the hardness of a hard coat using a silsesquioxane derivative that has attracted attention as an organic-inorganic hybrid material.

[0009] Therefore, the subject of the present disclosure is to provide a method for manufacturing a laminate with a hard coat and a laminate with a hard coat that uses a silsesquioxane derivative to obtain a hard coat having high hardness.

[0010] Means for Solving the Problems

[0011] The means for solving the above problems include the following methods.

[0012] <1>

[0013] A method for manufacturing a laminate with a hard coat, which is a method for manufacturing a laminate with a hard coat having a substrate, a primer coat, and a hard coat in this order, and which sequentially includes: a primer coating step of coating a primer containing a silane coupling agent on the substrate; a drying step of drying the primer to form the primer coat; a hard coat agent coating step of coating a hard coat agent containing a silsesquioxane derivative on the primer coat; and a curing step of curing the hard coat agent to form a hard coat.

[0014] <2>

[0015] <1> The method for manufacturing the laminated body with a hard coat, wherein the pencil hardness of the surface of the hard coat in the laminated body with a hard coat measured according to JIS K5600-5-4 (1999) is 5H or more.

[0016] <3>

[0017] <1> or <2> The method for manufacturing the laminated body with a hard coat, wherein the substrate is a glass substrate.

[0018] <4>

[0019] The method for manufacturing the laminated body with a hard coat according to any one of <1> to <3>, wherein the substrate is a glass substrate specified in JIS R3202:2011, and when the thickness of the hard coat is 5 μm or less, the pencil hardness of the surface of the hard coat in the laminated body with a hard coat is 7H or more.

[0020] <5>

[0021] The method for manufacturing the laminated body with a hard coat according to any one of <1> to <4>, wherein the silsesquioxane derivative is the silsesquioxane derivative represented by the following formula (1).

[0022]

[0023] (In formula (1), R 1 and R 2 are each independently an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, R 3 is an alkyl group having 1 to 6 carbon atoms, R 4 and R 5 are each independently a hydrogen atom, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a saturated or unsaturated cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, R 6 is an organic group having 2 to 12 carbon atoms having at least one of an ethylenic unsaturated bond and a carbon-carbon triple bond, R 7 and R 8 are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, and when there are a plurality of R 5 they may be the same as or different from each other, and when there are a plurality of R 7 they may be the same as or different from each other, and when there are a plurality of R 8 they may be the same as or different from each other, and R 1 to R8 Part of the structure may be independently substituted by a substituent or a halogen atom, and t, u, v, w, x, y, and z are each independently 0 or a positive number, and at least one of u and v is a positive number.

[0024] <6>

[0025] The method for manufacturing a laminated body with a hard coat according to any one of <1> to <5>, wherein the silane coupling agent is at least one selected from the group consisting of a silane coupling agent having an amino group, a silane coupling agent having a (meth)acryloyl group, and a silane coupling agent having a glycidyl group.

[0026] <7>

[0027] The method for manufacturing a laminated body with a hard coat according to any one of <1> to <6>, wherein the primer contains an organic solvent and water, and the organic solvent is at least one selected from the group consisting of an alcohol solvent, a ketone solvent, an ether solvent, and a nitrile.

[0028] <8>

[0029] The method for manufacturing a laminated body with a hard coat according to any one of <1> to <7>, wherein there is a plasma treatment step of subjecting the substrate to plasma treatment before the primer coating step.

[0030] <9>

[0031] A laminated body with a hard coat, which has: a substrate; a bottom coat provided on the substrate and containing a cured product of a silane coupling agent; and a hard coat provided on the bottom coat and containing a cured product of a hard coat agent containing a silsesquioxane derivative.

[0032] <10>

[0033] The laminated body with a hard coat according to <9>, wherein the pencil hardness of the surface of the hard coat measured according to JIS K5600-5-4 (1999) is 5H or more.

[0034] Advantages of the Invention

[0035] According to the present invention, there can be provided a method for manufacturing a laminated body with a hard coat and a laminated body with a hard coat, which can obtain a laminated body with a hard coat having a high hardness using a silsesquioxane derivative. Detailed Embodiments

[0036] Hereinafter, the embodiments for implementing the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments. In the following embodiments, unless otherwise specified, the constituent elements (including element steps, etc.) are not essential. The same applies to numerical values and their ranges, which do not limit the present disclosure.

[0037] In this specification, in the numerical range expressed by "~", the numerical values described before and after "~" are included as the minimum value and the maximum value, respectively.

[0038] In the numerical ranges described stepwise in this specification, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerically described stepwise range. In addition, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.

[0039] In addition, in this specification, the combination of two or more preferred modes is a more preferred mode.

[0040] <Method for manufacturing a laminated body with a hard coat / laminated body with a hard coat>

[0041] The method for manufacturing a laminated body with a hard coat according to the present disclosure is a method for manufacturing a laminated body with a hard coat that sequentially includes a substrate, a primer coat, and a hard coat, and sequentially has: a primer coating step of coating a primer containing a silane coupling agent on the substrate; a drying step of drying the primer to form the primer coat; a hard coat agent coating step of coating a hard coat agent containing a sesquisiloxane derivative on the primer coat; and a curing step of curing the hard coat agent to form the hard coat.

[0042] On the other hand, the laminated body with a hard coat obtained by the method for manufacturing a laminated body with a hard coat according to the present disclosure sequentially has: a substrate; a primer coat provided on the substrate and containing a cured product of a silane coupling agent; and a hard coat provided on the primer coat and containing a cured product of a hard coat agent containing a sesquisiloxane derivative.

[0043] In the method for manufacturing a laminated body with a hard coat according to the present disclosure, a laminated body with a hard coat having a hard coat with high hardness using a sesquisiloxane derivative can be obtained.

[0044] It is considered that by interposing a primer coat formed of a silane coupling agent between the substrate and the hard coat using a sesquisiloxane derivative, the adhesion between the substrate and the hard coat is improved. Therefore, the hardness of the hard coat is increased.

[0045] Hereinafter, the details of the method for manufacturing a laminated body with a hard coat according to the present disclosure will be described.

[0046] [Primer coating step]

[0047] In the primer coating step, a primer is coated on a substrate.

[0048] (Primer)

[0049] The primer contains a silane coupling agent. Specifically, the primer contains, for example, an organic solvent and water together with the silane coupling agent.

[0050] -Silane coupling agent-

[0051] As the silane coupling agent, a silane coupling agent having a silicon atom in one molecule and having an alkoxy group and an organic functional group (functional groups such as vinyl, epoxy group, methacryloyl group, acryloyl group, amino group, etc.) can be cited.

[0052] As the silane coupling agent, from the viewpoint of increasing the hardness of the hard coat, a silane coupling agent having two or more functional groups is preferred. In particular, as the silane coupling agent, at least one selected from the group consisting of a silane coupling agent having an amino group, a silane coupling agent having a (meth)acryloyl group, and a silane coupling agent having a glycidyl group is preferred.

[0053] As the silane coupling agent, it specifically includes -aminopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-aminopropyltriethoxysilane, γ-methacryloxypropyltriethoxysilane, and γ-acryloxypropyltriethoxysilane, etc.

[0054] -Organic solvent-

[0055] As the organic solvent, a solvent that dissolves the silane coupling agent and is water-soluble can be cited.

[0056] As the organic solvent, from the viewpoints of liquid stability and drying property, at least one selected from alcohol solvents, ketone solvents, ether solvents, ether solvents, and nitriles is preferred.

[0057] As the organic solvent, specifically, methanol, ethanol, acetone, propylene glycol monomethyl ether, tetrahydrofuran, acetonitrile, 2-propanol, methyl isobutyl ketone, methyl ethyl ketone, etc. can be cited.

[0058] -Water-

[0059] As the water, for example, distilled water, ion-exchanged water, ultrafiltered water, pure water, etc. can be cited.

[0060] (Amounts of each component in the primer)

[0061] The content x (mass %) of the silane coupling agent relative to 100 masses of the primer is preferably 0.1 < x < 30, more preferably 1 < x < 20, and further preferably 2.5 < x < 15.

[0062] The total content y (mass %) of the organic solvent and water relative to the primer is preferably 70 < y < 99.9, more preferably 80 < y < 99, and further preferably 90 < y < 98.

[0063] The content ratio z (mass %) of the organic solvent to the silane coupling agent is preferably z ≤ 40, more preferably z ≤ 36, and further preferably z ≤ 35.

[0064] The content ratio u (organic solvent / water) of the organic solvent to water is preferably 1 / 10 ≤ u ≤ 10 / 1 in terms of mass ratio, more preferably 1 / 6 ≤ u ≤ 6 / 1, and further preferably 1 / 5 ≤ u ≤ 5 / 1.

[0065] (Coating method of the primer)

[0066] The coating method of the primer can adopt well-known coating methods (rod coating method, Meyer rod coating method, coating method, doctor blade method, roll coating method, die coating method, comma coating method, gravure coating method, microgravure coating method, roller brush method, spraying method, air knife coating method, dipping method, curtain coating method, inkjet method, etc.).

[0067] (Substrate)

[0068] As the substrate, there is no particular limitation, and substrates composed of wood, metal, inorganic materials, plastics, paper, fibers, fabrics, etc. can be cited.

[0069] As the metal, copper, silver, iron, aluminum, silicon, silicon steel, stainless steel, etc. can be cited.

[0070] As the inorganic materials, metal oxides such as alumina, silica, magnesia, zirconia, zinc oxide, indium tin oxide, gallium oxide, metal nitrides such as aluminum nitride, gallium nitride, silicon nitride, ceramics such as silicon carbide and boron nitride, mortar, concrete, glass, etc. can be cited.

[0071] As specific examples of plastics, acrylic resins such as polymethyl methacrylate, polyester resins such as polyethylene terephthalate, polyvinyl chloride resins, polycarbonate resins, epoxy resins, polyamide resins such as nylon and aromatic polyamides, polyimide resins, polyamide-imide resins, fluororesins such as tetrafluoroethylene resin, polyolefin resins such as crosslinked polyethylene resin, vinylidene chloride resins, acrylonitrile-butadiene-styrene (ABS) resins, polystyrene resins, polyacrylonitrile resins, cycloolefin polymers (COP), cycloolefin copolymers (COC), acetate resins, polyarylate, cellophane, norbornene resins, acetylcellulose resins such as triacetyl cellulose (TAC), polychloroprene, polyphenylene sulfide, polysulfone, polyethersulfone, polyetheretherketone, polyurethane resins, and composite resins such as glass epoxy resins, and various fiber-reinforced resins, etc. can be cited.

[0072] As fibers, natural fibers, regenerated fibers, semi-synthetic fibers, metal fibers, glass fibers, carbon fibers, ceramic fibers, and well-known chemical fibers, etc. can be cited. The fabric can be a woven fabric or a non-woven fabric, and can be made using the aforementioned fibers, for example.

[0073] These materials can be used alone, or two or more of them can be used in combination, or they can be mixed or used in a composite manner.

[0074] Among them, at least one selected from the group consisting of a glass substrate, a polyimide resin substrate, a thiocarbamate resin substrate, a polyamide resin substrate, a cycloolefin resin substrate, and a polyolefin resin substrate is preferred, and a glass substrate is preferred. Generally, a glass substrate tends to have low adhesion to a hard coat formed from a hard coat agent containing a silsesquioxane derivative. However, by interposing a primer coat between the glass substrate and the hard coat, even when a hard coat is provided on the glass substrate, the adhesion between the glass substrate and the hard coat becomes high, and high hardness of the hard coat is achieved.

[0075] The shape of the substrate is not particularly limited, and examples thereof include plate-like, sheet-like, film-like, rod-like, spherical, fibrous, powdery, lens-like, and other regular or irregular shapes, etc.

[0076] [Plasma treatment step]

[0077] Before the primer coating step, a plasma treatment step of subjecting the substrate to plasma treatment can be provided. By performing the plasma treatment step, the surface of the substrate is cleaned and hydrophilized. As a result, since the adhesion between the primer coat substrate and the hard coat is further improved, it is easy to achieve high hardness of the hard coat.

[0078] Plasma treatment can employ plasma treatment under well-known conditions (such as vacuum plasma treatment and atmospheric pressure plasma treatment, etc.).

[0079] In addition, plasma treatment is a treatment that also includes corona discharge treatment, glow discharge treatment, and arc discharge treatment.

[0080] [Drying process]

[0081] In the drying process, the primer is dried to form a primer coat.

[0082] In the drying process, for example, at a temperature of 25°C to 200°C, the primer is dried for 1 minute to 120 minutes. As a result, various reactions such as the condensation of the silane coupling agent of the primer with the substrate and the volatilization of the solvent occur, and a primer coat can be formed.

[0083] The thickness of the primer coat is preferably 0.01 to 10 μm, more preferably 0.05 to 1 μm.

[0084] [Hard coat agent coating process]

[0085] In the hard coat agent coating process, a hard coat agent containing a sesquisiloxane derivative is coated on the primer coat.

[0086] (Hard coat agent)

[0087] The hard coat agent contains a sesquisiloxane derivative. In addition, the hard coat agent can contain a polymerization initiator together with the sesquisiloxane derivative, for example. In addition, the hard coat can contain various components (hereinafter also referred to as "other components") as needed.

[0088] -Sesquisiloxane derivative-

[0089] As the sesquisiloxane derivative, known sesquisiloxane derivatives can be cited (for example, a sesquisiloxane derivative having a T unit having 3 O atoms relative to 1 silicon atom). 1 / 2

[0090] In addition to the T unit, the sesquisiloxane derivative can also be a sesquisiloxane derivative having at least one unit of an M unit having 1 O atom relative to 1 silicon atom, a D unit having 2 O atoms relative to 1 silicon atom, and a Q unit having 4 (2 as oxygen atoms) O atoms relative to 1 silicon atom. 1 / 2 1 / 2 1 / 2

[0091] The sesquisiloxane derivative is preferably a sesquisiloxane derivative having a reactive group (such as a glycidyl group, an oxetanyl group, a (meth)acryloyl group, etc.).

[0092] In particular, as the sesquisiloxane derivative, from the viewpoint of increasing the hardness of the hard coat, the sesquisiloxane derivative represented by the following formula (1) is preferred.

[0093] ​​​​The silsesquioxane derivative represented by the following formula (1) also has excellent low curing shrinkage, storage stability, and ultraviolet curability.

[0094]

[0095] [In formula (1), R 1 and R 2 are each independently an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, R 3 is an alkyl group having 1 to 6 carbon atoms, R 4 and R 5 are each independently a hydrogen atom, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a saturated or unsaturated cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, R 6 is an organic group having 2 to 12 carbon atoms having at least one of an ethylenic unsaturated bond and a carbon-carbon triple bond, R 7 and R 8 are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, and when there are a plurality of R 5 they may be the same as or different from each other, and when there are a plurality of R 7 they may be the same as or different from each other, and when there are a plurality of R 8 they may be the same as or different from each other, and R 1 to R 8 may each independently be substituted in part of the structure by a substituent or a halogen atom, and t, u, v, w, x, y, and z are each independently 0 or a positive number, and at least one of u and v is a positive number. ]

[0096] Here, R 1 to R 8 in formula (1) may each independently be substituted in part of the structure by a substituent or a halogen atom. For example, R 1 to R 8 may each independently be substituted in part of the structure by an alkyl group, an aryl group, an aralkyl group, a vinyl group, an epoxy group, an oxetanyl group, a hydroxyl group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, an ammonium group, a mercapto group, an isocyanurate group, a ureido group, an isocyanate group, a carboxyl group, an acid anhydride group, or a halogen atom.

[0097] R 1 to R 8 in formula (1) may each independently be unsubstituted. For example, R 1 to R 3 or R 6 to R 8 (preferably R 1~R 3 and R 6 ~R 8 ) may also be unsubstituted.

[0098] Hereinafter, each structural unit that the silsesquioxane derivative of formula (1) may contain is referred to as structural units (a) to (g).

[0099]

[0100] In the silsesquioxane derivative of formula (1), in formula (1), t, u, v, w, x, y and z are each independently 0 or a positive number, and at least one of u and v is a positive number. That is, the silsesquioxane derivative of formula (1) contains at least one of structural unit (b) and structural unit (c) among the above structural units (a) to (g), and optionally contains at least one of structural unit (a), structural unit (d), structural unit (e), structural unit (f) and structural unit (g).

[0101] In formula (1), t, u, v, w, x, y and z represent the molar ratios of structural units (a) to (g). In addition, in formula (1), t, u, v, w, x, y and z represent the relative molar ratios of structural units (a) to (g) that the silsesquioxane derivative represented by formula (1) may contain. The molar ratio can be determined from the NMR (nuclear magnetic resonance) analysis value of the silsesquioxane derivative of formula (1). In addition, when the reaction rate of each raw material of the silsesquioxane derivative is clear, or when the yield is 100%, it can be determined from the input amount of the raw material.

[0102] For example, regarding the molar ratios of the respective structural units of the silsesquioxane derivative, it is possible to 1 perform 1H-NMR analysis on a sample dissolved in deuterated chloroform or the like, and further perform 29 Si-NMR analysis as needed for calculation.

[0103] It can also be decomposed into structural units with an alkali or the like, and the structure of the original silsesquioxane derivative can be deduced based on the ratio of the structural units and the like.

[0104] It is also possible to combine known methods such as mass spectrometry analysis and IR (infrared absorption spectroscopy) analysis as needed to determine the molar ratios of the respective structural units of the silsesquioxane derivative.

[0105] Regarding structural units (b) to (g) in formula (1), each may be only one type or two or more types. In addition, the arrangement order in formula (1) represents the composition of the structural units, and does not mean the arrangement order of the silsesquioxane derivative. Therefore, the condensation form of the structural units in the silsesquioxane derivative of formula (1) is not necessarily in the arrangement order of formula (1).

[0106] Hereinafter, the details of structural units (a) to (g) will be described.

[0107] -- Structural unit (a) --

[0108] Structural unit (a) is a Q unit having 4 O's (2 in terms of oxygen atoms) relative to 1 silicon atom. The Q unit refers to a unit having 4 O's relative to 1 silicon atom. 1 / 2 (In terms of oxygen atoms, it is 2). The Q unit refers to a unit having 4 O's relative to 1 silicon atom. 1 / 2 units.

[0109] The proportion of structural unit (a) in the silsesquioxane derivative of formula (1) is not particularly limited. For example, from the viewpoints of the viscosity of the silsesquioxane derivative and the hardness of the hard coat, the molar ratio (t / (t + u + v + w + x + y + z)) of structural unit (a) in all the structural units is preferably 0.1 or less, more preferably 0.05 or less, and still more preferably 0. Here, a molar ratio of 0 means that the corresponding structural unit is not included, and the same applies hereinafter.

[0110] -- Structural unit (b) --

[0111] Structural unit (b) is a T unit having 3 O's (1.5 in terms of oxygen atoms) relative to 1 silicon atom, and an acryloyloxy group is bonded to the silicon atom via R. The T unit refers to a unit having 3 O's relative to 1 silicon atom. 1 / 2 (In terms of oxygen atoms, it is 1.5), and an acryloyloxy group is bonded to the silicon atom via R. 1 The T unit refers to a unit having 3 O's relative to 1 silicon atom. 1 / 2 units.

[0112] In structural unit (b), R 1 is an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. R 1 is preferably an alkylene group having 1 to 10 carbon atoms or a cycloalkylene group having 3 to 10 carbon atoms, and more preferably an alkylene group having 1 to 10 carbon atoms.

[0113] The alkylene group having 1 to 10 carbon atoms is preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, and still more preferably a propylene group. The alkylene group having 1 to 10 carbon atoms may be linear or branched.

[0114] The cycloalkylene group having 3 to 10 carbon atoms is preferably a cycloalkylene group having 3 to 6 carbon atoms, more preferably a cycloalkylene group having 4 to 6 carbon atoms. The cycloalkylene group having 3 to 10 carbon atoms may have a branch.

[0115] The proportion of the structural unit (b) in the silsesquioxane derivative of the formula (1) is not particularly limited. For example, the molar ratio of the structural unit (b) in all the structural units (u / (t + u + v + w + x + y + z)), from the viewpoints of the curing shrinkage rate, storage stability, and UV curability of the silsesquioxane derivative in addition to the hardness of the hard coat, is preferably 0.2 to 0.99, more preferably 0.3 to 0.9, further preferably 0.3 to 0.7, and particularly preferably 0.45 to 0.65.

[0116] The molar ratio of the structural unit (b) in all the structural units may be 0.

[0117] In addition, from the viewpoints of the curing shrinkage rate and storage stability of the silsesquioxane derivative in addition to the hardness of the hard coat, it is preferable that u > v is satisfied, and it is more preferable that the molar ratio of the structural unit (b) (u / (t + u + v + w + x + y + z)) > the molar ratio of the structural unit (c) (v / (t + u + v + w + x + y + z)) + 0.05 is satisfied, and it is particularly preferable that the molar ratio of the structural unit (b) (u / (t + u + v + w + x + y + z)) > the molar ratio of the structural unit (c) (v / (t + u + v + w + x + y + z)) + 0.10 is satisfied.

[0119] --Structural unit (c)--

[0120] The structural unit (c) is the following T unit: having 3 O's relative to 1 silicon atom 1 / 2 (1.5 in terms of oxygen atoms), via R 2 , and the hydrogen atom is replaced by R 3 and an acryloyloxy group (such as a methacryloyloxy group) is bonded to the silicon atom.

[0121] In the structural unit (c), R 2 is an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms. The preferred mode of R 2 is the same as that of R 1 in the structural unit (b).

[0122] In the structural unit (c), R 3 is an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, and hexyl, with methyl and ethyl being preferred, and methyl being more preferred.

[0123] The proportion of the structural unit (c) in the silsesquioxane derivative of formula (1) is not particularly limited. For example, the molar ratio (v / (t + u + v + w + x + y + z)) of the structural unit (c) in all the structural units, from the viewpoints of the curing shrinkage rate, storage stability, and UV curability of the silsesquioxane derivative in addition to the hardness of the hard coat, is preferably 0 to 0.8, more preferably 0.05 to 0.7, still more preferably 0.2 to 0.7, and particularly preferably 0.35 to 0.55.

[0124] The molar ratio of the structural unit (c) in all the structural units may be 0.

[0125] In formula (1), at least one of u and v is a positive number, and from the viewpoint of the hardness of the hard coat, u and v are each independently preferably positive numbers.

[0126] The total molar ratio ((u + v) / (t + u + v + w + x + y + z)) of the structural unit (b) and the structural unit (c) in all the structural units, from the viewpoints of the curing shrinkage rate, storage stability, UV curability, and viscosity of the silsesquioxane derivative in addition to the hardness of the hard coat, is preferably 0.3 to 1, more preferably 0.5 to 1, still more preferably 0.7 to 1, and particularly preferably 0.9 to 1.

[0127] --Structural unit (d)--

[0128] The structural unit (d) is a T unit having 3 O's (1.5 in terms of oxygen atoms) bonded to one silicon atom and R 1 / 2 (bonded to the silicon atom). 4 In the structural unit (d), R

[0129] is a hydrogen atom, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a saturated or unsaturated cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. 4 The saturated or unsaturated alkyl group having 1 to 20 carbon atoms may be linear or may have a branched chain. The saturated or unsaturated alkyl group having 1 to 20 carbon atoms is preferably a saturated or unsaturated alkyl group having 1 to 10 carbon atoms, and more preferably a saturated alkyl group having 1 to 10 carbon atoms.

[0130] Examples of the saturated alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. From the viewpoints of the heat resistance and hardness of the hard coat, methyl or ethyl is preferred, and methyl is more preferred.

[0131] Examples of the unsaturated alkyl group having 1 to 10 carbon atoms include vinyl, 2-propenyl, and ethynyl.

[0132] As the unsaturated alkyl group having 1 to 10 carbon atoms, for example, vinyl, 2-propenyl, ethynyl, etc. can be cited.

[0133] The saturated or unsaturated cycloalkyl group having 3 to 8 carbon atoms may have a branched chain. The saturated or unsaturated cycloalkyl group having 3 to 8 carbon atoms is preferably a saturated or unsaturated cycloalkyl group having 4 to 6 carbon atoms.

[0134] The aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 10 carbon atoms.

[0135] Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a group in which one or more hydrogen atoms of the phenyl group are substituted with an alkyl group having 1 to 10 carbon atoms, and a naphthyl group. From the viewpoints of the heat resistance and hardness of the hard coat, a phenyl group is preferred.

[0136] The aralkyl group having 7 to 20 carbon atoms is preferably an aralkyl group having 7 to 10 carbon atoms.

[0137] Examples of the aralkyl group having 7 to 20 carbon atoms include a group in which one hydrogen atom of an alkyl group having 1 to 10 carbon atoms is substituted with an aryl group such as a phenyl group. For example, benzyl and phenethyl can be mentioned. From the viewpoints of the heat resistance and hardness of the hard coat, benzyl is preferred.

[0138] When a part of the structure shown by R 4 is substituted with a substituent or a halogen atom, examples of R 4 include 3-glycidoxypropyl, 2-(3,4-epoxycyclohexyl)ethyl, 3-(3-ethyloxetane-3-yl)methoxypropyl, 3-hydroxypropyl, 3-aminopropyl, 3-dimethylaminopropyl, 3-hydroxypropyl, hydrochloride of 3-aminopropyl, hydrochloride of 3-dimethylaminopropyl, p-styryl, N-2-(aminoethyl)-3-aminopropyl, N-phenyl-3-aminopropyl, hydrochloride of N-(vinylbenzyl)2-aminoethyl-3-aminopropyl, 3-ureidopropyl, 3-mercaptopropyl, 3-isocyanatopropyl, 3-carboxypropyl, and 3-chloropropyl.

[0139] The ratio of the structural unit (d) in the sesquioxane derivative of the formula (1) is not particularly limited. For example, the molar ratio of the structural unit (d) in all the structural units (w / (t + u + v + w + x + y + z)), from the viewpoint of the hardness of the hard coat, is preferably 0.1 or less, more preferably 0.05 or less, and still more preferably 0.

[0140] --Structural unit (e)--

[0141] The structural unit (e) is a D unit having 2 O 1 / 2 (1 in terms of oxygen atom) and 2 R 5 bonded to one silicon atom. The D unit means having 2 O 1 / 2unit.

[0142] In the structural unit (e), R 5 is a hydrogen atom, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a saturated or unsaturated cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. In the structural unit (d), there are a plurality of R 5 which may be the same as or different from each other. The preferred form of R 5 is the same as R 4 in the structural unit (d).

[0143] The proportion of the structural unit (e) in the silsesquioxane derivative of the formula (1) is not particularly limited. For example, from the viewpoint of the hardness of the hard coat, the molar ratio (x / (t + u + v + w + x + y + z)) of the structural unit (e) in all the structural units is preferably 0.1 or less, more preferably 0.05 or less, and still more preferably 0. On the other hand, from the viewpoints of the curing shrinkage rate of the hard coat agent and the bending resistance of the hard coat, x is preferably a positive number.

[0144] --Structural unit (f)--

[0145] The structural unit (f) is an M unit in which one O 1 / 2 (0.5 in terms of oxygen atom), one R 6 and two R 5 are bonded to a silicon atom. The M unit means a unit having one O 1 / 2 relative to one silicon atom.

[0146] In the structural unit (f), R 6 is an organic group having 2 to 12 carbon atoms having at least one of an ethylenic unsaturated bond and a carbon-carbon triple bond.

[0147] Examples of the organic group having 2 to 12 carbon atoms having an ethylenic unsaturated bond include vinyl, o-styryl, methylstyryl, p-styryl, acryloxymethyl, methacryloxymethyl, 2-acryloxyethyl, 2-methacryloxyethyl, 3-acryloxypropyl, 3-methacryloxypropyl, 8-acryloxyoctyl, 8-methacryloxyoctyl, 1-propenyl, 2-propenyl, 1-methylvinyl, 1-butenyl, 3-butenyl, 1-pentenyl, 4-pentenyl, 3-methyl-1-butenyl, 1-phenylvinyl, 2-phenylvinyl, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 3-butynyl, 1-pentynyl, 4-pentynyl, 3-methyl-1-butynyl, and phenylbutynyl. From the viewpoint of the hardness of the hard coat, vinyl, 2-propenyl, o-styryl, methylstyryl, or p-styryl is preferred, and vinyl is more preferred.

[0148] In the structural unit (f), R 7 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. In the structural unit (f), when there are a plurality of Rs 7 they may be the same as or different from each other.

[0149] Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. From the viewpoints of the heat resistance and hardness of the hard coat, methyl or ethyl is preferred, and methyl is more preferred.

[0150] Examples of the aryl group having 6 to 10 carbon atoms include phenyl, a group in which one or more hydrogen atoms of phenyl are substituted with an alkyl group having 1 to 4 carbon atoms, and naphthyl. From the viewpoints of the heat resistance and hardness of the hard coat, phenyl is preferred.

[0151] Examples of the aralkyl group having 7 to 10 carbon atoms include a group in which one hydrogen atom of an alkyl group having 1 to 4 carbon atoms is substituted with an aryl group such as phenyl. For example, benzyl and phenethyl can be mentioned. From the viewpoints of the heat resistance and hardness of the hard coat, benzyl is preferred.

[0152] The ratio of the structural unit (f) in the sesquisiloxane derivative of the formula (1) is not particularly limited. For example, the molar ratio (y / (t + u + v + w + x + y + z)) of the structural unit (f) in all the structural units is preferably 0.5 or less, more preferably 0.3 or less, and further preferably 0.1 or less, from the viewpoints of the curing shrinkage rate, storage stability, and UV curability of the sesquisiloxane derivative, in addition to the hardness of the hard coat.

[0153] --Structural unit (g)--

[0154] The structural unit (g) is an M unit having one O 1 / 2 (0.5 in terms of oxygen atom) and three Rs bonded to the silicon atom. 8 bonded to the silicon atom.

[0155] In the structural unit (g), R 8 is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. In the structural unit (g), when there are a plurality of Rs 8 they may be the same as or different from each other. The preferred mode of R 8 is the same as that of R in the structural unit (f). 7

[0156] ​The proportion of the structural unit (g) in the silsesquioxane derivative of formula (1) is not particularly limited. For example, from the viewpoint of the hardness of the hard coat, the molar ratio (z / (t + u + v + w + x + y + z)) of the structural unit (g) in all the structural units is preferably 0.1 or less, more preferably 0.05 or less, and still more preferably 0.

[0157] --Other structural unit (h)--

[0158] The silsesquioxane derivative of formula (1) may further contain (R 9 O 1 / 2 ) as a Si-free structural unit (hereinafter, also referred to as structural unit (h)).

[0159] Among them, R 9 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms can be any of an aliphatic group and an alicyclic group, and can be either linear or branched. Specific examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, and hexyl.

[0160] The structural unit (h) is an alkoxy group which is a hydrolyzable group contained in the silicon compound described later, or an alkoxy group formed by substituting the hydrolyzable group of the silicon compound with an alcohol contained in the reaction solvent, and can be a group that remains in the molecule without hydrolysis or polycondensation, or can be a hydroxyl group that remains in the molecule without polycondensation after hydrolysis.

[0161] In formula (1), from the viewpoints of the hardness of the hard coat, the curing shrinkage rate, storage stability, and UV curability of the silsesquioxane derivative, t, x, and z are 0, and w and y are each independently preferably 0 or a positive number, and t, w, x, y, and z are more preferably 0. In addition, in formula (1), from the viewpoints of the hardness of the hard coat, the curing shrinkage rate, storage stability, and UV curability of the silsesquioxane derivative, it is preferably satisfied that 0 ≤ y / (u + v + w) ≤ 0.5, more preferably satisfied that 0 ≤ y /

[0162] (u + v + w) ≤ 0.3, and still more preferably satisfied that 0 ≤ y / (u + v + w) ≤ 0.1.

[0163] In formula (1), in addition to the hardness of the hard coat, from the viewpoints of the curing shrinkage rate, storage stability, and UV curability of the silsesquioxane derivative, u and v are each independently preferably a positive number.

[0164] In addition, from the viewpoints of the curing shrinkage rate, storage stability, and UV curability of the silsesquioxane derivative, in addition to the hardness of the hard coat, u and v preferably satisfy 0 < v / u ≤ 1, more preferably satisfy 0.1 ≤ v / u ≤ 1, still more preferably satisfy 0.2 ≤ v / u ≤ 1, and particularly preferably satisfy 0.3 ≤ v / u ≤ 1.

[0165] (Weight-average molecular weight of the silsesquioxane derivative)

[0166] The weight-average molecular weight of the silsesquioxane derivative (hereinafter also referred to as "Mw") is not particularly limited, and for example, it can be 300 to 30,000, can be 500 to 15,000, can be 700 to 10,000, or can be 1,000 to 5,000.

[0167] The weight-average molecular weight (Mw) of the silsesquioxane derivative refers to the value obtained by converting the molecular weight measured by GPC (gel permeation chromatography) using polystyrene as a standard substance.

[0168] Specifically, the weight-average molecular weight (Mw) of the silsesquioxane derivative is measured as follows. Specifically, using a gel permeation chromatograph (manufactured by Tosoh Corporation, HLC-8320GPC, hereinafter simply referred to as "GPC"), separation is carried out in a tetrahydrofuran solvent at 40 °C using a GPC column "TSK gel SuperMultipore HZ-M" (manufactured by Tosoh Corporation), and the molecular weight in terms of standard polystyrene is calculated from the retention time.

[0169] (Viscosity of the silsesquioxane derivative)

[0170] In the silsesquioxane derivative, the viscosity at 25 °C is preferably 10 mPa·s to 50,000 mPa·s, more preferably 100 mPa·s to 40,000 mPa·s, still more preferably 1,000 mPa·s to 30,000 mPa·s, and particularly preferably 2,000 mPa·s to 20,000 mPa·s.

[0171] The viscosity at 25 °C refers to the value measured using an E-type viscometer (cone-plate viscometer, for example, TVE22H type viscometer manufactured by Toki Sangyo Co., Ltd.).

[0172] (Production method of the silsesquioxane derivative)

[0173] The silsesquioxane derivative can be produced by a known method. The production method of the silsesquioxane derivative is disclosed in detail as a production method of polysiloxane in International Publication No. 2013 / 031798 and the like.

[0174] Among them, in the production method of the silsesquioxane derivative of formula (1), R n SiX p(n represents an integer from 0 to 3, p represents an integer from 1 to 4, n + p = 4, R represents a group bonded to a silicon atom via a carbon atom in the sesquisiloxane derivative, and X represents a hydrolyzable group.) At least one organosilicon compound, preferably including a step of hydrolyzing by adding 2 to 30 molar equivalents of water relative to the total amount of hydrolyzable groups possessed by the above organosilicon compound (hereinafter, also referred to as "hydrolysis step").

[0175] As R, preferably listed are groups bonded to the silicon atom in the sesquisiloxane derivative of formula (1) via a carbon atom (H2C=CHCOO-R 1 -, H2C=C(R 3 )COO-R 2 - and R 4 ~R 8 etc.).

[0176] X preferably includes alkoxy, siloxy or halogen atom, more preferably alkoxy or siloxy.

[0177] In the hydrolysis step, preferably, not only the hydrolysis of the above organosilicon compound is carried out, but also the hydrolysis and polycondensation reactions of the above organosilicon compound and other silicon compounds as required are carried out.

[0178] In addition, in the hydrolysis step, after carrying out the hydrolysis and polycondensation reactions of the above organosilicon compound and other silicon compounds as required to obtain a sesquisiloxane derivative as an intermediate product, the hydrolysis and polycondensation reactions of the obtained intermediate product with the above organosilicon compound, etc. can be further carried out.

[0179] In the case of obtaining an intermediate product as described above, after carrying out the hydrolysis and polycondensation reactions of the organosilicon compound and other silicon compounds as required, the hydrolysis and polycondensation reactions of the obtained intermediate product with the compound in which n is 3 and p is 1 in the above organosilicon compound can be further carried out. Thereby, a sesquisiloxane derivative sealed with a structural unit (f) derived from a compound in which n is 3 and p is 1 at the terminal portion in the above organosilicon compound can be appropriately synthesized, the viscosity increase of the sesquisiloxane derivative is suppressed, and the storage stability becomes better.

[0180] The manufacturing method of the sesquisiloxane derivative of formula (1) preferably includes a distillation removal step of distilling off the reaction solvent, by-products, residual monomers, water, etc. in the reaction solution after carrying out the hydrolysis and polycondensation reactions of the silicon compound in the presence of a reaction solvent.

[0181] Among the above-mentioned silicone compounds, examples of the silicone compound having an acryloyl group include (3-acryloyloxypropyl)trimethoxysilane, (3-acryloyloxypropyl)triethoxysilane, (8-acryloyloxyoctyl)trimethoxysilane, and (3-acryloyloxypropyl)trichlorosilane.

[0182] Among the above-mentioned silicone compounds, examples of the silicone compound having a methacryloyl group include (3-methacryloyloxypropyl)trimethoxysilane, (3-methacryloyloxypropyl)triethoxysilane, (8-methacryloyloxyoctyl)trimethoxysilane, and (3-methacryloyloxypropyl)trichlorosilane.

[0183] Examples of the silicone compound that provides two structural units (f) by hydrolysis include 1,3-divinyltetramethyldisiloxane, 1,3-bis(p-styryl)tetramethyldisiloxane, 1,3-bis(3-acryloyloxypropyl)tetramethyldisiloxane, 1,3-bis(3-methacryloyloxypropyl)tetramethyldisiloxane, etc.; methoxydimethylvinylsilane, ethoxydimethylvinylsilane, chlorodimethylvinylsilane, dimethylvinylsilanol, (3-acryloyloxypropyl)dimethylmethoxysilane, (3-methacryloyloxypropyl)dimethylmethoxysilane, p-styryldimethylmethoxysilane, ethynyldimethylmethoxysilane, etc.

[0184] Examples of the silicon compound that provides the structural unit (a) by hydrolysis include tetramethylsiloxane, tetraethoxysilane, etc.

[0185] As the compound where n is 3 and p is 1 in the organosilicon compound, examples include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, octyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane, cyclohexyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, p-styryltrimethoxysilane, ethynyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, tris(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropyltrimethoxysilane, 3-ethyl-3-[(3-(trimethoxysilyl)propoxy)methyl]oxetane, 3-ethyl-3-[(3-(triethoxysilyl)propoxy)methyl]oxetane, etc.

[0186] As the compound where n is 2 and p is 2 in the organosilicon compound, examples include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, propylmethyldimethoxysilane, octylmethyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, benzylmethyldimethoxysilane, cyclohexylmethyldimethoxysilane, vinylmethyldimethoxysilane, allylmethyldimethoxysilane, p-styrylmethyldimethoxysilane, ethynylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropylmethyldimethoxysilane, hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropylmethyldimethoxysilane, 3-ureidopropylmethyldimethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, (3-acryloxypropyl)methyldimethoxysilane, (3-methacryloxypropyl)methyldiethoxysilane, etc.

[0187] As the compound where n is 1 and p is 3 in the above organosilicon compound, examples include hexamethyldisiloxane, trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane, dimethylphenylmethoxysilane, etc.

[0188] In the hydrolysis step, it is preferable to use an alcohol as the organic solvent. An alcohol is a narrow-sense alcohol represented by the general formula R-OH and is a compound having no functional group other than an alcoholic hydroxyl group.

[0189] The alcohol is not particularly limited. For example, methanol, ethanol, 1-propanol, 2-propanol, 2-butanol, 2-pentanol, 3-pentanol, 2-methyl-2-butanol, 3-methyl-2-butanol, cyclopentanol, 2-hexanol, 3-hexanol, 2-methyl-2-pentanol, 3-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-3-pentanol, 2-ethyl-2-butanol, 2,3-dimethyl-2-butanol, and cyclohexanol can be mentioned. Among them, secondary alcohols such as 2-propanol, 2-butanol, 2-pentanol, 3-pentanol, 3-methyl-2-butanol, cyclopentanol, 2-hexanol, 3-hexanol, 3-methyl-2-pentanol, and cyclohexanol are preferred.

[0190] In the hydrolysis step, one kind of these alcohols can be used, or two or more kinds can be used in combination.

[0191] The organic solvent used in the hydrolysis step may be only an alcohol, or may further be a mixed solvent with at least one co-solvent. The co-solvent can be either a polar solvent or a non-polar solvent, or a combination of both.

[0192] Examples of the alcohol-containing organic solvent include xylene, toluene, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether, etc.

[0193] The hydrolysis and condensation reactions in the hydrolysis step are carried out in the presence of water.

[0194] In the hydrolysis step, it is preferable to add 1.5 to 30 molar equivalents of water for hydrolysis and then condensation with respect to the total amount of the hydrolyzable groups of the above-mentioned organosilicon compound.

[0195] In addition, in the hydrolysis step, from the viewpoints of the curing shrinkage rate, hardness, storage stability, and curl inhibition during curing of the obtained silsesquioxane derivative, the amount of water added is preferably 1.7 to 8 molar equivalents, more preferably 1.9 to 7 molar equivalents, further preferably 2.0 to 7 molar equivalents, particularly preferably 2.2 to 7 molar equivalents, and most preferably 2.4 to 6 molar equivalents with respect to the total amount of the hydrolyzable groups of the above-mentioned organosilicon compound.

[0196] In addition, the hydrolysis and polycondensation reactions of the silicon compound can be carried out without a catalyst or with a catalyst. When using a catalyst, inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, and phosphoric acid; acid catalysts exemplified by organic acids such as formic acid, acetic acid, oxalic acid, and p-toluenesulfonic acid; base catalysts such as ammonia, tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate are preferably used, and acid catalysts are more preferably used.

[0197] The amount of the catalyst used is preferably an amount equivalent to 0.01 mol% to 20 mol%, more preferably an amount equivalent to 0.1 mol% to 10 mol%, based on the total amount (in moles) of the silicon atoms contained in the silicon compound.

[0198] The completion of the hydrolysis and polycondensation reactions in the hydrolysis step can be appropriately detected by methods described in various publications and the like. In the hydrolysis step of the method for producing the silsesquioxane derivative of formula (1), an auxiliary agent can be added to the reaction system.

[0199] After the hydrolysis step in the production of the silsesquioxane derivative of formula (1), by having the above-mentioned distillation removal step, the stability of the produced silsesquioxane derivative of formula (1) can be improved. The distillation removal can be carried out under normal pressure or reduced pressure, can be carried out at room temperature or with heating, or can be carried out under cooling.

[0200] The method for producing the silsesquioxane derivative can have a neutralization step for neutralizing the catalyst before the distillation removal step. In addition, a step for removing the salt formed by neutralization by washing with water or the like can also be provided.

[0201] In addition, the silsesquioxane derivative represented by formula (1) can contain a group formed by ring-opening of an acid or the like on an oxetanyl or epoxy group in the side chain functional group derived from the silicon compound used as a raw material in the preparation, can contain a hydroxyalkyl group formed by decomposition of an organic group having a (meth)acryloyl group, and can also contain a group formed by addition of an acid or the like to an unsaturated hydrocarbon group or the like. As a specific example thereof, for example, a compound containing the structure represented by the following formula (A) and / or the structure represented by the following formula (B) in a part of formula (1) can be cited. As the content ratio thereof, with respect to the amount of the original organic group having an oxetanyl or epoxy group, the original organic group having a (meth)acryloyl group, or the original organic group having an unsaturated hydrocarbon group derived from the silicon compound used as a raw material, if it is 50 mol% or less, there is no problem in implementing the present disclosure, preferably 30 mol% or less, more preferably 10 mol% or less. In formulas (A) and (B), T units are exemplified, but D units, M units, etc. can also be the same.

[0202]

[0203] (Content of silsesquioxane derivative)

[0204] The content of the silsesquioxane derivative is preferably 1 to 95% by mass, more preferably 10 to 80% by mass, based on the total amount of the hard coat agent.

[0205] (Polymerization initiator)

[0206] As the polymerization initiator, a known polymerization initiator is used according to the type of the silsesquioxane derivative.

[0207] For example, when the silsesquioxane derivative represented by the formula (1) is applied as the silsesquioxane derivative, as the polymerization initiator, for example, a photo radical polymerization initiator and a thermal radical polymerization initiator can be applied.

[0208] Examples of the photo radical polymerization initiator include acetophenone compounds such as 2,2 - dimethoxy - 1,2 - diphenylethane - 1 - one, 1 - hydroxycyclohexyl phenyl ketone, 2 - hydroxy - 2 - methyl - 1 - phenylpropan - 1 - one, 1 - [4 - (2 - hydroxyethoxy)phenyl] - 2 - hydroxy - 2 - methyl - 1 - propan - 1 - one, 2 - methyl - 1 - [4 - (methylthio)phenyl] - 2 - morpholinopropan - 1 - one, 2 - benzyl - 2 - dimethylamino - 1 - (4 - morpholinophenyl) - butan - 1 - one, diethoxyacetophenone, oligo[2 - hydroxy - 2 - methyl - 1 - [4 - (1 - methylethenyl)phenyl]acetone], and 2 - hydroxy - 1 - {4 - [4 - (2 - hydroxy - 2 - methyl - propionyl)benzyl]phenyl} - 2 - methyl - propan - 1 - one; benzophenone compounds such as benzophenone, 4 - phenylbenzophenone, 2,4,6 - trimethylbenzophenone, and 4 - benzoyl - 4'-methyldiphenyl sulfide; α - keto ester compounds such as methyl benzoylformate, 2 - [2 - oxo - 2 - phenylacetoxyethoxy]ethyl hydroxyphenylacetate, and 2 - [2 - hydroxyethoxy]ethyl hydroxyphenylacetate; phosphine oxide compounds such as 2,4,6 - trimethylbenzoyl diphenylphosphine oxide, bis(2,4,6 - trimethylbenzoyl)phenylphosphine oxide, and bis(2,6 - dimethoxybenzoyl) - 2,4,4 - trimethylpentylphosphine oxide; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; titanocene compounds; photoinitiators of the acetophenone / benzophenone mixture type such as 1 - (4 - (4 - benzoylphenylthio)phenyl) - 2 - methyl - 2 - (4 - methylphenylsulfinyl)propane - 1 - one; oxime ester photo - polymerization initiators such as 1 - (4 - phenylthiophenyl) - 2 - (O - benzoyloxy) - 1,2 - octanedione; and camphorquinone. These can be used alone or in combination of two or more.

[0209] There is no particular limitation on the thermal radical polymerization initiator, and examples thereof include peroxides and azo - type initiators.

[0210] As peroxides, hydrogen peroxide can be mentioned; inorganic peroxides such as sodium persulfate, ammonium persulfate, potassium persulfate; 1,1-bis(tert-butylperoxy)-2-methylcyclohexane, 1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-hexylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(4,4-di-tert-butylperoxycyclohexyl)propane, 1,1-bis(tert-butylperoxy)cyclododecane, tert-hexylperoxyisopropyl monocarbonate, tert-butylperoxymaleic acid, tert-butylperoxy-3,3,5-trimethylhexanoate, tert-butylperoxylaurate, 2,5-dimethyl-2,5-di(m-toluoylperoxy)hexane, tert-hexylperoxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, tert-butylperoxyacetate, 2,2-bis(tert-butylperoxy)butane, tert-butylperoxybenzoate, n-butyl-4,4-bis(tert-butylperoxy)valerate, di-tert-butylperoxyisophthalate, α,α'-bis(tert-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hex-3-yne, diisopropylbenzene hydroperoxide, tert-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, tert-hexyl hydroperoxide, tert-butyl hydroperoxide and other organic peroxides.

[0211] These can be used alone or in combination of two or more.

[0212] As azo initiators, azo compounds such as 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, azobis(tert-octane), azobis(tert-butane) can be mentioned. These can be used alone or in combination of two or more.

[0213] In addition, an oxidation-reduction reaction can also be formed by combining with an oxidation-reduction polymerization initiation system in which a peroxide is used in combination with a reducing agent such as ascorbic acid, sodium ascorbate, sodium erythorbate, tartaric acid, citric acid, metal salts of formaldehyde sulfoxylate, sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium metabisulfite, iron chloride.

[0214] The content of the polymerization initiator is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the silsesquioxane derivative.

[0215] (Other components)

[0216] There is no particular limitation on other components that can be contained in the hard coat agent. For example, solvents, polymerizable compounds other than silsesquioxane derivatives, resins, silicones, monomers, fillers, surfactants, antistatic agents (such as conductive polymers), leveling agents, photosensitizers, ultraviolet absorbers, antioxidants, heat resistance improvers, stabilizers, lubricants, pigments, dyes, plasticizers, suspending agents, adhesion imparting agents, nanoparticles, nanofibers, nanosheets, etc. can be cited.

[0217] The hard coat agent may contain silane reactive diluents such as tetraalkoxysilanes, trialkoxysilanes, dialkoxysilanes, monoalkoxysilanes, and disiloxanes.

[0218] The hard coat agent may or may not contain a solvent.

[0219] Examples of the solvent include various organic solvents such as aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, chlorinated hydrocarbon solvents, alcohol solvents, ether solvents, amide solvents, ketone solvents, ester solvents, and cellosolve solvents.

[0220] The hard coat agent may or may not contain polymerizable compounds other than silsesquioxane derivatives (hereinafter, also referred to as "other polymerizable compounds").

[0221] As the other polymerizable compounds, there is no particular limitation as long as they can undergo a polymerization reaction in the presence of the silsesquioxane derivative and the polymerization initiator. Examples of the other polymerizable compounds include silsesquioxane derivatives other than those represented by the formula (1), (meth)acrylate compounds, compounds having an ethylenically unsaturated group, epoxy compounds (compounds having an epoxy group), compounds having an oxetanyl group (compounds containing an oxetanyl group), compounds having a vinyl ether group (vinyl ether compounds), etc.

[0222] There is no particular limitation on the (meth)acrylate compound. Examples include compounds having one (meth)acryloyl group (hereinafter, also referred to as "monofunctional (meth)acrylate"), and compounds having two or more (meth)acryloyl groups (hereinafter, also referred to as "polyfunctional (meth)acrylate").

[0223] As monofunctional (meth)acrylates, for example, (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc.;

[0224] Monofunctional (meth)acrylates having an alicyclic group such as cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and tricyclodecane hydroxymethyl (meth)acrylate;

[0225] Monofunctional (meth)acrylates having an aromatic group such as benzyl (meth)acrylate and phenyl (meth)acrylate;

[0226] (Meth)acrylates of alkylene oxide adducts of phenol derivatives such as (meth)acrylates of phenol ethylene oxide adducts, (meth)acrylates of phenol propylene oxide adducts, (meth)acrylates of modified nonylphenol ethylene oxide adducts, (meth)acrylates of nonylphenol propylene oxide adducts, (meth)acrylates of cumylphenol alkylene oxide adducts, o-phenylphenyl (meth)acrylate, and (meth)acrylates of o-phenylphenyl alkylene oxide adducts; Monofunctional (meth)acrylates having an alkoxyalkyl group such as 2-ethylhexyl carbitol (meth)acrylate;

[0227] Monofunctional (meth)acrylates having a heterocycle such as tetrahydrofurfuryl (meth)acrylate and N-(2-(meth)acryloyloxyethyl)hexahydrophthalimide;

[0228] (Meth)acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 2-hydroxyhexyl (meth)acrylate;

[0229] Monofunctional (meth)acrylates having a hydroxyl group and an aromatic group such as 2-hydroxy-3-phenoxypropyl (meth)acrylate;

[0230] Alkylene glycol mono(meth)acrylates such as diethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, and tripropylene glycol mono(meth)acrylate; and

[0231] Monofunctional (meth)acrylates having a carboxyl group such as ω-carboxy polycaprolactone mono(meth)acrylate and phthalic acid mono-hydroxyethyl (meth)acrylate, etc.

[0232] As polyfunctional (meth)acrylates, for example, polyethylene glycol di(meth)acrylates such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate;

[0233] Polypropylene glycol di(meth)acrylate such as dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate;

[0234] 1,4-Butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, di(meth)acrylate of ethylene oxide-modified neopentyl glycol, di(meth)acrylate of ethylene oxide-modified bisphenol A, di(meth)acrylate of propylene oxide-modified bisphenol A, di(meth)acrylate of ethylene oxide-modified hydrogenated bisphenol A, trimethylolpropane di(meth)acrylate, trimethylolpropane allyl ether di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexaacrylate, etc.

[0235] As the polyfunctional (meth)acrylate, urethane (meth)acrylate can also be used.

[0236] Examples of the urethane (meth)acrylate include compounds obtained by the addition reaction of an organic polyisocyanate and a hydroxy group-containing (meth)acrylate, compounds obtained by the addition reaction of an organic polyisocyanate, a polyol and a hydroxy group-containing (meth)acrylate, etc.

[0237] The monofunctional (meth)acrylate, polyfunctional (meth)acrylate, etc. can be used alone, or two or more kinds can be used in combination, and different kinds of substances can also be used in combination.

[0238] Here, as the polyol, low molecular weight polyols, polyether polyols, polyester polyols, polycarbonate polyols, etc. can be mentioned.

[0239] Examples of the low molecular weight polyols include ethylene glycol, propylene glycol, neopentyl glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, etc.

[0240] As the polyether polyol, polypropylene glycol, polytetramethylene glycol, etc. can be mentioned.

[0241] As the polyester polyol, reaction products of these low molecular weight polyols and / or polyether polyols with acid components such as dibasic acids or their acid anhydrides such as adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid, terephthalic acid, etc. can be cited.

[0242] These can be used alone, or two or more kinds can be used in combination, and different kinds of substances can also be used in combination.

[0243] Examples of the organic polyisocyanate include tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate, etc.

[0244] Examples of the hydroxy group-containing (meth)acrylate include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; and hydroxy group-containing polyfunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate, the di(meth)acrylate of the 3-mole addition product of an alkylene oxide of isocyanuric acid, and dipentaerythritol penta(meth)acrylate, etc.

[0245] These may be used alone, or two or more of them may be used in combination, and different types of substances may also be used in combination.

[0246] In the case of using a (meth)acrylate compound in combination in the hard coat agent, its mixing ratio is not particularly limited. For example, the mixing ratio of the (meth)acrylate compound relative to 100 parts by mass of the sesquisiloxane derivative is preferably 0 part by mass to 100 parts by mass, more preferably 0 part by mass to 50 parts by mass, and still more preferably 0 part by mass to 20 parts by mass. From the viewpoints of improving the adhesion to the hard coat and the hardness of the hard coat, the mixing ratio of the (meth)acrylate compound is preferably low, and it is preferably not contained or preferably 10% by mass or less relative to the total amount of the hard coat agent, more preferably not contained or 5% by mass or less relative to the total amount of the hard coat agent, still more preferably not contained or 1% by mass or less relative to the total amount of the hard coat agent, and particularly preferably not contained.

[0247] A compound having one ethylenically unsaturated group in one molecule other than the above (meth)acrylate compound may also be added to the hard coat agent.

[0248] As the above ethylenically unsaturated group, (meth)acryloyl, maleimido, (meth)acrylamido, or vinyl is preferred.

[0249] Specific examples of the compound having an ethylenically unsaturated group include (meth)acrylic acid, a Michael addition-type dimer of acrylic acid, N-(2-hydroxyethyl)citraconimide, N,N-dimethylacrylamide, acryloylmorpholine, N-vinylpyrrolidone, and N-vinylcaprolactam, etc.

[0250] These may be used alone, or two or more of them may be used in combination.

[0251] Examples of the epoxy compound include monofunctional epoxy compounds and polyfunctional epoxy compounds, etc.

[0252] Examples of the compound containing an oxetanyl group include a monofunctional oxetane compound, a polyfunctional oxetane compound, and the like.

[0253] Examples of the vinyl ether compound include a monofunctional vinyl ether compound, a polyfunctional vinyl ether compound, and the like.

[0254] As these compounds, for example, the compounds described in JP-A-2011-42755 can be used.

[0255] When the hard coat agent contains other polymerizable compounds, the content of the other polymerizable compounds is preferably 0.01 part by mass to 100 parts by mass, more preferably 0.1 part by mass to 50 parts by mass, and still more preferably 1 part by mass to 25 parts by mass with respect to 100 parts by mass of the silsesquioxane derivative.

[0256] (Coating method of the hard coat agent)

[0257] As the coating method of the hard coat agent, a known coating method (bar coating method, Meyer bar coating method, casting method, doctor blade method, roll coating method, die coating method, comma coating method, gravure coating method, microgravure coating method, roller brush method, spraying method, air knife coating method, dipping method, curtain coating method, inkjet method, etc.) can be adopted.

[0258] [Curing step]

[0259] In the curing step, the hard coat agent is cured to form a hard coat layer.

[0260] In the curing step, for example, the hard coat agent is cured by at least one of active energy ray irradiation (such as ultraviolet ray irradiation) and heating. Thereby, the hard coat agent is cured and a hard coat layer can be formed.

[0261] In the curing step, according to whether the silsesquioxane derivative of the hard coat agent is curable by active energy rays and / or heat, the curing method and curing conditions are selected. In addition, the curing conditions (in the case of curability by active energy rays, for example, the type of light source and the light irradiation amount, etc.; in the case of curability by heat, the heating temperature and heating time, etc.) are appropriately selected according to the type and amount of the polymerization initiator of the hard coat agent and the type of other polymerizable compounds.

[0262] (Active energy ray curing method)

[0263] When the hard coat agent is a hard coat agent curable by active energy rays, as its curing method, active energy ray irradiation can be performed using a known active energy ray irradiation device or the like. Examples of the active energy rays include electron rays, and light such as ultraviolet rays, visible rays, and X-rays. Light is preferred, and ultraviolet rays are more preferred from the viewpoint of being able to use an inexpensive device.

[0264] Examples of ultraviolet irradiation devices include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, ultraviolet (UV) electrodeless lamps, chemical lamps, black lights, microwave-excited mercury lamps, and light-emitting diodes (LEDs).

[0265] The light irradiation intensity of the hard coat agent can be selected according to the purpose, use, etc. For the light wavelength region effective for activating the active energy ray polymerization initiator (referred to as a photoinitiator in the case of photocurability), the light irradiation intensity in the wavelength range of 220 nm to 460 nm is preferably 0.1 mW / cm 2 ~1000 mW / cm 2 .

[0266] The irradiation energy should be appropriately set according to the type of active energy ray, the composition of the hard coat agent, etc. The light irradiation time can also be selected according to the purpose, use, etc., and it is preferably set in such a way that the cumulative light amount represented by the product of the light irradiation intensity and the light irradiation time in the light wavelength region is 10 mJ / cm 2 ~7,000 mJ / cm 2 . The cumulative light amount is more preferably 200 mJ / cm 2 ~

[0267] 5000 mJ / cm 2 , and further preferably 500 mJ / cm 2 ~4000 mJ / cm 2 . If the cumulative light amount is within the above range, the hard coat agent is cured smoothly, and a uniform cured product can be easily obtained.

[0268] In addition, heat curing can be appropriately combined before and / or after photocuring.

[0269] For example, the following two-stage curing can also be carried out: when irradiating light, after the hard coat agent penetrates into the substrate having a shaded part, irradiate light to first cure the hard coat agent in the light-irradiated part, and then apply heat to cure the hard coat agent in the non-light-irradiated part. There is no particular limitation on such a substrate, and examples include substrates having complex shapes such as cloth-like, fibrous, powdery, porous, and uneven shapes, and may also be a shape formed by combining two or more of these shapes.

[0270] (Thermal curing method)

[0271] When the hard coat agent is a thermosetting hard coat agent, its curing method and curing conditions are not particularly limited.

[0272] The curing temperature is preferably 80°C to 200°C, more preferably 100°C to 180°C, and further preferably 110°C to 150°C. The curing temperature can be kept constant or raised. It is also possible to combine heating and cooling.

[0273] The curing time is appropriately selected according to the type of thermal polymerization initiator of the hard coat agent and the content ratio of other components, etc., and is preferably 10 minutes to 360 minutes, more preferably 30 minutes to 300 minutes, and further preferably 60 minutes to 240 minutes. By curing the composition under the above preferred conditions, a uniform cured film without swelling, cracks, etc. can be formed.

[0274] In addition, the thickness of the hard coat is preferably 0.5 to 100 μm, more preferably 1 to 70 μm.

[0275] Through the above processes, the high-hardness laminated body with a hard coat of the present disclosure using a sesquioxane derivative is obtained.

[0276] Specifically, in the laminated body with a hard coat of the present disclosure, the pencil hardness of the surface of the hard coat in the laminated body with a hard coat measured according to JIS K5600-5-4 (1999) is preferably 5H or more, more preferably 7H or more, and further preferably 8H or more.

[0277] Especially when the substrate is a glass substrate specified in JIS R3202:2011 and the thickness of the hard coat is 5 μm or less, the pencil hardness of the surface of the hard coat in the laminated body with a hard coat is preferably 7H or more, more preferably 8H or more.

[0278] The upper limit of the pencil hardness of the surface of the hard coat is, for example, 10H or less.

[0279] The pencil hardness of the surface of the hard coat is measured according to JIS K5600-5-4 (1999) on a specimen in a state where a substrate, a primer coat, and a hard coat are laminated, collected from the laminated body with a hard coat at normal temperature (25°C).

[0280] In addition, for the laminated body with a hard coat of the present disclosure, even when a 180° bending test is repeatedly performed 50,000 times with a curvature radius of 5 mm with the hard coat on the inner side with respect to the laminated body, it is preferably free of cracks. Thus, the adhesion between the substrate and the hard coat is high, and the hard coat has high hardness.

[0281] [Examples]

[0282] Next, the present disclosure will be specifically described based on examples and comparative examples. The present disclosure is not limited to the following examples.

[0283] [Synthesis Example 1: Synthesis of Sesquioxane Derivative (S1)]

[0284] In a 1 L four-necked round-bottom flask equipped with a thermometer, a dropping funnel, and a stirring blade, (3-acryloyloxy)propyltrimethoxysilane (140.6 g, 0.6 mol), 3-methacryloyloxypropyltrimethoxysilane (99.3 g, 0.4 mol), 2-propanol (64.6 g), and hydroquinone (0.085 g) were measured, and the mixture was stirred well in a water bath at about 30 °C. Separately, an aqueous solution was prepared by mixing 35% hydrochloric acid (1.0 g, 9.6 mmol as hydrogen chloride) and pure water (150.7 g). While dropping the prepared aqueous solution from the dropping funnel over about 1 hour, the reaction solution was stirred, and then left standing overnight at room temperature. The amount of water added was 2.8 molar times the total amount of hydrolyzable groups of the raw material organosilicon compounds. Then, while heating the reaction solution to 60 °C, the solvent and the like in the reaction solution were removed by distillation under reduced pressure to obtain 170 g of a colorless transparent liquid sesquisiloxane derivative (S1).

[0285] Through 1H-NMR analysis of S1, it was confirmed that each structural unit was quantitatively introduced according to the input ratio of the raw materials. Regarding the synthesized sesquisiloxane derivative (S1), the viscosity at 25 °C was 6270 mPa·s, and the weight-average molecular weight (Mw) was 2010.

[0286] <Preparation of primer>

[0287] Relative to 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-903") as a silane coupling agent, methanol (MeOH) as an organic solvent and pure water as water were added, and the mixture was stirred using a rotation-revolution mixer to prepare a primer. In addition, the amount ratios of the respective components are as described in Table 1.

[0288] [Preparation of hard coat agent]

[0289] According to Table 1, relative to 1 part by mass of the sesquisiloxane derivative obtained in Synthesis Example 1 (labeled "Synthesis Example 1" in Table 1) or polyfunctional acrylate (manufactured by Toagosei Co., Ltd., "ARONIX (registered trademark) M-405"), 0.03 part by mass of 2-hydroxy-2-methyl-1-phenylpropan-1-one and 1 part by mass of propylene glycol monobutyl ether were added, and the mixture was stirred using a rotation-revolution mixer to separately prepare a photocurable hard coat agent.

[0290] [Preparation of laminate]

[0291] As a base material, a glass plate (glass plate specified in "R3202" manufactured by Engineering Test Service Co., Ltd. and JIS R3202:2011) was subjected to corona discharge treatment, and then the above-mentioned primer was applied using a No. 8 bar coater, and heated and dried at the temperature and time shown in Table 1 to form a bottom coat layer with a thickness of 1 μm or less. Then, a photocurable hard coat agent was applied using a No. 8 bar coater. After evaporating the solvent by heating at 60°C for 5 minutes in a forced-air oven, ultraviolet rays were irradiated under the following conditions to cure and form a hard coat layer with a thickness of 5 μm.

[0292] The primer used was the primer adjusted after the number of days shown in Table 1.

[0293] In addition, in Comparative Example 5, the formation of the bottom coat layer was not carried out.

[0294] - Ultraviolet Irradiation Conditions -

[0295] Lamp: High-pressure mercury lamp (ECS-4011GX manufactured by EYEGRAPHICS Co., Ltd.)

[0296] Lamp height: 10 cm

[0297] Conveyor belt speed: 5.75 m / min

[0298] Cumulative light quantity per pass: 360 mJ / cm 2 (Measured value of UV-A, UV POWER PUCKII manufactured by EIT Co., Ltd.)

[0299] Atmosphere: In the air

[0300] Number of cycles: 10 times

[0301] [Crosshatch Adhesion Test]

[0302] For the hard coat layer of the obtained laminate, the crosshatch adhesion test was carried out in accordance with JIS K5600-5-6 (1999). The results were calculated according to the following formula.

[0303] Formula: Residual square rate (%) = [(Number of non-peeled squares) / (Total number of squares)] × 100

[0304] [Pencil Hardness Test]

[0305] For the hard coat layer of the obtained laminate, the pencil hardness test was carried out in accordance with JIS K5600-5-4 (1999). The test was carried out 5 times for each of the pencils of 6H, 7H, and 8H. When there was no damage more than 4 times, it was evaluated as the pencil hardness or higher of that pencil, and recorded as "Y" in the table. On the other hand, when there were less than 4 scratches, it was evaluated as less than the pencil hardness of that pencil, and recorded as "N" in the table.

[0306] [Heat Resistance Test]

[0307] After heating the obtained laminate in a hot air oven at 125°C for 1000 hours, visually observe whether cracks occur in the coating. In the case where no cracks occur, mark it as "Y", and in the case where cracks occur, mark it as "N".

[0308] [Table 1]

[0309]

[0310] In the above results, from the comparison between Comparative Example 1 and Comparative Example 2, it can be seen that if the drying time of the primer is shortened, the adhesion between the substrate and the hard coat decreases, and the hardness of the hard coat decreases.

[0311] From the comparison between Comparative Examples 1 to 3 using a hard coat agent containing a general polyfunctional acrylate and Examples 1 to 3 using a hard coat agent containing a silsesquioxane derivative, it can be seen that Examples 1 to 3 have higher adhesion between the substrate and the hard coat and higher hardness of the hard coat compared to Comparative Examples 2 to 4.

[0312] From the comparison between Comparative Example 2 and Comparative Example 3 using a hard coat agent containing a general polyfunctional acrylate, in Comparative Example 3 using a primer after 3 days from preparation and Comparative Example 2 using a primer on the day of preparation, the adhesion between the substrate and the hard coat decreases, and the hardness of the hard coat decreases.

[0313] In contrast, from the comparison between Example 1 and Example 2 using a hard coat agent containing a silsesquioxane derivative, Example 2 using a primer after 3 days from preparation has the same adhesion between the substrate and the hard coat and the hardness of the hard coat as Example 1 using a primer on the day of preparation. From this, it can be seen that if a silsesquioxane derivative is used, even if a deteriorated primer is used, the adhesion between the substrate and the hard coat and the hardness of the hard coat are improved.

[0314] From the comparison between Examples 1 to 3 using a primer and Comparative Example 5 not using a primer, it can be seen that by using a primer, the adhesion and hardness of the substrate of the hard coat formed from a hard coat agent containing a silsesquioxane derivative are improved.

[0315] The disclosure of Japanese Patent Application No. 2022 - 195244 is incorporated herein by reference in its entirety.

[0316] All documents, patent applications, and technical standards described in this specification are incorporated by reference to the same extent as if each document, patent application, and technical standard is specifically and separately described as being incorporated by reference.

Claims

1. A method for manufacturing a laminate with a hard coating, which is a method for manufacturing a laminate with a hard coating having a substrate, a bottom coating, and a hard coating sequentially provided thereon, wherein, in sequence having: a primer coating step of coating a primer containing a silane coupling agent on the substrate; a drying step of drying the primer to form the primer coat; a hard coat agent coating step of coating a hard coat agent containing a sesquisiloxane derivative on the primer coat; and a curing step of curing the hard coat agent to form a hard coat.

2. The method for manufacturing a laminate with a hard coating according to claim 1, wherein, The pencil hardness of the surface of the hard coat in the laminate with the hard coat measured according to JIS K5600-5-4 (1999) is 5H or more.

3. The manufacturing method of the laminate with a hard coating according to claim 1, wherein, The substrate is a glass substrate.

4. The manufacturing method of the laminate with a hard coating according to claim 1, wherein, The substrate is a glass substrate specified in JIS R3202:2011. When the thickness of the hard coat is 5 μm or less, the pencil hardness of the surface of the hard coat in the laminate with the hard coat is 7H or more.

5. The method for manufacturing a laminate with a hard coat according to claim 1, wherein, The sesquisiloxane derivative is a sesquisiloxane derivative represented by the following formula (1), In formula (1), R 1 and R 2 are each independently an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, R 3 is an alkyl group having 1 to 6 carbon atoms, R 4 and R 5 are each independently a hydrogen atom, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a saturated or unsaturated cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, R 6 is an organic group having 2 to 12 carbon atoms having at least one of an ethylenic unsaturated bond and a carbon-carbon triple bond, R 7 and R 8 are each independently an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. When there are a plurality of R 5 , they may be the same as or different from each other. When there are a plurality of R 7 , they may be the same as or different from each other. When there are a plurality of R 8 , they may be the same as or different from each other. R 1 to R 8 may each independently be substituted in part of the structure by a substituent or a halogen atom. t, u, v, w, x, y, and z are each independently 0 or a positive number, and at least one of u and v is a positive number.

6. The manufacturing method of the laminate with a hard coating according to claim 1, wherein, The silane coupling agent is at least one selected from the group consisting of a silane coupling agent having an amino group, a silane coupling agent having a (meth)acryloyl group, and a silane coupling agent having a glycidyl group.

7. The method for manufacturing a laminate with a hard coating according to claim 1, wherein, The primer contains an organic solvent and water, and the organic solvent is at least one selected from the group consisting of an alcohol solvent, a ketone solvent, an ether solvent, and a nitrile.

8. The method for manufacturing a laminate with a hard coat according to claim 1, wherein, Before the primer coating step, there is a plasma treatment step of subjecting the substrate to plasma treatment.

9. A laminate with a hard coat, which has a substrate; a primer coat provided on the substrate and containing a cured product of a silane coupling agent; and a hard coat provided on the primer coat and containing a cured product of a hard coat agent containing a sesquisiloxane derivative.

10. The laminated body with a hard coating according to claim 9, wherein, The pencil hardness of the surface of the hard coat measured according to JIS K5600-5-4 (1999) is 5H or more.

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