Silsesquioxane derivative, method for producing same, curable composition, hard coat agent, cured product, hard coat layer, and substrate

Abstract

The present invention relates to: a silsesquioxane derivative which is represented by formula (1) and in which a cured product obtained after curing has an elastic modulus of more than 4.0 GPa at 23 DEG C; a method for producing the silsesquioxane derivative; a curable composition comprising the silsesquioxane derivative and a polymerization initiator; a hard coat agent comprising the curable composition; a hard coating layer obtained by curing the hard coating agent; and a base material provided with the hard coating layer. In formula (1), at least one of u and v is a positive number. # imgabs0 #

Description

Technical Field

[0001] The present disclosure relates to a silsesquioxane derivative and a method for producing the same, a curable composition, a hard coating agent, a cured product, a hard coating layer, and a substrate. Background Art

[0002] The hard coating agent is used in various parts requiring hardness, such as displays and housings. Various curable compositions are known as compositions used in the hard coating agent, and for example, polyfunctional acrylates are known.

[0003] Organic-inorganic composite materials in which an inorganic filler is mixed with an organic resin and organic-inorganic hybrid materials in which an organic unit and an inorganic unit coexist or are chemically bonded at the nanometer level are also attracting attention. For example, silsesquioxane derivatives are known as such organic-inorganic hybrid materials.

[0004] As a method for forming a hard coat layer, it is known that, for example, after applying a curable composition on a substrate using various known coating methods, the applied curable composition is irradiated with active energy rays such as ultraviolet rays for curing. If the substrate is in a film-like shape, a coating and curing method based on a roll-to-roll method can be used. It is known that a nanoimprint method can also be applied to the formation of a hard coat layer.

[0005] For example, Japanese Patent Laid-Open No. 10-030068 discloses a coating composition obtained by hydrolyzing an organic silicon compound having a hydrolyzable group by adding 50 to 5,000 parts by weight of water to 100 parts by weight of the organic silicon compound without using an organic solvent, the coating composition having a number average molecular weight of 500 or more, containing 5 to 100 mol % of silicon atoms having a (meth)acrylic functional substituent in all silicon atoms, and containing 30 to 100 mol % of R 1 The unit represented by SiX3 (X is a group selected from a hydroxyl group, a hydrolyzable group and a siloxane residue, and at least one of X is a siloxane residue) is represented by R 1 30 to 80 mol% of SiX3 contains a 1 The main component is an organopolysiloxane resin having silanol group units represented by Si(OH)Y2 (Y is a siloxane residue). Summary of the invention Technical problem to be solved by the invention

[0006] A hard coating agent and a silsesquioxane derivative having high hardness and low curing shrinkage are required.

[0007] The following contents are disclosed in the Japanese Patent Laid-Open No. 10-030068 Gazette: After applying a coating agent with an organopolysiloxane resin as the main component on the surface of a clean plastic molding, wood products, ceramics, glass, or metal, irradiating with high-energy rays to polymerize and cure the (meth) acrylic acid group, then heating to condense and cure the silanol group, thereby obtaining an article covered with a cured film having high hardness and excellent weather resistance. In addition, the following contents are disclosed: The coating agent composition disclosed in the Japanese Patent Laid-Open No. 10-030068 Gazette has scratch resistance, close adhesion, weather resistance, flame retardancy, storage stability, and flexibility, and can form a high hardness and flexible film on the surface of a plastic molding, wood products, ceramics, glass, or metal. However, there is neither a record nor a suggestion about the curing shrinkage rate.

[0008] The present disclosure is completed in view of the above situation, and its purpose is to provide a silsesquioxane derivative and a method for producing a cured product having a low cure shrinkage and excellent hardness, a curable composition containing the silsesquioxane derivative and a cured product formed by curing the same, a hard coating agent containing the silsesquioxane derivative, a hard coating layer formed by curing the same, and a substrate having the hard coating layer. Solutions to technical problems

[0009] Means for solving the above-mentioned problems include the following. <1> A silsesquioxane derivative represented by the following formula (1), wherein the elastic modulus of a cured product obtained after curing exceeds 4.0 GPa at 23°C.

[0010]

Chemical formula 1

[0011] [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 aralkylene group having 7 to 12 carbon atoms, and 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, and R 6 is an organic group having 2 to 12 carbon atoms and having at least one of an ethylenically unsaturated bond and a carbon-carbon triple bond, R 7 and R 8Each independently represents 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. 5 They can be the same or different. There are multiple R 7 They can be the same or different. There are multiple R 8 They can be the same or different. 1 ~R 8 A part of the structure may be substituted by a substituent or a halogen atom, each independently; 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.

[0012] <2> according to <1> The curing shrinkage rate of the silsesquioxane derivative is less than 7.3%. <3> according to <1> or <2> In the silsesquioxane derivative, t, x and z are 0 and satisfy 0≤y / (u+v+w)≤0.5. <4> according to <1> or <2> In the silsesquioxane derivative, t, y and z are 0 and satisfy 0≤x / (u+v+w)≤0.5. <5> according to <1> ~ <4> In any one of the silsesquioxane derivatives described in, u and v are each independently a positive number. <6> according to <5> The silsesquioxane derivative satisfies 0<v / u≤1. <7> A curable composition comprising <1> ~ <6> The silsesquioxane derivative described in any one of items and a polymerization initiator. <8> A hard coating agent comprising <7> The curable composition. <9> A solidified substance <7> The curable composition is cured. <10> A hard coating that <8> The hard coating agent is cured. <11> A substrate having <10> The hard coating. <12> A sort of <1> ~ <6> The method for producing a silsesquioxane derivative according to any one of the above, comprising the steps of: using an organic solvent, n SiX p At least one organosilicon compound represented by is hydrolyzed by adding 2 to 30 molar equivalents of water relative to the total amount of hydrolyzable groups possessed by the organosilicon compound, wherein n represents an integer of 0 to 3, p represents an integer of 1 to 4, n+p=4, R represents a group bonded to the silicon atom via a carbon atom in the silsesquioxane derivative, and X represents a hydrolyzable group. Effects of the Invention

[0013] According to the present disclosure, there can be provided a silsesquioxane derivative capable of producing a cured product having a low cure shrinkage and excellent hardness, a method for producing the same, a curable composition comprising the silsesquioxane derivative, and a cured product obtained by curing the same, a hard coating agent comprising the silsesquioxane derivative, a hard coating layer obtained by curing the same, and a substrate having the hard coating layer. DETAILED DESCRIPTION

[0014] Hereinafter, the method for implementing the present disclosure is described in detail. However, the present disclosure is not limited to the following embodiments. In the following embodiments, its constituent elements (including element steps, etc.) are not necessary except for the cases specifically indicated. The same is true for numerical values ​​and their ranges, and the present disclosure is not limited. In the present specification, in a numerical range expressed using "to", the numerical values ​​described before and after "to" are included as the minimum value and the maximum value. In the numerical range recorded in this specification, the upper limit or lower limit recorded in one numerical range can be replaced by the upper limit or lower limit of the numerical range recorded in other stages. In addition, in the numerical range recorded in this specification, the upper limit or lower limit of the numerical range can be replaced by the value shown in the embodiment. In addition, in this specification, a combination of two or more preferred aspects is a more preferred aspect.

[0015] In this specification, R in formula (1) 1 ~R 8 Each of them may be independently substituted with a substituent or a halogen atom. 1 ~R 8 A part of the structure may be substituted independently 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 thiol group, an isocyanurate group, a urea group, an isocyanate group, a carboxyl group, an acid anhydride group or a halogen atom. R in formula (1) 1 ~R 8 They may also be independently unsubstituted, for example, R 1 ~R 3 or R 6 ~R 8 (Preferably R 1 ~R 3 and R 6 ~R 8 ) may also be unsubstituted.

[0016] 〔Silsesquioxane derivatives〕 The silsesquioxane derivative disclosed in the present invention is represented by the following formula (1), and the elastic modulus of a cured product obtained after curing exceeds 4.0 GPa at 23°C.

[0017]

Chemical formula 2

[0018] [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 aralkylene group having 7 to 12 carbon atoms, and 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, and R 6 is an organic group having 2 to 12 carbon atoms and having at least one of an ethylenically unsaturated bond and a carbon-carbon triple bond, R 7 and R 8 Each independently represents 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. 5 They can be the same or different. There are multiple R 7 They can be the same or different. There are multiple R 8 They can be the same or different. 1 ~R 8 A part of the structure may be substituted by a substituent or a halogen atom, each independently; 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.

[0019] As described above, the hardness and / or cure shrinkage ratio of the cured products of the conventional silsesquioxane derivatives are insufficient. The present inventors have conducted intensive studies and have found that, by adopting the above-mentioned configuration, it is possible to provide a silsesquioxane derivative capable of producing a cured product having a low cure shrinkage and excellent hardness. At least one of u and v in the formula (1) is a positive number, and by adding 2 to 30 molar equivalents of water relative to the total amount of hydrolyzable groups possessed by the organic silicon compound for hydrolysis, a moderate cross-linked structure can be obtained after curing. Therefore, it is presumed that a cured product with low curing shrinkage and excellent hardness can be produced.

[0020] Furthermore, the silsesquioxane derivative of the present disclosure is also excellent in storage stability and curability by active energy rays such as ultraviolet rays (hereinafter, also referred to as UV).

[0021] (Elastic modulus of cured product) The elastic modulus of the cured product obtained after curing of the silsesquioxane derivative disclosed in the present invention at 23°C exceeds 4.0 GPa. From the viewpoint of cure shrinkage, hardness, storage stability and curling suppression during curing, it is preferably greater than 4.1 GPa, more preferably greater than 4.1 GPa and less than 9.0 GPa, further preferably greater than 4.15 GPa and less than 8.0 GPa, and particularly preferably greater than 4.20 GPa and less than 7.0 GPa.

[0022] The method for measuring the elastic modulus of the cured product of the silsesquioxane derivative of the present disclosure at 23° C. is as follows. In the present disclosure, a silsesquioxane derivative capable of producing a cured product having excellent hardness means that the cured product of the silsesquioxane derivative has excellent elastic modulus.

[0023] <Preparation of Photocurable Coating Agent> 0.03 parts by mass of 2-hydroxy-2-methyl-1-phenylpropane-1-one and 1 part by mass of propylene glycol monobutyl ether were added to 1 part by mass of the silsesquioxane derivative to be measured, and the mixture was stirred with an autorotating and orbiting mixer to prepare a photocurable coating agent.

[0024] <Production of Photocurable Film> After applying the photocurable coating agent to a TAC (triacetyl cellulose) film using a No. 20 bar coater, the applied photocurable coating agent was dried at 60° C. for 10 minutes and then cured by ultraviolet irradiation under the following conditions to prepare a photocured film. Under the above coating conditions, the film thickness was about 10 μm. -UV irradiation conditions- Lamp: High-pressure mercury lamp (ECS-4011GX manufactured by EYE GRAPHICS Co., Ltd.) Height of lamp: 10cm Conveyor belt speed: 5.75m / min Accumulated light volume per pass: 360mJ / cm 2 (UV-A, measured value of UV POWER PUCK II manufactured by EIT) Atmosphere: Atmospheric Pass times: 10 times

[0025] <Measurement of elastic modulus> The obtained photocured film was used to measure the indentation hardness at 23° C. and a strain rate of 0.05 / s using a nanoindenter (Nano Indenter G200 manufactured by Agilent Technologies, using a Berkovich indenter). The modulus values ​​at indentation depths of 500 nm to 800 nm were averaged to calculate the elastic modulus.

[0026] (Curing shrinkage) From the viewpoint of hardness and curling suppression during curing, the curing shrinkage of the silsesquioxane derivative disclosed herein is preferably 7.3% or less, more preferably 7.0% or less, and particularly preferably 6.6% or less. The lower limit of the curing shrinkage is 0%.

[0027] The method for measuring the cure shrinkage of the silsesquioxane derivative disclosed in the present invention is as follows.

[0028] <Measurement of density> For the silsesquioxane derivative to be measured, the density measurement was performed in accordance with JIS K0061-7 (2001).

[0029] <Preparation of Photocurable Composition> 0.03 parts by mass of 2-hydroxy-2-methyl-1-phenylpropane-1-one was added to 1 part by mass of the measured silsesquioxane derivative, and the mixture was stirred with an autorotating-revolutionary mixer to prepare photocurable compositions.

[0030] <Production of Photocured Materials> A photocurable composition was injected into a silicone mold on a release polyethylene terephthalate (PET) film, and the release PET film was overlapped and fixed by sandwiching them with glass plates. Then, the composition was irradiated with ultraviolet rays under the following conditions for curing to prepare a photocured product. -UV irradiation conditions- Lamp: High-pressure mercury lamp (ECS-4011GX manufactured by EYE GRAPHICS Co., Ltd.) Height of lamp: 10cm Conveyor belt speed: 5.75m / min Accumulated light volume per pass: 360mJ / cm 2 (UV-A, measured value of UV POWER PUCK II manufactured by EIT) Atmosphere: Atmospheric Pass times: 20 times

[0031] <Measurement of Density of Photocured Material> The density of the photocured product was measured in accordance with JIS K0061-8 (2001).

[0032] <Calculation of curing shrinkage> The calculation was performed based on (density of cured product - density before curing) / density before curing×100.

[0033] Each structural unit that may be contained in the silsesquioxane derivative of the present disclosure is referred to as structural units (a) to (g) as described below.

[0034]

Chemical formula 3

[0035] In the silsesquioxane derivative disclosed herein, 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 disclosed herein comprises at least one of the structural unit (b) and the structural unit (c) among the structural units (a) to (g) described above, and may also comprise at least one of the structural unit (a), the structural unit (d), the structural unit (e), the structural unit (f) and the structural unit (g), as required.

[0036] In formula (1), t, u, v, w, x, y and z represent the molar ratio of the constituent units (a) to (g). In addition, in formula (1), t, u, v, w, x, y and z represent the relative molar ratio of the constituent units (a) to (g) that the silsesquioxane derivative represented by formula (1) may contain. The molar ratio can be obtained, for example, from the NMR (nuclear magnetic resonance) analysis value of the silsesquioxane derivative disclosed in the present invention. In addition, when the reaction rate of each raw material of the silsesquioxane derivative is clear or the yield is 100%, it can be obtained from the input amount of the raw materials. For example, the molar ratio of each constituent unit of the silsesquioxane derivative can also be determined by dissolving a sample in deuterated chloroform or the like. 1 H-NMR analysis, and further 29 Si-NMR analysis was used for calculation. It is also possible to decompose the silsesquioxane derivative into its constituent units using a base or the like, and to estimate the structure of the original silsesquioxane derivative from the ratio of the constituent units or the like. The molar ratio of each structural unit of the silsesquioxane derivative may be determined by combining known methods such as mass spectrometry analysis and IR (infrared absorption spectroscopy) analysis as necessary.

[0037] Each of the constituent units (b) to (g) in formula (1) may be one or more. In addition, the arrangement order in formula (1) represents the composition of the constituent units and does not mean the arrangement order of the silsesquioxane derivatives. Therefore, the condensed form of the constituent units in the silsesquioxane derivatives disclosed in the present invention does not necessarily need to follow the arrangement order of formula (1). Next, the structural units (a) to (g) are described in detail.

[0038] (Constituent unit (a)) The constituent unit (a) is composed of four O atoms per silicon atom. 1 / 2 (two oxygen atoms are counted). In addition, a Q unit refers to a unit having four O atoms per silicon atom. 1 / 2unit.

[0039] The ratio of the constituent unit (a) in the silsesquioxane derivative disclosed in the present invention is not particularly limited. For example, from the viewpoint of the viscosity of the silsesquioxane derivative and the hardness of the cured product, the molar ratio of the constituent unit (a) in all the constituent units (t / (t+u+v+w+x+y+z)) is preferably 0.1 or less, more preferably 0.05 or less, and further preferably 0. Here, a molar ratio of 0 means that the corresponding constituent unit is not included, and the same meaning is also meant below.

[0040] (Constituent unit (b)) The constituent unit (b) is a unit having three O atoms per silicon atom. 1 / 2 (1.5 as oxygen atoms), and the acryloyloxy group is 1 A T unit is a unit having three O atoms bonded to a silicon atom. 1 / 2 unit.

[0041] In constituent unit (b), R 1 It 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 aralkylene group having 7 to 12 carbon atoms. 1 An alkylene group having 1 to 10 carbon atoms or a cycloalkylene group having 3 to 10 carbon atoms is preferred, and an alkylene group having 1 to 10 carbon atoms is more preferred.

[0042] 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. The cycloalkylene group having 3 to 10 carbon atoms is preferably a cycloalkylene group having 3 to 6 carbon atoms, and more preferably a cycloalkylene group having 4 to 6 carbon atoms. The cycloalkylene group having 3 to 10 carbon atoms may have a branch.

[0043] The ratio of the structural unit (b) in the silsesquioxane derivative disclosed in the present invention is not particularly limited. For example, from the viewpoint of cure shrinkage, hardness, storage stability, and UV or other active energy ray curing, the molar ratio of the structural unit (b) in all structural units (u / (t+u+v+w+x+y+z)) 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. The molar ratio of the structural unit (b) in all the structural units may be 0.

[0044] In addition, from the viewpoint of cure shrinkage, hardness, storage stability and curability with active energy rays such as UV, it is preferred to satisfy u>v, more preferably the molar ratio of the constituent unit (b) (u / (t+u+v+w+x+y+z))>the molar ratio of the constituent unit (c) (v / (t+u+v+w+x+y+z))+0.05 is satisfied, and particularly preferably the molar ratio of the constituent unit (b) (u / (t+u+v+w+x+y+z))>the molar ratio of the constituent unit (c) (v / (t+u+v+w+x+y+z))+0.10 is satisfied.

[0045] (Constituent unit (c)) The constituent unit (c) is a unit having three O atoms per silicon atom. 1 / 2 (1.5 in terms of oxygen atoms), and the hydrogen atoms are R 3 Substituted acryloyloxy (methacryloyloxy, etc.) 2 T units bonded to silicon atoms.

[0046] In the constituent unit (c), R 2 R 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 aralkylene group having 7 to 12 carbon atoms. 2 The preferred embodiment is the same as R in the constituent unit (b). 1 same.

[0047] In the constituent unit (c), R 3 It 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, preferably methyl and ethyl, and more preferably methyl.

[0048] The ratio of the structural unit (c) in the silsesquioxane derivative disclosed in the present invention is not particularly limited. For example, from the viewpoint of cure shrinkage, hardness, storage stability, and UV or other active energy ray curing, the molar ratio (v / (t+u+v+w+x+y+z)) of the structural unit (c) in all the structural units is preferably 0 to 0.8, more preferably 0.05 to 0.7, further preferably 0.2 to 0.7, and particularly preferably 0.35 to 0.55. The molar ratio of the structural unit (c) in all the structural units may be 0.

[0049] In the formula (1), at least one of u and v is a positive number, and from the viewpoint of the hardness of a cured product, it is preferred that u and v are each independently a positive number.

[0050] From the viewpoints of cure shrinkage, hardness, storage stability, UV and other active energy ray curing properties, and viscosity, the total molar ratio of constituent units (b) and constituent units (c) in all constituent units ((u+v) / (t+u+v+w+x+y+z)) is preferably 0.3 to 1, more preferably 0.5 to 1, further preferably 0.7 to 1, and particularly preferably 0.9 to 1.

[0051] (Constituent unit (d)) The constituent unit (d) is a unit having three O atoms per silicon atom. 1 / 2 (1.5 in terms of oxygen atoms), and R 4 T units bonded to silicon atoms.

[0052] In the constituent unit (d), R 4 It 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.

[0053] The saturated or unsaturated alkyl group having 1 to 20 carbon atoms may be linear or branched. 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.

[0054] 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 viewpoint of heat resistance and hardness of the cured product, a methyl group or an ethyl group is preferred, and a methyl group is more preferred.

[0055] Examples of the unsaturated alkyl group having 1 to 10 carbon atoms include vinyl, 2-propenyl, and ethynyl.

[0056] The saturated or unsaturated cycloalkyl group having 3 to 8 carbon atoms may have a branch. 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.

[0057] The aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 10 carbon atoms.

[0058] 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 a phenyl group are substituted with an alkyl group having 1 to 10 carbon atoms, and a naphthyl group. From the viewpoint of heat resistance and hardness of a cured product, a phenyl group is preferred.

[0059] The aralkyl group having 7 to 20 carbon atoms is preferably an aralkyl group having 7 to 10 carbon atoms.

[0060] Examples of the aralkyl group having 7 to 20 carbon atoms include groups 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. Examples include benzyl and phenethyl groups, and benzyl groups are preferred from the viewpoint of heat resistance and hardness of a cured product.

[0061] In R 4 When a part of the structure represented by is substituted by a substituent or a halogen atom, R 4 , for example, 3-glycidoxypropyl, 2-(3,4-epoxycyclohexyl)ethyl, 3-(3-ethyloxetan-3-yl)methoxypropyl, 3-hydroxypropyl, 3-aminopropyl, 3-dimethylaminopropyl, 3-hydroxypropyl, 3-aminopropyl hydrochloride, 3-dimethylaminopropyl hydrochloride, p-phenylvinyl, N-2-(aminoethyl)-3-aminopropyl, N-phenyl-3-aminopropyl, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyl hydrochloride, 3-ureidopropyl, 3-mercaptopropyl, 3-isocyanatepropyl, 3-carboxypropyl and 3-chloropropyl.

[0062] The proportion of the structural unit (d) in the silsesquioxane derivative disclosed herein is not particularly limited. For example, from the viewpoint of the hardness of the cured product, the molar ratio of the structural unit (d) to the total structural units (w / (t+u+v+w+x+y+z)) is preferably 0.1 or less, more preferably 0.05 or less, and even more preferably 0.

[0063] (Constituent unit (e)) The constituent unit (e) is a unit having two O atoms per silicon atom. 1 / 2 (one oxygen atom), and two R 5 A D unit is a unit having two O atoms bonded to a silicon atom. 1 / 2 unit.

[0064] In the constituent 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. 5 They may be the same or different from each other. 5 The preferred embodiment is the same as R in the constituent unit (d). 4 same.

[0065] The proportion of the constituent unit (e) in the silsesquioxane derivative disclosed in the present invention is not particularly limited. For example, from the viewpoint of hardness when a cured product is prepared, the molar ratio of the constituent unit (e) in all the constituent units (x / (t+u+v+w+x+y+z)) is preferably 0.1 or less, more preferably 0.05 or less, more preferably 0.025 or less, more preferably 0.005 or less, and further preferably 0. On the other hand, from the viewpoint of cure shrinkage and bending resistance, x is preferably a positive number, and the molar ratio of the constituent unit (e) in all the constituent units (x / (t+u+v+w+x+y+z)) is more preferably 0.005 or more, and further preferably 0.025 or more.

[0066] (Constituent unit (f)) The constituent unit (f) is a unit having one O for each silicon atom. 1 / 2 (0.5 in terms of oxygen atoms), and one R 6 and two R 7 The M unit is an M unit bonded to a silicon atom. 1 / 2 unit.

[0067] In the constituent unit (f), R 6 It is an organic group having 2 to 12 carbon atoms and having at least one of an ethylenically unsaturated bond and a carbon-carbon triple bond.

[0068] As the organic group having 2 to 12 carbon atoms and having an ethylenically unsaturated bond, for example, vinyl, o-styryl, m-styryl, p-styryl, acryloyloxymethyl, methacryloyloxymethyl, 2-acryloyloxyethyl, 2-methacryloyloxyethyl, 3-acryloyloxypropyl, 3-methacryloyloxypropyl, 8-acryloyloxyoctyl, 8-methacryloyloxyoctyl, 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 can be mentioned. From the viewpoint of hardness when a cured product is prepared, vinyl, 2-propenyl, o-styryl, m-styryl or p-styryl is preferred, and vinyl is more preferred.

[0069] In the constituent 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), there are a plurality of R 7 They can be the same or different from each other.

[0070] 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 viewpoint of heat resistance and hardness of the cured product, a methyl group or an ethyl group is preferred, and a methyl group is more preferred.

[0071] Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a group in which one or more hydrogen atoms of a phenyl group are substituted with an alkyl group having 1 to 4 carbon atoms, and a naphthyl group. From the viewpoint of heat resistance and hardness of a cured product, a phenyl group is preferred.

[0072] Examples of the aralkyl group having 7 to 10 carbon atoms include groups in which one hydrogen atom of an alkyl group having 1 to 4 carbon atoms is substituted with an aryl group such as a phenyl group. Examples include benzyl and phenethyl groups, and benzyl groups are preferred from the viewpoint of heat resistance and hardness of a cured product.

[0073] The proportion of the constituent unit (f) in the silsesquioxane derivative disclosed herein is not particularly limited. For example, from the viewpoint of cure shrinkage, hardness, storage stability, and UV and other active energy ray curing properties, the molar ratio of the constituent unit (f) in all the constituent units (y / (t+u+v+w+x+y+z)) is preferably 0.5 or less, more preferably 0.3 or less, and further preferably 0.1 or less. The molar ratio of the constituent unit (f) in all the constituent units (y / (t+u+v+w+x+y+z)) may be 0 or greater than 0.001.

[0074] (Constituent unit (g)) The constituent unit (g) is a unit having one O for each silicon atom. 1 / 2 (0.5 in terms of oxygen atoms), and three R 8 The M unit is bonded to the silicon atom.

[0075] In the constituent 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), there are a plurality of R 8 They may be the same or different from each other. 8 The preferred embodiment is the same as R in the constituent unit (f). 7 same.

[0076] The ratio of the constituent unit (g) in the silsesquioxane derivative disclosed herein is not particularly limited. For example, from the viewpoint of the hardness of the cured product, the molar ratio of the constituent unit (g) to the total constituent units (z / (t+u+v+w+x+y+z)) is preferably 0.1 or less, more preferably 0.05 or less, and even more preferably 0.

[0077] (Other constituent units (h)) The silsesquioxane derivatives disclosed herein may further include (R 9 O 1 / 2 ) as a structural unit not containing Si (hereinafter, also referred to as structural unit (h)). Here, R 9 It is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms may be either an aliphatic group or an alicyclic group, and may be either a straight chain or a branched chain. Specific examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, and hexyl.

[0078] The constituent unit (h) is an alkoxy group contained in the silicon compound described later, or an alkoxy group generated by substitution of an alcohol contained in the reaction solvent for a hydrolyzable group of the silicon compound. It may be an alkoxy group that remains in the molecule without being hydrolyzed or polycondensed, or it may be a hydroxyl group that remains in the molecule after being hydrolyzed but not polycondensed.

[0079] In formula (1), from the viewpoint of cure shrinkage, hardness, storage stability, and UV or other active energy ray curing, preferably, t, x, and z are 0, and w and y are each independently 0 or a positive number, and more preferably, t, w, x, y, and z are 0. In addition, in formula (1), from the viewpoint of cure shrinkage, hardness, storage stability, and UV or other active energy ray curing, preferably, 0≤y / (u+v+w)≤0.5 is satisfied, more preferably, 0≤y / (u+v+w)≤0.3 is satisfied, and even more preferably, 0≤y / (u+v+w)≤0.1 is satisfied.

[0080] Alternatively, in formula (1), from the viewpoint of curing shrinkage, hardness, storage stability, and UV or other active energy ray curing, preferably, t, y, and z are 0, and w and x are each independently 0 or a positive number. In addition, in formula (1), from the viewpoint of curing shrinkage, hardness, storage stability, and UV or other active energy ray curing, preferably, 0≤x / (u+v+w)≤0.5 is satisfied, more preferably, 0≤x / (u+v+w)≤0.3 is satisfied, and further preferably, 0≤x / (u+v+w)≤0.1 is satisfied.

[0081] In formula (1), from the viewpoint of cure shrinkage, hardness, storage stability, and UV curability, it is preferred that u and v are each independently a positive number. In addition, from the viewpoint of cure shrinkage, hardness, storage stability and curability by active energy rays such as UV, u and v preferably satisfy 0<v / u≤1, more preferably satisfy 0.1≤v / u≤1, further preferably satisfy 0.2≤v / u≤1, and particularly preferably satisfy 0.3≤v / u≤1.

[0082] (Weight average molecular weight of silsesquioxane derivative) The weight average molecular weight (hereinafter also referred to as "Mw") of the silsesquioxane derivative disclosed in the present invention is not particularly limited, and may be, for example, 300 to 30,000, 500 to 15,000, 700 to 10,000, or 1,000 to 5,000. In addition, Mw in the present disclosure refers to a value converted from a molecular weight measured by GPC (gel permeation chromatography) using polystyrene as a standard substance. As measurement conditions of Mw, for example, measurement conditions in [Examples] described later can be used.

[0083] (Viscosity of silsesquioxane derivatives) The silsesquioxane derivative disclosed herein has a viscosity at 25° C. of preferably 10 to 50,000 mPa·s, more preferably 100 to 40,000 mPa·s, further preferably 1,000 to 30,000 mPa·s, and particularly preferably 2,000 to 20,000 mPa·s. In addition, in this disclosure, the viscosity at 25° C. refers to a value measured using an E-type viscometer (cone-plate type viscometer, for example, TVE22H type viscometer manufactured by Toki Sangyo Co., Ltd.).

[0084] (Method for producing silsesquioxane derivative) The silsesquioxane derivative disclosed in the present invention can be produced by a known method. The method for producing a silsesquioxane derivative is disclosed in detail as a method for producing polysiloxane in International Publication No. 2013 / 031798 and the like.

[0085] The method for producing the silsesquioxane derivative disclosed herein preferably comprises the following steps: using an organic solvent to n SiX p At least one organosilicon compound represented by (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 silsesquioxane derivative, and X represents a hydrolyzable group) is hydrolyzed by adding 2 to 30 molar equivalents of water relative to the total amount of hydrolyzable groups possessed by the organosilicon compound (hereinafter also referred to as "hydrolysis step"). As R, preferably, there is mentioned a group (H2C=CHCOO-R 1 -、H2C=C(R 3 )COO-R 2 - and R 4 ~R 8 wait). Preferred examples of X include an alkoxy group, a siloxy group or a halogen atom, and more preferably an alkoxy group or a siloxy group.

[0086] In the hydrolysis step, it is preferred that not only the hydrolysis of the organosilicon compound but also the hydrolysis and polycondensation reaction of the organosilicon compound and, if necessary, other silicon compounds be performed. In the hydrolysis step, after the organosilicon compound and, if necessary, other silicon compounds are subjected to hydrolysis and polycondensation to obtain a silsesquioxane derivative as an intermediate product, the intermediate product may be subjected to further hydrolysis and polycondensation with the organosilicon compound and the like.

[0087] When the intermediate product is obtained as described above, after the hydrolysis and polycondensation reaction of the organosilicon compound and other silicon compounds as needed, the hydrolysis and polycondensation reaction of the intermediate product obtained and the compound in which n is 3 and p is 1 in the organosilicon compound can be further performed. Thus, the silsesquioxane derivative whose terminal portion is blocked with the structural unit (f) derived from the compound in which n is 3 and p is 1 in the organosilicon compound can be appropriately synthesized, the viscosity increase of the silsesquioxane derivative is suppressed, and the storage stability becomes better.

[0088] The method for producing a silsesquioxane derivative disclosed herein preferably comprises a distillation step of distilling off the reaction solvent, by-products, residual monomers, water, etc. in the reaction solution after hydrolysis and polycondensation of the silicon compound in the presence of a reaction solvent.

[0089] Examples of the compound having an acryl group among the organic silicon compounds include (3-acryloxypropyl)trimethoxysilane, (3-acryloxypropyl)triethoxysilane, (8-acryloxyoctyl)trimethoxysilane, and (3-acryloxypropyl)trichlorosilane.

[0090] Examples of the organosilicon compound having a methacryl group among the organosilicon compounds include (3-methacryloxypropyl)trimethoxysilane, (3-methacryloxypropyl)triethoxysilane, (8-methacryloxyoctyl)trimethoxysilane, and (3-methacryloxypropyl)trichlorosilane.

[0091] Examples of the organosilicon compound that provides two structural units (f) by hydrolysis include 1,3-divinyltetramethyldisiloxane, 1,3-bis(p-phenylene)tetramethyldisiloxane, 1,3-bis(3-acryloxypropyl)tetramethyldisiloxane, 1,3-bis(3-methacryloxypropyl)tetramethyldisiloxane, and the like; and methoxydimethylvinylsilane, ethoxydimethylvinylsilane, chlorodimethylvinylsilane, dimethylvinylsilanol, (3-acryloxypropyl)dimethylmethoxysilane, (3-methacryloxypropyl)dimethylmethoxysilane, p-phenylene dimethylmethoxysilane, and ethynyl dimethylmethoxysilane.

[0092] Examples of the silicon compound that provides the structural unit (a) by hydrolysis include tetramethoxysilane and tetraethoxysilane.

[0093] Examples of the organic silicon compound in which n is 3 and p is 1 include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, octyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane, cyclohexyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, p-phenyltrimethoxysilane, ethynyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane. alkyl, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatepropyltriethoxysilane, tris(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropyltrimethoxysilane, 3-ethyl-3-[{3-(trimethoxysilyl)propoxy}methyl]oxetane, and 3-ethyl-3-[{3-(triethoxysilyl)propoxy}methyl]oxetane.

[0094] Examples of the organic silicon compound wherein n is 2 and p is 2 include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, propylmethyldimethoxysilane, octylmethyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, benzylmethyldimethoxysilane, cyclohexylmethyldimethoxysilane, vinylmethyldimethoxysilane, allylmethyldimethoxysilane, p-phenylphenylmethyldimethoxysilane, ethynylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, silane, 3-glycidoxypropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropylmethyldimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropylmethyldimethoxysilane hydrochloride, 3-ureidopropylmethyldialkoxysilane, 3-isocyanatepropylmethyldiethoxysilane, (3-acryloxypropyl)methyldimethoxysilane and (3-methacryloxypropyl)methyldiethoxysilane.

[0095] Examples of the organic silicon compound in which n is 1 and p is 3 include hexamethyldisiloxane, trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane, and dimethylphenylmethoxysilane.

[0096] In the hydrolysis step, the reaction solvent is not particularly limited, but alcohol is preferably used as the organic solvent. Alcohol is an alcohol in a narrow sense represented by the general formula R-OH, and is a compound having no functional group other than an alcoholic hydroxyl group. The alcohol is not particularly limited, and examples thereof include 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. Among these, 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. In the hydrolysis step, these alcohols may be used alone or in combination of two or more.

[0097] The organic solvent used in the hydrolysis step may be alcohol alone or may be a solvent mixed with at least one sub-solvent. The sub-solvent may be any one of a polar solvent and a non-polar solvent, or may be a combination of both. Examples of the organic solvent other than alcohol include xylene, toluene, methyl ethyl ketone, methyl isobutyl ketone, and propylene glycol monomethyl ether.

[0098] The hydrolysis and condensation reactions in the hydrolysis step are carried out in the presence of water. In the hydrolysis step, it is preferred that 1.5 to 30 molar equivalents of water are added to carry out hydrolysis and further condensation based on the total amount of the hydrolyzable groups of the organosilicon compound. Furthermore, in the hydrolysis step, from the viewpoint of the cure shrinkage, hardness, storage stability and curling 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 relative to the total amount of the hydrolyzable groups possessed by the organosilicon compound.

[0099] In addition, the hydrolysis and polycondensation reaction of the silicon compound can be carried out without a catalyst or with a catalyst. When a catalyst is used, it is preferred to use an inorganic acid such as sulfuric acid, nitric acid, hydrochloric acid, and phosphoric acid; an acid catalyst exemplified by an organic acid such as formic acid, acetic acid, oxalic acid, and p-toluenesulfonic acid; an alkali catalyst such as ammonia, tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate, and the like, and it is more preferred to use an acid catalyst. The amount of the catalyst used is preferably an amount corresponding to 0.01 mol % to 20 mol %, more preferably an amount corresponding to 0.1 mol % to 10 mol %, based on the total amount (mol) of silicon atoms contained in the silicon compound.

[0100] The completion of the hydrolysis and polycondensation reaction in the hydrolysis step can be appropriately detected by methods described in various publications, etc. In the hydrolysis step of the method for producing a silsesquioxane derivative of the present disclosure, an auxiliary agent may be added to the reaction system.

[0101] The distillation step can be performed at normal pressure or reduced pressure, at room temperature, under heating, or under cooling.

[0102] The method for producing a silsesquioxane derivative may include a neutralization step of neutralizing the catalyst before the distillation removal step. Alternatively, the method may include a step of removing a salt generated by neutralization by washing with water or the like.

[0103] In addition, the silsesquioxane derivative represented by formula (1) may include a group that is ring-opened by adding an acid or the like to an oxetane group or an epoxy group in a side chain functional group of a silicon compound used as a raw material for production, and may also include a hydroxyalkyl group generated by decomposing an organic group having a (meth)acryloyl group, and may also include a group that is added with an acid or the like to an unsaturated hydrocarbon group or the like. As a specific example, for example, a structure represented by the following formula (A) and / or a structure represented by formula (B) may be cited as a part of formula (1). As a content ratio, if the amount of the organic group having an original oxetane group or an epoxy group, an original (meth)acryloyl group, or an original unsaturated hydrocarbon group corresponding to the amount of the organic group having an original oxetane group or an epoxy group, an original (meth)acryloyl group, or an original unsaturated hydrocarbon group from the silicon compound as a raw material is 50 mol% or less, there is no problem in implementing the present disclosure, preferably 30 mol% or less, and more preferably 10 mol% or less. Formula (A) and formula (B) both exemplify T units, but they may also be similar D units, M units, etc.

[0104]

Chemical formula 4

[0105]

Chemical formula 5

[0106] [Curing composition] The curable composition of the present disclosure includes the silsesquioxane derivative of the present disclosure and a polymerization initiator. The curable composition of the present disclosure can be suitably used as a hard coating agent. The curable composition of the present disclosure may contain various components (hereinafter also referred to as “other components”) as necessary.

[0107] (Polymerization initiator) The polymerization initiator is not particularly limited, and examples thereof include photopolymerization initiators and thermal polymerization initiators. Examples of the photopolymerization initiator include photoradical polymerization initiators. As a thermal polymerization initiator, a thermal radical polymerization initiator is mentioned, for example. As the photopolymerization initiator and the thermal polymerization initiator, known compounds can be used.

[0108] Examples of the photoradical polymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholino)phenyl Acetophenone compounds such as 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone] and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)benzyl]phenyl}-2-methyl-propane-1-one; benzophenones such as benzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone and 4-benzoyl-4'-methyldiphenyl sulfide α-ketoester compounds such as methyl benzoyl formate, 2-[2-oxo-2-phenylacetoxyethoxy]ethyl hydroxyphenylacetate and 2-[2-hydroxyethoxy]ethyl hydroxyphenylacetate; phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; benzoin, benzoin Benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; titanocene compounds; acetophenone / benzophenone hybrid photoinitiators such as 1-(4-(4-benzoylphenylsulfanyl)phenyl)-2-methyl-2-(4-methylphenylsulfinyl)propane-1-one; oxime ester photopolymerization initiators such as 1-(4-phenylthiophenyl)-2-(O-benzoyloxime)-1,2-octanedione; and camphorquinone. These may be used alone or in combination of two or more.

[0109] The thermal radical polymerization initiator is not particularly limited, and examples thereof include peroxides and azo initiators.

[0110] Examples of the peroxide include hydrogen peroxide; inorganic peroxides such as sodium persulfate, ammonium persulfate, and 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; Hexane, 2,2-bis(4,4-di-butylperoxycyclohexyl)propane, 1,1-bis(tert-butylperoxy)cyclododecane, tert-hexylperoxyisopropylmonocarbonate, tert-butylperoxymaleic acid, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxylaurate, 2,5-dimethyl-2,5-bis(m-toluic acid peroxy)hexane, tert-butylperoxyisopropylmonocarbonate, tert-butylperoxymaleic acid, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxylaurate, 2-Ethylhexyl monocarbonate, tert-hexyl peroxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, tert-butyl peroxyacetate, 2,2-bis(tert-butylperoxy)butane, tert-butyl peroxybenzoate, n-butyl-4,4-bis(tert-butylperoxy)valerate, di-tert-butyl peroxyisophthalate, α,α'-bis(tert-butylperoxy)diisopropylbenzene, peroxy Organic peroxides such as diisopropylbenzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butyl isopropylbenzene peroxide, di-tert-butyl peroxide, terpane hydroperoxide, 2,5-dimethyl-2,5-di-tert-butyl peroxyhexane-3, diisopropylbenzene hydroperoxide, tert-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, isopropylbenzene hydroperoxide, tert-hexyl hydroperoxide and tert-butyl hydroperoxide. These may be used alone or in combination of two or more.

[0111] Examples of the azo initiator include azo compounds such as 2,2'-azobisisobutyronitrile, 1,1'-azo(cyanocyclohexane), 2-(carbamoylazo)isobutyronitrile (2-(carbamoylazo)isobutylonitril), 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, azodi-tert-octane and azodi-tert-butylene. These may be used alone or in combination of two or more. In addition, the redox reaction can also be carried out by combining with a redox polymerization initiation system using a peroxide and a reducing agent, wherein the reducing agent is ascorbic acid, sodium ascorbate, sodium isoascorbate, tartaric acid, citric acid, metal salts of formaldehyde sulfoxylate, sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium pyrosulfite, ferric chloride, etc.

[0112] In the curable composition of the present disclosure, 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 even more preferably 1 to 5 parts by mass, based on 100 parts by mass of the silsesquioxane derivative represented by formula (1).

[0113] (Other ingredients) There are no particular restrictions on other components, and examples thereof include solvents, polymerizable compounds other than the silsesquioxane derivative represented by formula (1), resins, silicones, monomers, fillers, surfactants, antistatic agents (e.g., conductive polymers), leveling agents, photosensitizers, ultraviolet absorbers, antioxidants, heat resistance enhancers, stabilizers, lubricants, pigments, dyes, plasticizers, suspending agents, adhesion-imparting agents, nanoparticles, nanofibers, nanosheets, etc. The curable composition of the present disclosure may contain silane reactive diluents such as tetraalkoxysilanes, trialkoxysilanes, dialkoxysilanes, monoalkoxysilanes, and disiloxanes.

[0114] The curable composition of the present disclosure may or may not contain a solvent. 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.

[0115] The curable composition of the present disclosure may or may not contain a polymerizable compound other than the silsesquioxane derivative represented by formula (1) (hereinafter, also referred to as “other polymerizable compound”). There are no particular restrictions on other polymerizable compounds, as long as they are compounds that can undergo polymerization reaction in the presence of the silsesquioxane derivative represented by formula (1) and a polymerization initiator. Other polymerizable compounds include silsesquioxane derivatives other than the silsesquioxane derivative represented by formula (1), (meth)acrylate compounds, compounds having ethylenically unsaturated groups, epoxy compounds (compounds having epoxy groups), compounds having oxetane groups (compounds containing oxetane groups), and compounds having vinyl ether groups (vinyl ether compounds).

[0116] Examples of the silsesquioxane derivative other than the silsesquioxane derivative represented by the formula (1) include a silsesquioxane derivative composed only of T units and a silsesquioxane derivative containing T units and D units.

[0117] The (meth)acrylate compound is not particularly limited, and examples thereof 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").

[0118] Examples of the monofunctional (meth)acrylate include: Alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; Monofunctional (meth)acrylates having an alicyclic group, such as cyclohexyl (meth)acrylate, tert-butyl cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and tricyclodecane hydroxymethyl (meth)acrylate; Monofunctional (meth)acrylates having an aromatic group such as benzyl (meth)acrylate and phenyl (meth)acrylate; (meth)acrylates of alkylene oxide adducts of phenol derivatives such as phenol ethylene oxide adduct (meth)acrylates, phenol propylene oxide adduct (meth)acrylates, modified nonylphenol ethylene oxide adduct (meth)acrylates, nonylphenol propylene oxide adduct (meth)acrylates, p-cumylphenol alkylene oxide adduct (meth)acrylates, o-phenylphenol (meth)acrylates, and o-phenylphenol alkylene oxide adduct (meth)acrylates; Monofunctional (meth)acrylates having an alkoxyalkyl group such as 2-ethylhexyl carbitol (meth)acrylate; Monofunctional (meth)acrylates having a heterocyclic ring, such as tetrahydrofurfuryl (meth)acrylate and N-(2-(meth)acryloyloxyethyl)hexahydrophthalimide; Hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate and hydroxyhexyl (meth)acrylate; Monofunctional (meth)acrylates having a hydroxyl group and an aromatic group, such as 2-hydroxy-3-phenoxypropyl (meth)acrylate; 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 Monofunctional (meth)acrylates having a carboxyl group, such as ω-carboxy polycaprolactone mono(meth)acrylate and monohydroxyethyl phthalate (meth)acrylate, and the like.

[0119] Examples of the polyfunctional (meth)acrylate include: Polyethylene glycol di(meth)acrylates such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate; Polypropylene glycol di(meth)acrylates such as dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and tetrapropylene glycol di(meth)acrylate; 1,4-Butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide modified neopentyl glycol di(meth)acrylate, ethylene oxide modified bisphenol A di(meth)acrylate, propylene oxide modified bisphenol A di(meth)acrylate, ethylene oxide modified hydrogenated bisphenol A di(meth)acrylate, 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 and dipentaerythritol hexaacrylate, etc.

[0120] As the polyfunctional (meth)acrylate, urethane (meth)acrylate can also be used. Examples of the urethane (meth)acrylate include compounds obtained by addition reaction of an organic polyisocyanate and a hydroxyl-containing (meth)acrylate, and compounds obtained by addition reaction of an organic polyisocyanate, a polyol, and a hydroxyl-containing (meth)acrylate. The monofunctional (meth)acrylate, the polyfunctional (meth)acrylate, and the like may be used alone or in combination of two or more, or different types may be used in combination.

[0121] Here, examples of the polyol include low molecular weight polyols, polyether polyols, polyester polyols, and polycarbonate polyols. Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, neopentyl glycol, cyclohexanedimethanol, and 3-methyl-1,5-pentanediol. Examples of the polyether polyol include polypropylene glycol and polytetramethylene glycol. Examples of the polyester polyol include reaction products of these low molecular weight polyols and / or polyether polyols with dibasic acids such as adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid, and terephthalic acid, or acid components such as their anhydrides. These may be used alone or in combination of two or more, or different types may be used in combination.

[0122] Examples of the organic polyisocyanate include tolylene diisocyanate, xylene diisocyanate, tetramethylxylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Examples of the hydroxyl-containing (meth)acrylate include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; and hydroxyl-containing polyfunctional (meth)acrylates such as pentaerythritol tri(meth)acrylate, di(meth)acrylate of a 3-mole adduct of alkylene oxide with isocyanuric acid, and dipentaerythritol penta(meth)acrylate. These may be used alone or in combination of two or more, or different types may be used in combination.

[0123] In the curable composition of the present invention, when a (meth)acrylate compound is used in combination, the proportion thereof is not particularly limited. For example, the proportion of the (meth)acrylate compound relative to 100 parts by mass of the silsesquioxane derivative represented by formula (1) is preferably 0 to 100 parts by mass, more preferably 0 to 50 parts by mass, and further preferably 0 to 20 parts by mass. From the viewpoint of adhesion with the inorganic substance layer, the proportion of the (meth)acrylate compound is preferably low, preferably not containing or its content is 10% by mass or less relative to the total amount of the composition, more preferably not containing or its content is 5% by mass or less relative to the total amount of the composition, further preferably not containing or its content is 1% by mass or less relative to the total amount of the composition, and particularly preferably not containing.

[0124] A compound having one ethylenically unsaturated group per molecule other than the (meth)acrylate compound may be added to the curable composition. The ethylenically unsaturated group is preferably a (meth)acryloyl group, a maleimide group, a (meth)acrylamide group or a vinyl group. Specific examples of the compound having the ethylenically unsaturated group include (meth)acrylic acid, Michael addition dimer of acrylic acid, N-(2-hydroxyethyl)citraconimide, N,N-dimethylacrylamide, acryloylmorpholine, N-vinylpyrrolidone, and N-vinylcaprolactam. These may be used alone or in combination of two or more.

[0125] Examples of the epoxy compound include monofunctional epoxy compounds and polyfunctional epoxy compounds. Examples of the oxetane group-containing compound include monofunctional oxetane compounds and polyfunctional oxetane compounds. Examples of the vinyl ether compound include monofunctional vinyl ether compounds and polyfunctional vinyl ether compounds. As these compounds, for example, compounds described in Japanese Patent Application Laid-Open No. 2011-42755 can be used. There is no particular limitation on the silicone, and known silicones can be used, for example, polydimethyl silicone, polydiphenyl silicone, and polymethylphenyl silicone, etc., preferably having a functional group at the end and / or side chain thereof. There is no particular limitation on the functional group, for example, (meth)acryloyl, epoxy, oxetane, vinyl, hydroxyl, carboxyl, amino, and thiol groups, etc. can be mentioned.

[0126] When the curable composition of the present disclosure contains other polymerizable compounds, the content of the other polymerizable compounds is preferably 0.01 to 100 parts by mass, more preferably 0.1 to 50 parts by mass, and even more preferably 1 to 25 parts by mass, based on 100 parts by mass of the silsesquioxane derivative represented by formula (1).

[0127] [Cured material] The cured product of the present disclosure is obtained by curing the curable composition of the present disclosure. For example, the cured product of the present disclosure can be obtained by irradiating the curable composition of the present disclosure with active energy rays or heating the curable composition of the present disclosure.

[0128] When curing the curable composition of the present disclosure, the curable composition may be applied to a substrate. The curable composition of the present disclosure may or may not contain a solvent. When containing a solvent, it is preferably cured after removing the solvent.

[0129] When the curable composition of the present invention is applied to a substrate, the coating method of the curable composition is not particularly limited. As the coating method, common coating methods such as casting, spin coating, rod coating, dip coating, spray coating, roll coating, flow coating and gravure coating can be cited. The coating thickness of the curable composition of the present disclosure is not particularly limited and can be appropriately set depending on the purpose. The substrate to which the curable composition of the present disclosure is applied is not particularly limited, and examples thereof include wood, metal, inorganic materials, plastics, paper, fiber, and cloth. Examples of metals include copper, silver, iron, aluminum, silicon, silicon steel, and stainless steel. Examples of inorganic materials include metal oxides such as aluminum oxide, silicon oxide, magnesium oxide, zirconium oxide, zinc oxide, indium tin oxide, and gallium oxide, metal nitrides such as aluminum nitride, gallium nitride, and silicon nitride, ceramics such as silicon carbide and boron nitride, mortar, concrete, and glass. Specific examples of plastics include 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 aramid, polyimide resins, polyamide-imide resins, fluororesins such as tetrafluoroethylene resins, polyolefin resins such as cross-linked polyethylene resins, vinylidene chloride resins, acrylonitrile-butadiene-styrene (ABS) resins, polystyrene resins, polyacrylonitrile resins, cycloolefin polymers (COP), cycloolefin copolymers (COC), acetate resins, polyarylates, cellophane, norbornene resins, cellulose acetate resins such as triacetyl cellulose (TAC), polychloroprene, polyphenylene sulfide, polysulfone, polyethersulfone, polyetheretherketone, polyurethane resins, glass epoxy resins and other composite resins, various fiber-reinforced resins, and the like. Examples of the fiber include natural fiber, regenerated fiber, semisynthetic fiber, metal fiber, glass fiber, carbon fiber, ceramic fiber, and known chemical fiber, etc. The fabric may be a woven fabric or a nonwoven fabric, and may be produced, for example, using the aforementioned fibers. These materials may be used alone or in combination, mixture or composite of two or more. 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.

[0130] (Curing method) In the present disclosure, the curing method and curing conditions are selected according to whether the curable composition is active energy ray curable and / or thermosetting. In addition, the curing conditions (for example, the type of light source and the amount of light irradiation in the case of active energy ray curable, and the heating temperature and heating time in the case of thermosetting) are appropriately selected according to the type and amount of the polymerization initiator contained in the present composition and the type of other polymerizable compounds.

[0131] (1) Active energy ray curing method When the present composition is an active energy ray-curable composition, as a curing method, active energy ray irradiation can be performed using a known active energy ray irradiation device, etc. Examples of active energy rays include electron beams, ultraviolet rays, visible rays, and X-rays, etc., preferably light, and more preferably ultraviolet rays from the viewpoint of being able to use an inexpensive device. Examples of ultraviolet irradiation devices include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultrahigh-pressure mercury lamps, metal halide lamps, ultraviolet (UV) electrodeless lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, and light-emitting diodes (LEDs). The light irradiation intensity for the film coated with the present composition can be selected according to the purpose, application, etc., and the light irradiation intensity in the light wavelength region effective for activation of the active energy ray polymerization initiator (in the case of photocurable, referred to as photopolymerization initiator) (depending on the type of photopolymerization initiator, preferably using light with a wavelength of 220nm to 460nm) is preferably 0.1mW / cm 2 ~1000mW / cm 2 . In addition, the irradiation energy should be appropriately set according to the type of active energy rays, the formulation, etc. The light irradiation time of the coating can also be selected according to the purpose, use, etc., and it is preferred to set the light irradiation time so that the cumulative light amount expressed as the product of the light irradiation intensity and the light irradiation time in the light wavelength region is 10 mJ / cm 2 ~7,000mJ / cm 2 The cumulative light intensity is more preferably 200 mJ / cm 2 ~5,000mJ / cm 2 , more preferably 500mJ / cm 2 ~4,000mJ / cm 2 When the integrated light amount is within the above range, curing of the composition proceeds smoothly and a uniform cured product can be easily obtained.

[0132] Furthermore, heat curing can also be appropriately combined before and / or after photocuring. For example, the following two-stage curing can also be performed: after the present composition is infiltrated into a substrate having a shadowed portion when irradiated with light, the light is irradiated, and the present composition in the portion irradiated with light is first cured, and then heat is applied to cure the present composition in the portion not irradiated with light. Such a substrate is not particularly limited, and for example, a substrate having a complex shape such as a cloth, a fiber, a powder, a porous shape, and a concave-convex shape can be cited, and a shape combining two or more of these shapes can also be used.

[0133] (2) Thermal curing method When the present composition is a thermosetting composition, the curing method and curing conditions are not particularly limited. The curing temperature is preferably 80° C. to 200° C., more preferably 100° C. to 180° C., and even more preferably 110° C. to 150° C. The curing temperature may be kept constant or increased, or a combination of temperature increase and temperature decrease may be used. The curing time is appropriately selected according to the type of thermal polymerization initiator and the content ratio of other components, and the curing time 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 preferred conditions, a uniform cured film without expansion, cracks, etc. can be formed.

[0134] (Application of silsesquioxane derivatives, etc.) The hardened material of the present invention has excellent hardness, and thus can be applied to hard coatings, optical components, and the like. In addition, by curing the hard coating agent containing the curable composition of the present invention, a hard coating layer having excellent hardness is obtained. The hard coating agent of the present invention can be disposed on a substrate, for example, by curing the hard coating agent applied on the substrate, a substrate having a hard coating layer is obtained. The hard coating agent of the present invention can contain various components as required. The cured product or hard coating of the present disclosure has excellent weather resistance. This is presumably because the silsesquioxane derivative of the present disclosure has a low curing shrinkage, so the residual stress at the interface between the cured product or hard coating of the present disclosure and the substrate is reduced, thereby improving the adhesion, and the adhesion is not easily reduced even under severe conditions. The silsesquioxane derivative disclosed in the present invention can produce a cured product having low viscosity and excellent hardness. The low viscosity makes it excellent in coating properties without a solvent, and even when a solvent is used, the amount of solvent used can be reduced. The silsesquioxane derivatives disclosed herein have low viscosity and can therefore be suitable for applications requiring low viscosity. For example, they can be applied to adhesive applications, printing applications such as inkjet and 3D printing, coating agent applications, nano-printing applications, etc. In addition, in the case of nano-printing applications, since the silsesquioxane derivatives disclosed herein have low viscosity, they have excellent fine transferability. In addition, the silsesquioxane derivatives disclosed herein can be used without solvent, so they can be directly cured after being poured into a mold. The silsesquioxane derivative of the present disclosure may be used in combination with a filler, other polymerizable compounds, etc. Furthermore, since the silsesquioxane derivative of the present disclosure has a low viscosity, it can also be mixed with a large amount of fillers.

[0135] The elastic modulus at 23° C. of the cured product or the hard coat layer of the present disclosure is preferably greater than 4.0 GPa, more preferably greater than 4.1 GPa, further preferably greater than 4.1 GPa and 9.0 GPa or less, particularly preferably 4.15 GPa or more and 8.0 GPa or less, and most preferably 4.20 GPa or more and 7.0 GPa or less. Example

[0136] Next, the present disclosure will be specifically described based on Examples and Comparative Examples. The present disclosure is not limited to the following Examples.

[0137] (Measurement of weight average molecular weight) The weight average molecular weight (Mw) of the silsesquioxane derivatives in each example and each comparative example was measured as follows. Specifically, separation was performed by gel permeation chromatography (manufactured by Tosoh Corporation, HLC-8320GPC, hereinafter referred to as "GPC") in tetrahydrofuran solvent at 40°C using a GPC column "TSK gel SuperMultiporeHZ-M" (manufactured by Tosoh Corporation), and the molecular weight converted to standard polystyrene was calculated based on the retention time.

[0138] (Viscosity measurement) The viscosity of the silsesquioxane derivative in each Example and each Comparative Example at 25° C. was measured using a TVE22H viscometer manufactured by Toki Sangyo Co., Ltd.

[0139] (Measurement of density) The density of the silsesquioxane derivatives in the examples and comparative examples was measured in accordance with JIS K0061-7.

[0140] (Calculation of the molar ratio of each structural unit of the silsesquioxane derivative) The molar ratio of each constituent unit of the silsesquioxane derivative in each Example and each Comparative Example was determined by dissolving a sample in deuterated chloroform. 1 H-NMR, further performed as needed 29 Si-NMR analysis was used for calculation.

[0141] <Example 1> (Synthesis of Silsesquioxane Derivatives) In a 1L four-necked round-bottom flask equipped with a thermometer, a dropping funnel and a stirring blade, (3-acryloxy)propyltrimethoxysilane (140.6 g, 0.6 mol), 3-methacryloxypropyltrimethoxysilane (99.3 g, 0.4 mol), 2-propanol (64.6 g) and hydroquinone (0.085 g) were weighed and stirred thoroughly at about 30°C in a water bath. Separately, 35% hydrochloric acid (1.0 g, 9.6 mmol as hydrogen chloride) and pure water (150.7 g) were mixed to prepare an aqueous solution. The aqueous solution prepared as a mixed solution was dripped from the dropping funnel for about 1 hour while stirring the reaction solution, and then allowed to stand at room temperature overnight. The amount of water added was 2.8 times the total amount of the hydrolyzable groups of the raw material organosilicon compound. Then, the reaction solution was heated to 60°C and the solvent and the like in the reaction solution were removed by distillation under reduced pressure to obtain 170 g of silsesquioxane derivative 1 (S1) as a colorless transparent liquid. 1H-NMR analysis confirmed that each structural unit was quantitatively introduced according to the charging ratio of the raw materials. The viscosity of the synthesized silsesquioxane derivative at 25° C. was 6,270 mPa·s, and the weight average molecular weight (Mw) was 2,010.

[0142] <Examples 2 to 9> Silsesquioxane derivatives 2 to 9 (S2 to S9) were obtained in the same manner as in Example 1, except that the amount of raw materials charged was changed to that shown in Table 1 instead of Example 1, and the amount of solvent etc. was appropriately changed. In Examples 5 to 7 and 9, 1,3-divinyltetramethyldisiloxane was used as a raw material for the M unit constituting the silsesquioxane derivative. Table 1 shows the amount of water added during the synthesis, the molar ratio of each structural unit in the silsesquioxane derivative, the viscosity at 25° C., and the weight average molecular weight (Mw) of the synthesized silsesquioxane derivatives 2 to 9.

[0143] <Examples 10 to 12> Silsesquioxane derivatives 10 to 12 (S10 to S12) were obtained in the same manner as in Example 1, except that the input amounts of the raw materials were changed to those shown in Table 1 instead of Example 1, and the amounts of the solvents, etc. were appropriately changed. In Examples 10 to 12, dimethyldimethoxysilane was used as a raw material for the D unit constituting the silsesquioxane derivatives. Table 1 shows the amount of water added during synthesis, the molar ratio of each structural unit in the silsesquioxane derivative, the viscosity at 25° C., and the weight average molecular weight (Mw) of the synthesized silsesquioxane derivatives 10 to 12.

[0144] <Comparative Examples 1, 3 and 4> Silsesquioxane derivatives C1, C3 and C4 (SC1, SC3 and SC4) were obtained in the same manner as in Example 1 except that the amounts of raw materials charged were changed as shown in Table 1 instead of Example 1 and the amounts of solvents and the like were appropriately changed. Table 1 shows the amount of water added during synthesis, the molar ratio of each structural unit in the silsesquioxane derivative, the viscosity at 25° C., and the weight average molecular weight (Mw) of the synthesized silsesquioxane derivatives C1, C3, and C4.

[0145] <Comparative Example 2> According to the method of Example 1 described in Japanese Patent Laid-Open No. 10-030068, silsesquioxane derivative C2 (SC2) was synthesized without using an organic solvent as a reaction solvent. The amount of water added during the synthesis, the molar ratio of each constituent unit in the silsesquioxane derivative, the viscosity at 25° C., and the weight average molecular weight (Mw) of the synthesized silsesquioxane derivative 9 are shown in Table 1.

[0146] (Evaluation of storage stability) For each of the silsesquioxane derivatives in each example and each comparative example, 1 g of each was weighed in a 9 mL screw-thread vial, and after standing in a thermostatic bath at 60° C. for 7 days, the viscosity at 25° C. was measured in the same manner as above (i.e., the viscosity of the silsesquioxane derivative subjected to the accelerated test was measured). The storage stability was evaluated based on the viscosity increase ratio before and after the accelerated test ((viscosity after the test) / (viscosity before the test)) according to the following criteria. The results are shown in Table 1. -Evaluation Criteria- A: less than 1.3 B: 1.3 or above or gel component is generated

[0147] (Preparation of Photocurable Composition) 0.03 parts by mass of 2-hydroxy-2-methyl-1-phenylpropane-1-one was added to 1 part by mass of the synthesized silsesquioxane derivative, and the mixture was stirred with a rotary mixer to prepare photocurable compositions. In each photocurable composition, the solvent and the like were removed by distillation when synthesizing each silsesquioxane derivative, and therefore each photocurable composition did not substantially contain a solvent.

[0148] (Production of light-cured materials) The photocurable composition prepared in the above manner was injected into a silicone mold on a release polyethylene terephthalate (PET) film, and after overlapping the release PET films and clamping and fixing them with glass plates, each photocurable composition was irradiated with ultraviolet rays under the following conditions to cure it, thereby producing a photocured product. -UV irradiation conditions- Lamp: High-pressure mercury lamp (ECS-4011GX manufactured by EYE GRAPHICS Co., Ltd.) Height of lamp: 10cm Conveyor belt speed: 5.75m / min Accumulated light volume per pass: 360mJ / cm 2 (UV-A, measured value of UV POWER PUCK II manufactured by EIT) Atmosphere: Atmospheric Pass times: 20 times

[0149] (Measurement of density of photocured material) The density of the photocured product prepared as described above was measured in accordance with JIS K0061-8.

[0150] (Evaluation of UV curability) MCR-301 manufactured by Anton Paar is connected to Lightning cure LC5 manufactured by Hamamatsu Photonics Co., Ltd. By applying shear strain to each photocurable composition prepared in the above manner while irradiating it with ultraviolet light (UV), and recording the increase in storage modulus during UV irradiation, the UV curing speed (UV curability) of each photocurable composition is evaluated. The storage modulus of each photocurable composition was measured by applying a strain of 0.05% at 1 Hz under the conditions of 25°C and nitrogen flow. A high-pressure mercury lamp was used as a UV light source, and each photocurable composition was irradiated with only a short wavelength of 365 nm through a heat ray cutoff filter, a bandpass filter, and a light reduction filter. The UV irradiation intensity at this time was 10 mW / cm 2 The UV curability was evaluated based on the storage modulus value of each photocurable composition when irradiated with UV for 10 seconds according to the following criteria. In the order of A>B>C, the UV curability was excellent. The experimental results are shown in Table 1. -Evaluation Criteria- A: 5.0×10 6 Pa or above B: 1.0×10 6 Pa or more and less than 5.0×10 6 Pa C: less than 1.0×10 6 Pa

[0151] (Preparation of photocurable coating agent) 0.03 parts by mass of 2-hydroxy-2-methyl-1-phenylpropane-1-one and 1 part by mass of propylene glycol monobutyl ether were added to 1 part by mass of the synthesized silsesquioxane derivative, and the mixture was stirred with an autorotating and orbiting mixer to prepare photocurable coating agents.

[0152] (Production of light-cured films) The photocurable coating agents prepared in the above manner were applied to 80 μm thick TAC (triacetyl cellulose) films. Specifically, after applying each photocurable coating agent using a No. 20 bar coater, each applied photocurable coating agent was dried at 60° C. for 10 minutes, and then irradiated with ultraviolet rays under the following conditions for curing to prepare a photocurable film. The film thickness was about 10 μm. -UV irradiation conditions- Lamp: High-pressure mercury lamp (ECS-4011GX manufactured by EYE GRAPHICS Co., Ltd.) Height of lamp: 10cm Conveyor belt speed: 5.75m / min Accumulated light volume per pass: 360mJ / cm2 (UV-A, measured value of UV POWER PUCK II manufactured by EIT) Atmosphere: Atmospheric Pass times: 10 times

[0153] (Pencil hardness test) The photocured film produced as described above was subjected to a pencil hardness test in accordance with JIS K5600-5-4 (1999) (ISO / DIS15184: 1996).

[0154] (Measurement of elastic modulus) The elastic modulus of the photocured film prepared in the above manner was measured as follows. Specifically, the indentation hardness was measured at a strain rate of 0.05 / s at 23°C using a nanoindenter (manufactured by Agilent Technologies, Nano Indenter G200, Berkovich indenter). The modulus values ​​at indentation depths of 500nm to 800nm ​​were averaged to calculate the elastic modulus. The experimental results are shown in Table 1.

[0155] (Calculation of curing shrinkage) The calculation was based on (density of cured product - density before curing) / density before curing × 100. Table 1 shows the results.

[0156] (Weather resistance test) The photocured films of Examples 1 to 12 and Comparative Examples 1 to 4 were prepared in the same manner as the preparation of the photocured film except that a 1 mm thick polycarbonate (PC) plate (Iupilon manufactured by Engineering Test Service Co., Ltd.) was used as the substrate. The prepared photocured films were tested using a metal weather tester manufactured by DAIPLA WINTES Co., Ltd. under the following conditions: The film is irradiated with ultraviolet light. Light source: Metal halide lamp Illuminance: 138mW / cm 2 Irradiation time: 90 hours continuously, 2 minutes of water spray every 2 hours Temperature: 63℃ Humidity: 70% Before and after ultraviolet irradiation, the adhesion of the photocured film before and after the cross-cut peeling weather resistance test was evaluated by the cross-cut method according to JIS K5600-5-6 (1999) (ISO 2409: 1992). The number of remaining squares in 25 squares was 15 or more, and the number of squares exceeding 0 and less than 15 was set as B, and the number of squares completely peeled off was set as C.

[0157] (Comprehensive evaluation) Based on the seven evaluation results of storage stability, UV curability, elastic modulus, cure shrinkage, pencil hardness, checkerboard peeling weather resistance test before and after the checkerboard peeling weather resistance test for Examples 1 to 12 and Comparative Examples 1 to 4, a comprehensive evaluation was performed according to the following evaluation criteria. The results of the comprehensive evaluation are shown in Table 1. In addition, the respective criteria for "excellent" for each of the seven evaluation results are as follows, and the comprehensive evaluation was performed based on this. -Excellent Standards- The evaluation {before the checkerboard peeling weather resistance test} was A. The evaluation {after the cross-cut peeling weather resistance test} was A. -Evaluation criteria for comprehensive evaluation- S: All seven evaluation results were excellent. A: Six of the seven evaluation results were excellent. B: Five of the seven evaluation results were excellent. C: Four or less of the seven evaluation results were excellent.

[0158]

Table 1

[0159] As shown in Table 1, the silsesquioxane derivatives obtained in Examples 1 to 12 had lower cure shrinkage than those in Comparative Examples 1 to 4, and the hardness of the cured products was excellent. Furthermore, the silsesquioxane derivatives obtained in Examples 1 to 7 and 9 to 12 also had excellent storage stability. Furthermore, the silsesquioxane derivatives obtained in Examples 1 to 3 and 5 to 12 were also excellent in UV curability. Furthermore, the cured products of the silsesquioxane derivatives obtained in Examples 1 to 8 and 10 also had excellent pencil hardness. Furthermore, the silsesquioxane derivatives obtained in Examples 1 to 12 also exhibited excellent weather resistance in the form of cured products. Moreover, compared with Comparative Examples 1 to 4, the silsesquioxane derivatives obtained in Examples 1 to 12 were also excellent in comprehensive evaluations of storage stability, UV curability, elastic modulus, cure shrinkage, pencil hardness, and before and after the cross-cut peeling weather resistance test.

[0160] In addition, the disclosure of Japanese Patent Application No. 2022-094443 filed on June 10, 2022 is incorporated herein by reference in its entirety. In addition, all documents, patent applications, and technical specifications described in this specification are incorporated herein by reference to the same extent as when each document, patent application, and technical specification incorporated by reference is specifically and individually described.

Claims

1. A silsesquioxane derivative represented by the following formula (1): The elastic modulus of the cured product at 23°C exceeds 4.0 GPa. 【Chemical 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 aralkylene group having 7 to 12 carbon atoms, and 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, and R 6 is an organic group having 2 to 12 carbon atoms and having at least one of an ethylenically unsaturated bond and a carbon-carbon triple bond, R 7 and R 8 Each independently represents 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. 5 They can be the same or different. There are multiple R 7 They can be the same or different. There are multiple R 8 They can be the same or different. 1 ~R 8 A part of the structure may be substituted by a substituent or a halogen atom, each independently; 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. 2 . The silsesquioxane derivative according to claim 1 , wherein the curing shrinkage is 7.3% or less. 3 . The silsesquioxane derivative according to claim 1 , wherein t, x and z are 0 and satisfy 0≤y / (u+v+w)≤0.

5. The silsesquioxane derivative according to claim 1 , wherein t, y and z are 0, and 0≤x / (u+v+w)≤0.

5. The silsesquioxane derivative according to claim 1 , wherein u and v are each independently a positive number. The silsesquioxane derivative according to claim 5 , satisfying 0<v / u≤1.

7. A curable composition comprising: The silsesquioxane derivative according to any one of claims 1 to 6; and Polymerization initiator. A hard coating agent comprising the curable composition according to claim 7.

9. A cured product obtained by curing the curable composition according to claim 7.

10. A hard coating layer formed by curing the hard coating agent according to claim 8.

11. A substrate comprising the hard coating layer according to claim 10.

12. A method for producing a silsesquioxane derivative according to any one of claims 1 to 6, comprising the steps of: using an organic solvent, n SiX p At least one organosilicon compound represented by is hydrolyzed by adding 2 to 30 molar equivalents of water relative to the total amount of hydrolyzable groups possessed by the organosilicon compound, wherein: n represents an integer of 0 to 3, p represents an integer of 1 to 4, n+p=4, R represents a group bonded to a silicon atom via a carbon atom in the silsesquioxane derivative, and X represents a hydrolyzable group.

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