Curable composition, cured product, hard coat agent, hard coat, article, and laminate

Abstract

Provided are: a curable composition containing, in relation to the total solid content of the curable composition, 0.1 mass% to less than 10 mass% of a polysiloxane represented by formula (1); a cured product obtained by curing said curable composition; a hard coat agent in which the curable composition is used; a hard coat; an article; and a laminate. At least one R1 is a monovalent organic group having a polymerizable group, each R2 independently represents a C1-20 hydrocarbon group substituted with a fluorine atom, w represents a positive number, v, x, y and z each independently represent 0 or a positive number, x and / or y represents a positive number, a structure represented by formula (S) is included when x is 0, and n represents a number of 3 or greater.

Description

Curable composition, cured product, hard coating agent, hard coating, article, and laminate

[0001] The present disclosure relates to a curable composition, a cured product, a hard coating agent, a hard coating, an article, and a laminate.

[0002] Displays of various devices that display images are provided with a transparent coating layer that has excellent scratch resistance and hardness as a surface protection layer. To prevent a decrease in visibility due to contamination of the display surface, it is preferable for the coating layer to have anti-fouling properties. In particular, for devices with touch panel functionality, it is desirable to prevent the adhesion of sebum and make it easy to remove. For this reason, leveling agents, which are substances with low surface free energy, are incorporated into the coating of many display surfaces to increase surface smoothness and impart anti-fouling properties. Fluorine-based resins and silicone resins have traditionally been used as such leveling agents.

[0003] However, these leveling agents are not chemically fixed to the base resin, and have problems such as bleeding out and falling off or loss of function due to repeated use. To solve these problems, leveling agents having a polymerizable functional group and a fluorinated alkyl group or a silicone chain have come to be used. Examples of conventional leveling agents include those described in Patent Documents 1 to 4.

[0004] Patent Document 1 discloses a composition for forming a hard coat layer, which contains a polyorganosilsesquioxane having a polymerizable epoxy group and a nonionic fluorine-containing compound as a leveling agent.

[0005] Patent Document 2 discloses a leveling agent having a fluorine atom, which is obtained by polymerizing a monomer having two or more groups with a radically polymerizable double bond and containing at least one nitrogen atom, and also discloses a composition containing this leveling agent and a polyorganosilsesquioxane.

[0006] Patent Document 3 discloses a hard coat composition containing, as a leveling agent, a polymer having at least one of a silicone group and a perfluoropolyether group and a reactive group on its side chain, and polyorganosilsesquioxane having a polymerizable group.

[0007] Patent Document 4 discloses a composition for forming a hard coat layer, which contains a polysilsesquioxane having a perfluoropolyether group.

[0008] International Publication No. 2021 / 193173 International Publication No. 2019 / 235108 International Publication No. 2020 / 059726 International Publication No. 2021 / 193478

[0009] In particular, for displays that are directly touched, such as touch panels, from the perspective of physical strength and durability, it is desirable for the leveling agent that is unevenly distributed on the coating surface to have excellent hardness and weather resistance in addition to high anti-fouling properties.

[0010] Patent Document 1 discloses a hard coating composition in which a nonionic fluorine-containing compound is added as a leveling agent to a polyorganosilsesquioxane having a polymerizable epoxy group. However, in a hard coating obtained by curing the composition, since there is no covalent bond between the silsesquioxane, which is the main component, and the leveling agent, performance degradation occurs due to bleeding out of the leveling agent, etc.

[0011] Patent Document 2 discloses a leveling agent having a fluorine atom, which is obtained by polymerizing a monomer having two or more groups with a radically polymerizable double bond and containing at least one nitrogen atom. However, in a hard coat obtained by curing the composition, since there is no covalent bond between the silsesquioxane, which is the main component, and the leveling agent, performance degradation occurs due to bleed-out of the leveling agent, etc. Furthermore, since the leveling agent has a nitrogen atom in its molecule, there is a risk that deterioration will be accelerated during long-term use due to hydrolysis, etc. of the hard coat obtained by curing the composition.

[0012] Patent Document 3 discloses a hard coating composition in which a leveling agent having a polymerizable functional group and silicone or perfluoropolyether is added to a polysilsesquioxane derivative. However, the crosslinking density of the leveling agent is low, and there is a risk that the hardness of the coating surface will decrease.

[0013] Patent Document 4 discloses a composition for forming a hard coat layer containing a polysilsesquioxane having a perfluoropolyether group, but it is not possible to achieve both surface hardness and a low coefficient of dynamic friction (i.e., high surface smoothness).

[0014] The present disclosure has been made in view of the above, and aims to provide a curable composition that provides a cured product having excellent durability and excellent suppression of a decrease in the indentation modulus of the cured product, and a cured product obtained by curing the cured composition; a hard coating agent containing the curable composition and a hard coating obtained by curing the hard coating; and an article and a laminate including the hard coating.

[0015] Means for solving the above problems include the following aspects: <1> A curable composition comprising a polysiloxane represented by the following formula (1) in an amount of 0.1 mass % or more and less than 10 mass % relative to the total solid content of the curable composition, and wherein x / (v+w+x+y+z) is less than 0.6:

[0016]

[0017] In formula (1), R １ each independently represents at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a monovalent organic group having a polymerizable group; R １ At least one of R is a monovalent organic group having a polymerizable group, １ The alkyl group, the aralkyl group, the aryl group, and the monovalent organic group having a polymerizable group in the formula (I) may be substituted with a structure selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, an aryloxy group, an aralkyloxy group, and an oxy group, and R ２each independently represents a hydrocarbon group having 1 to 20 carbon atoms substituted with a fluorine atom, R ３ , R ４ and R ５ each independently represents at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a monovalent organic group having a polymerizable group; R ３ , R ４ and R ５ wherein the alkyl group, the aralkyl group, the aryl group, and the monovalent organic group having a polymerizable group may be substituted with a structure selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, an aryloxy group, an aralkyloxy group, and an oxy group, w represents a positive number, v, x, y, and z each independently represent 0 or a positive number, at least one of x and y represents a positive number, and when x is 0, the compound contains a structure represented by the following formula (S):

[0018]

[0019] n represents a number of 3 or more.

[0020] <2> The curable composition according to <1>, further comprising a polysiloxane represented by the following formula (2) in addition to the polysiloxane represented by the formula (1):

[0021]

[0022] In formula (2), R ６ , R ７ and R ８ each independently represents at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a monovalent organic group having a polymerizable group; R ６ , R ７ and R ８ At least one of R is a monovalent organic group having a polymerizable group, ６ , R ７ and R ８wherein the alkyl group, the aralkyl group, the aryl group, and the monovalent organic group having a polymerizable group may be substituted with a structure selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, an aryloxy group, an aralkyloxy group, and an oxy group, q represents a positive number, and p, r, and s each independently represent 0 or a positive number.

[0023] <3> R in the formula (1) １ The curable composition according to <1> or <2>, wherein the polymerizable group in formula (1) is at least one selected from the group consisting of an acryloyl group, a methacryloyl group, an epoxy group, an oxetanyl group, a vinyl group, and an allyl group. <4> The curable composition according to any one of <1> to <3>, wherein the value of (x + y) / (v + w + x + y + z) in formula (1) is 0.20 to 0.80. <5> The curable composition according to any one of <1> to <4>, further comprising a polymerization initiator. <6> A cured product obtained by curing the curable composition according to any one of <1> to <5>. <7> A hard coating agent comprising the curable composition according to any one of <1> to <5>. <8> A hard coating obtained by curing the hard coating agent according to <7>. <9> An article having the hard coating according to <8>. <10> A laminate having the hard coating according to <9> and a substrate. <11> The cured product according to <6>, wherein the pencil hardness of the cured product produced on a steel plate is 5H or more and the dynamic friction coefficient is 0.35 or less. <12> The cured product according to <6> or <11>, wherein the decrease in the water contact angle before and after an abrasion test using absorbent cotton soaked in acetone, an abrasion test using absorbent cotton soaked in hexane, and an abrasion test using steel wool is 10% or less.

[0024] According to the present disclosure, it is possible to provide a curable composition that provides a cured product with excellent durability and excellent suppression of a decrease in the indentation modulus of the cured product, a cured product obtained by curing the cured composition, a hard coating agent containing the curable composition and a hard coating obtained by curing the hard coating, and an article and a laminate that include the hard coating.

[0025] Modes for carrying out the present disclosure are described in detail below. However, the present disclosure is not limited to the following embodiments. In the following embodiments, components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit the present disclosure. In this specification, numerical ranges indicated using "to" include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In numerical ranges described in stages in this specification, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in numerical ranges described in this specification, the upper or lower limit value of that numerical range may be replaced with a value shown in the examples. In this specification, the term "total solids content" refers to the total mass of all components of the composition excluding the solvent. Furthermore, in this specification, a combination of two or more preferred embodiments is a more preferred embodiment.

[0026] In this specification, R in formula (1) or formula (2) １ ~R ８ may each independently be partially substituted with a substituent or a halogen atom. １ ~R ８ may each independently be partially substituted with 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 ureido group, an isocyanate group, a carboxy group, an acid anhydride group, or a halogen atom. １ ~R ８ may each independently be unsubstituted.

[0027] [Curable Composition] The curable composition of the present disclosure contains a polysiloxane represented by the following formula (1) in an amount of 0.1 mass % or more and less than 10 mass % relative to the total solid content of the curable composition, and x / (v+w+x+y+z) is less than 0.6:

[0028]

[0029] In formula (1), R １ each independently represents at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a monovalent organic group having a polymerizable group; R １ At least one of R is a monovalent organic group having a polymerizable group, １ The alkyl group, the aralkyl group, the aryl group, and the monovalent organic group having a polymerizable group in the formula (I) may be substituted with a structure selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, an aryloxy group, an aralkyloxy group, and an oxy group, and R ２ each independently represents a hydrocarbon group having 1 to 20 carbon atoms substituted with a fluorine atom, R ３ , R ４ and R ５ each independently represents at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a monovalent organic group having a polymerizable group; R ３ , R ４ and R ５ wherein the alkyl group, the aralkyl group, the aryl group, and the monovalent organic group having a polymerizable group may be substituted with a structure selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, an aryloxy group, an aralkyloxy group, and an oxy group, w represents a positive number, v, x, y, and z each independently represent 0 or a positive number, at least one of x and y represents a positive number, and when x is 0, the compound contains a structure represented by the following formula (S):

[0030]

[0031] n represents a number of 3 or more.

[0032] As described above, conventional curable compositions have not provided sufficient durability for the resulting cured product. After extensive research, the present inventors have discovered that by adopting the above-described configuration, it is possible to provide a curable composition in which the resulting cured film has excellent durability. By including a polysiloxane having a silsesquioxane structure having a fluorine-substituted hydrocarbon group having 1 to 20 carbon atoms and / or a silicone chain and a polymerizable group in an amount of 0.1% by mass or more but less than 10% by mass, based on the total solids content of the curable composition, it is possible to obtain a suitable crosslinked structure after curing. Furthermore, the uneven distribution of the polysiloxane represented by formula (1) on the surface results in a cured product with excellent surface solvent resistance and abrasion resistance, making it possible to produce a cured product with excellent durability. Furthermore, by using a polysiloxane represented by formula (1), the decrease in indentation modulus of the resulting cured product is suppressed compared to conventional leveling agents.

[0033] Furthermore, the curable composition of the present disclosure also provides a cured product that is excellent in hardness, surface smoothness, water repellency, and stain resistance.

[0034] The curable composition of the present disclosure preferably further comprises a polysiloxane represented by formula (2) described below. The curable composition of the present disclosure preferably further comprises a polymerization initiator described below. The curable composition of the present disclosure may further comprise various components (hereinafter also referred to as "other components") as needed. The curable composition of the present disclosure can be suitably used as a hard coating agent.

[0035] <Polysiloxane Represented by Formula (1)> The curable composition of the present disclosure contains a polysiloxane represented by formula (1). The structural units in the polysiloxane represented by formula (1) are referred to as structural units (a) to (e) below.

[0036]

[0037] In the polysiloxane represented by formula (1), w represents a positive number, v, x, y, and z each independently represent 0 or a positive number, and at least one of x and y is a positive number. In other words, the polysiloxane represented by formula (1) contains the structural unit (b) and at least one of the structural unit (c) and the structural unit (d) among the structural units (a) to (e) described above, and may contain at least one of the structural unit (a) and the structural unit (e) as necessary. Furthermore, since the polysiloxane represented by formula (1) contains at least the structural unit (b), it is sometimes referred to as silsesquioxane instead of polysiloxane.

[0038] In formula (1), v, w, x, y, and z represent the molar ratio of the structural units (a) to (e). In formula (1), v, w, x, y, and z represent the relative molar ratio of the structural units (a) to (e) that may be contained in the polysiloxane represented by formula (1). The molar ratio can be determined, for example, from the NMR (nuclear magnetic resonance) analysis value of the polysiloxane represented by formula (1). Furthermore, when the reaction rate of each raw material for the polysiloxane represented by formula (1) is known, or when the yield is 100%, the molar ratio can be determined from the amount of the raw material charged. For example, the molar ratio of each structural unit of the polysiloxane represented by formula (1) can be determined by measuring the molar ratio of a sample dissolved in deuterated chloroform or the like. １ H-NMR analysis is carried out, and further analysis is carried out as necessary. ２９ It may also be calculated by Si-NMR analysis. The original structure of the polysiloxane represented by formula (1) may be estimated from the ratio of the constituent units after decomposing the polysiloxane into constituent units with an alkali or the like. If necessary, the molar ratio of each constituent unit of the polysiloxane represented by formula (1) may be determined by combining known techniques such as mass spectrometry and IR (infrared absorption spectroscopy) analysis.

[0039] Each of the structural units (b) to (e) in formula (1) may be of only one type, or may be of two or more types. Furthermore, the order of the structural units in formula (1) indicates the composition of the structural units, and does not mean that the condensation form of the structural units in the polysiloxane represented by formula (1) is limited to this order. Therefore, in the curable composition of the present disclosure, the condensation form of the structural units in the polysiloxane represented by formula (1) does not necessarily have to be the same as the order of the structural units in formula (1). Details of the structural units (a) to (e) are described below.

[0040] (Structural Unit (a)) The structural unit (a) is a unit in which O is bonded to one silicon atom. １／２ The Q unit has four silicon atoms (two oxygen atoms). １／２ It means a unit having four of these.

[0041] The proportion of the structural unit (a) in the polysiloxane represented by formula (1) is not particularly limited. For example, the molar ratio of the structural unit (a) to all structural units (v / (v+w+x+y+z)) is preferably 0.1 or less, more preferably 0.05 or less, and even more preferably 0, from the viewpoint of viscosity and hardness when cured. Here, a molar ratio of 0 means that the corresponding structural unit is not contained, and the same applies hereinafter.

[0042] In the polysiloxane represented by formula (1), for example, the mass ratio of the structural unit (a) is preferably 10 mass% or less, more preferably 5 mass% or less, and even more preferably 0 mass%, relative to the total mass of the polysiloxane represented by formula (1), from the viewpoints of viscosity and hardness when formed into a cured product. Here, a mass ratio of 0 mass% means that the corresponding structural unit is not contained, and the same applies hereinafter.

[0043] (Structural Unit (b)) The structural unit (b) is a unit in which O is substituted with 1 silicon atom. １／２ Three oxygen atoms (1.5 oxygen atoms), R １is a T unit in which O is bonded to a silicon atom. １／２ It means a unit having three of these.

[0044] In the structural unit (b), R １ each independently represents at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms (also referred to as the number of carbon atoms), an aralkyl group having 7 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a monovalent organic group having a polymerizable group; R １ At least one of R is a monovalent organic group having a polymerizable group, １ The alkyl group, the aralkyl group, the aryl group, and the monovalent organic group having a polymerizable group in the formula (I) may be substituted with a structure selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, an aryloxy group, an aralkyloxy group, and an oxy group.

[0045] The alkyl group having 1 to 10 carbon atoms may be linear or branched. Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. From the viewpoints of heat resistance and hardness of the cured product, a methyl group or an ethyl group is preferred, and a methyl group is more preferred.

[0046] 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 viewpoints of heat resistance and hardness of the cured product, a phenyl group is preferred.

[0047] Examples of aralkyl groups 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 groups and phenethyl groups, and from the viewpoints of heat resistance and hardness of the cured product, benzyl groups are preferred.

[0048] Examples of the polymerizable group in the monovalent organic group having a polymerizable group include an ethylenically unsaturated group, an alkynyl group, and a cyclic ether group. １From the viewpoints of reactivity and hardness, the polymerizable group in is preferably at least one selected from the group consisting of an acryloyl group, a methacryloyl group, an epoxy group, an oxetanyl group, a vinyl group, and an allyl group, more preferably at least one selected from the group consisting of an acryloyl group, a methacryloyl group, and an oxetanyl group, and particularly preferably at least one selected from the group consisting of an acryloyl group and a methacryloyl group. The monovalent organic group having a polymerizable group is preferably a monovalent organic group having 2 to 12 carbon atoms and having an ethylenically unsaturated group, an alkynyl group, or a cyclic ether group, more preferably a monovalent organic group having 2 to 12 carbon atoms and having an ethylenically unsaturated group or a cyclic ether group, and particularly preferably a monovalent organic group having 2 to 12 carbon atoms and having an ethylenically unsaturated group.

[0049] Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, a styryl group, a (meth)acryloxy group, and a (meth)acrylamide group. Among these, from the viewpoint of curability, a vinyl group or a (meth)acryloxy group is preferred. Examples of the organic group having 2 to 12 carbon atoms and an ethylenically unsaturated group include a vinyl group, an orthostyryl group, a metastyryl group, a parastyryl group, an acryloyloxymethyl group, a methacryloyloxymethyl group, a 2-acryloyloxyethyl group, a 2-methacryloyloxyethyl group, a 3-acryloyloxypropyl group, a 3-methacryloyloxypropyl group, an 8-acryloyloxyoctyl group, an 8-methacryloyloxyoctyl group, Examples of such groups include 1-propenyl, 2-propenyl (allyl), 1-methylethenyl, 1-butenyl, 3-butenyl, 1-pentenyl, 4-pentenyl, 3-methyl-1-butenyl, 1-phenylethenyl, 2-phenylethenyl, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 3-butynyl, 1-pentynyl, 4-pentynyl, 3-methyl-1-butynyl, and phenylbutynyl. Among these, from the viewpoint of curability, preferred are alkyl groups having a (meth)acryloxy group, vinyl groups, and allyl groups, more preferred are 3-(meth)acryloxypropyl, vinyl groups, and allyl groups, and particularly preferred is 3-(meth)acryloxypropyl group.

[0050] Examples of the cyclic ether group include an epoxy group and an oxetanyl group. Among these, an oxetanyl group is preferred from the viewpoints of reactivity and storage stability. Examples of the organic group having 2 to 12 carbon atoms and a cyclic ether group include a 3-(3-ethyl-3-oxetanylmethoxy)propyl group.

[0051] The proportion of the structural unit (b) in the polysiloxane represented by formula (1) is not particularly limited. For example, the molar ratio of the structural unit (b) to all structural units (w / (v+w+x+y+z)) is preferably 0.2 to 0.99, more preferably 0.3 to 0.9, even more preferably 0.3 to 0.7, and particularly preferably 0.45 to 0.65, from the viewpoints of cure shrinkage, hardness, storage stability, and curability with active energy rays such as UV.

[0052] In the polysiloxane represented by formula (1), for example, from the viewpoints of cure shrinkage, hardness, storage stability, and curability with active energy rays such as UV, the mass ratio of the structural unit (b) is preferably 5% by mass to 99% by mass, more preferably 10% by mass to 90% by mass, even more preferably 15% by mass to 85% by mass, and particularly preferably 25% by mass to 80% by mass, relative to the total mass of the polysiloxane represented by formula (1).

[0053] (Structural Unit (c)) The structural unit (c) is a unit in which O is bonded to one silicon atom. １／２ Three oxygen atoms (1.5 oxygen atoms), R ２ is a T unit bonded to the silicon atom.

[0054] In the structural unit (c), R ２ R each independently represents a hydrocarbon group having 1 to 20 carbon atoms substituted with a fluorine atom. ２There is no particular limitation on the number of fluorine atoms R has, as long as it has 1 or more, and from the viewpoints of surface smoothing, durability, water repellency, and antifouling properties, it is preferable that R has 3 or more fluorine atoms, and more preferably 5 or more fluorine atoms. Furthermore, from the viewpoints of durability, water repellency, antifouling properties, and the transparency of the cured film obtained by curing the resulting polysiloxane or curable composition, ２ The number of fluorine atoms contained in R is preferably 3 to 50, more preferably 5 to 40, still more preferably 7 to 30, and particularly preferably 9 to 21. ２ is not particularly limited as long as it has one or more carbon atoms, and from the viewpoints of durability, water repellency, and antifouling properties, it is preferably a hydrocarbon group having a fluoroalkyl group having two or more carbon atoms, and more preferably a hydrocarbon group having a fluoroalkyl group having four or more carbon atoms. Furthermore, from the viewpoints of durability, water repellency, antifouling properties, and the transparency of the cured film obtained by curing the resulting polysiloxane or curable composition, it is preferable that R ２ is preferably a fluoroalkyl group having 2 to 30 carbon atoms, more preferably a fluoroalkyl group having 4 to 20 carbon atoms, even more preferably a fluoroalkyl group having 5 to 16 carbon atoms, and particularly preferably a fluoroalkyl group having 6 to 12 carbon atoms. ２ is preferably a group in which an alkylene group and a fluoroalkyl group are bonded from the viewpoint of availability. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 2 to 4 carbon atoms, and is particularly preferably an ethylene group.

[0055] The molar ratio (x / (v+w+x+y+z)) of the structural unit (c) to all structural units in the polysiloxane represented by formula (1) is less than 0.6, and from the viewpoints of durability, water repellency, stain resistance, hardness, and surface smoothness, is preferably 0.05 or greater but less than 0.6, more preferably 0.10 to 0.55, even more preferably 0.20 to 0.50, and particularly preferably 0.25 to 0.45. The molar ratio of the structural unit (c) to all structural units may be 0, but in that case, y is a positive number, i.e., the molar ratio of the structural unit (d) is a number greater than 0.

[0056] Furthermore, in the polysiloxane represented by formula (1), for example, when x>0, from the viewpoints of durability, water repellency, antifouling properties, hardness, and surface smoothness, the mass ratio of the structural unit (c) relative to the total mass of the polysiloxane represented by formula (1) is preferably 10% by mass to 75% by mass, more preferably 15% by mass to 70% by mass, even more preferably 20% by mass to 68% by mass, and particularly preferably 30% by mass to 65% by mass.

[0057] (Structural Unit (d)) The structural unit (d) is a unit in which O is bonded to one silicon atom. １／２ (one as an oxygen atom) and two R ３ is a D unit in which O is bonded to a silicon atom. １／２ It means a unit having two of these.

[0058] In the structural unit (d), R ３ each independently represents at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a monovalent organic group having a polymerizable group; R ３ The alkyl group, aralkyl group, aryl group, and monovalent organic group having a polymerizable group in R may be substituted with a structure selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, an aryloxy group, an aralkyloxy group, and an oxy group. ３ are each independently preferably at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group, even more preferably a methyl group or a phenyl group, and particularly preferably a methyl group. ３ In the above, preferred embodiments of the alkyl group having 1 to 10 carbon atoms, the aralkyl group having 7 to 10 carbon atoms, the aryl group having 6 to 10 carbon atoms, and the monovalent organic group having a polymerizable group are R １These are the same as the preferred embodiments of the alkyl group having 1 to 10 carbon atoms, the aralkyl group having 7 to 10 carbon atoms, the aryl group having 6 to 10 carbon atoms, and the monovalent organic group having a polymerizable group in formula (1). Furthermore, when x is 0 in formula (1), from the viewpoints of surface smoothness imparting ability, durability, water repellency, and stain resistance, the structural unit (d) has at least a structure represented by formula (S) below.

[0059]

[0060] n represents a number of 3 or more.

[0061] Furthermore, when x is 0 in the polysiloxane represented by formula (1), the polysiloxane contains a structure represented by formula (S) from the viewpoints of surface smoothness, durability, water repellency, and antifouling properties. The structure represented by formula (S) is a so-called silicone chain structure, formed by linking three or more structural units (d). There are no particular restrictions on n, as long as it is 3 or more. Furthermore, from the viewpoints of ease of availability and the transparency of the cured film obtained by curing the resulting polysiloxane or curable composition, n is preferably 300 or less, more preferably 200 or less, and even more preferably 100 or less. In the structure represented by formula (S), n may be a single value or a mixture of multiple values. When n is present, the average value N of n is preferably 3 or more, and from the viewpoints of durability, hardness, and surface smoothness of the cured product of the curable composition, it is preferably 4 or more, more preferably 5 to 50, and particularly preferably 6 to 30. N can be calculated, for example, from the average molecular weight of silicone used as a raw material when producing a silsesquioxane derivative represented by formula (1) described below. The structures represented by formula (S) may include structures where n is 1 or 2 in addition to structures where n is 3 or more.

[0062] There are no particular limitations on the proportion of the structural unit (d) in the polysiloxane represented by formula (1). For example, when x > 0, the molar ratio of the structural unit (d) to all structural units (y / (v + w + x + y + z)) is preferably 0 to 0.80, more preferably 0 to 0.70, even more preferably 0 to 0.55, and particularly preferably 0 to 0.50, from the viewpoints of durability, water repellency, antifouling properties, hardness, and surface smoothness.

[0063] In the polysiloxane represented by formula (1), when x is 0, the molar ratio of the structural unit (d) to all structural units (y / (v+w+x+y+z)) is preferably 0.10 to 0.80, more preferably 0.15 to 0.75, even more preferably 0.20 to 0.60, and particularly preferably 0.25 to 0.50, from the viewpoints of durability, water repellency, antifouling properties, hardness, and surface smoothness.

[0064] Furthermore, in the polysiloxane represented by formula (1), for example, when y>0, from the viewpoints of durability, water repellency, antifouling properties, hardness, and surface smoothness, the mass ratio of the structural unit (d) relative to the total mass of the polysiloxane represented by formula (1) is preferably 2% by mass to 80% by mass, more preferably 5% by mass to 70% by mass, even more preferably 8% by mass to 50% by mass, and particularly preferably 10% by mass to 30% by mass.

[0065] From the viewpoints of durability, water repellency, stain resistance, hardness, and surface smoothness, the total molar ratio ((x+y) / (v+w+x+y+z)) of the structural units (c) and (d) to all structural units is preferably 0.10 to 0.80, more preferably 0.15 to 0.70, and particularly preferably 0.20 to 0.50.

[0066] From the viewpoints of durability, water repellency, stain resistance, hardness, and surface smoothness, the total mass ratio of the structural units (c) and (d) in all structural units is preferably 5% by mass to 80% by mass, more preferably 10% by mass to 70% by mass, and particularly preferably 15% by mass to 65% by mass, relative to the total mass of the polysiloxane represented by formula (1).

[0067] The total molar ratio ((w+x+y) / (v+w+x+y+z)) of the structural units (b), (c), and (d) to all structural units is, from the viewpoints of durability, water repellency, stain resistance, hardness, and surface smoothness, preferably from 0.3 to 1, more preferably from 0.5 to 1, even more preferably from 0.7 to 1, and particularly preferably from 0.9 to 1.

[0068] From the viewpoints of durability, water repellency, stain resistance, hardness, and surface smoothness, the total mass ratio of the structural units (b), (c), and (d) in all structural units is preferably 30% by mass to 100% by mass, more preferably 50% by mass to 100% by mass, even more preferably 70% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass, relative to the total mass of the polysiloxane represented by formula (1).

[0069] (Structural Unit (e)) The structural unit (e) is a unit in which O is bonded to one silicon atom. １／２ (0.5 oxygen atoms), and one R ６ and two R ５ is an M unit in which O is bonded to a silicon atom. １／２ It means a unit having one

[0070] In the structural unit (e), R ４ and R ５ each independently represents at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a monovalent organic group having a polymerizable group; R ４ and R ５ The alkyl group, the aralkyl group, the aryl group, and the monovalent organic group having a polymerizable group in R may be substituted with a structure selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, an aryloxy group, an aralkyloxy group, and an oxy group. ４are each independently preferably at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group, even more preferably a methyl group or a phenyl group, and particularly preferably a methyl group. ５ are each independently preferably an alkyl group having 1 to 10 carbon atoms, a phenyl group, or an organic group having 2 to 12 carbon atoms and an ethylenically unsaturated group, more preferably a methyl group, a phenyl group, or a vinyl group, and particularly preferably a methyl group or a vinyl group. ５ From the viewpoints of reactivity and hardness, the polymerizable group in R is preferably at least one selected from the group consisting of a vinyl group, an acryloyl group, a methacryloyl group, an epoxy group, and an oxetanyl group, more preferably at least one selected from the group consisting of a vinyl group, an acryloyl group, a methacryloyl group, and an oxetanyl group, and particularly preferably a vinyl group. ４ and R ５ In addition to the above, preferred embodiments of the alkyl group having 1 to 10 carbon atoms, the aralkyl group having 7 to 10 carbon atoms, the aryl group having 6 to 10 carbon atoms, and the monovalent organic group having a polymerizable group in R １ These are the same as the preferred embodiments of the alkyl group having 1 to 10 carbon atoms, the aralkyl group having 7 to 10 carbon atoms, the aryl group having 6 to 10 carbon atoms, and the monovalent organic group having a polymerizable group in the above formula.

[0071] The proportion of the structural unit (e) in the polysiloxane represented by formula (1) is not particularly limited. For example, the molar ratio (z / (v+w+x+y+z)) of the structural unit (e) to all structural units is preferably 0.5 or less, more preferably 0.3 or less, and even more preferably 0.1 or less, from the viewpoints of cure shrinkage, hardness, storage stability, and curability with active energy rays such as UV. The molar ratio (z / (v+w+x+y+z)) of the structural unit (e) to all structural units may be 0 or may be 0.001 or more.

[0072] In the polysiloxane represented by formula (1), for example, from the viewpoints of cure shrinkage, hardness, storage stability, and curability with active energy rays such as UV, the mass ratio of the structural unit (e) is preferably 50 mass% or less, more preferably 30 mass% or less, and even more preferably 10 mass% or less, relative to the total mass of the polysiloxane represented by formula (1).

[0073] (Other structural units (f)) The polysiloxane represented by formula (1) may further contain (R ９ O １／２ ) (hereinafter, also referred to as structural unit (f)). ９ 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 linear or branched. Specific examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.

[0074] The structural unit (f) is an alkoxy group, which is a hydrolyzable group contained in the silicon compound described below, or an alkoxy group generated by substitution of the hydrolyzable group of the silicon compound with an alcohol contained in the reaction solvent, and may be one that remains in the molecule without being hydrolyzed or polycondensed, or may be a hydroxyl group that remains in the molecule after hydrolysis without being polycondensed.

[0075] The proportion of the structural unit (f) in the polysiloxane represented by formula (1) is not particularly limited. For example, from the viewpoint of viscosity and hardness of the cured product, the molar ratio of the structural unit (f) to all structural units is preferably 0.15 or less, more preferably 0.1 or less, and even more preferably 0.05 or less, or may be 0.01 or more.

[0076] In the polysiloxane represented by formula (1), the mass ratio of the structural unit (f) is preferably 10 mass% or less, more preferably 5 mass% or less, or may be 0 mass% or more, relative to the total mass of the polysiloxane represented by formula (1), from the viewpoints of viscosity and hardness when formed into a cured product. Alternatively, it may be 0.1 mass% or more.

[0077] (Weight-Average Molecular Weight of Polysiloxane Represented by Formula (1)) The weight-average molecular weight (hereinafter also referred to as "Mw") of the polysiloxane represented by Formula (1) is not particularly limited, but from the viewpoints of durability, water repellency, anti-fouling properties, hardness, and surface smoothness, it is preferably 300 to 30,000, more preferably 500 to 20,000, even more preferably 800 to 15,000, and particularly preferably 1,000 to 10,000. The number-average molecular weight (hereinafter also referred to as "Mn") of the polysiloxane represented by Formula (1) is not particularly limited, but from the viewpoints of durability, water repellency, anti-fouling properties, hardness, and surface smoothness, it is preferably 300 to 30,000, more preferably 400 to 20,000, even more preferably 500 to 15,000, and particularly preferably 800 to 10,000. In the present disclosure, Mw and Mn refer to values ​​obtained by converting molecular weights measured by GPC (gel permeation chromatography) using polystyrene as a standard substance. The measurement conditions for Mw can be, for example, the measurement conditions in the examples described below.

[0078] (Content of polysiloxane represented by formula (1)) The curable composition of the present disclosure contains 0.1 mass % or more and less than 10 mass % of the polysiloxane represented by formula (1), relative to the total solid content of the curable composition. From the viewpoints of durability, water repellency, antifouling properties, hardness, and surface smoothness, the content of the polysiloxane represented by formula (1) is preferably 0.1 mass % to 8 mass %, more preferably 0.2 mass % to 6 mass %, and particularly preferably 0.5 mass % to 5 mass %, relative to the total solid content of the curable composition.

[0079] (Method for producing polysiloxane represented by formula (1)) The polysiloxane represented by formula (1) can be produced by a known method. Methods for producing polysiloxane are disclosed in detail in WO 2013 / 031798, JP 2000-044689, etc.

[0080] The method for producing the polysiloxane represented by formula (1) comprises the steps of: ｍ Six k (where m represents an integer of 0 to 3, k represents an integer of 1 to 4, m+k=4, R represents a group bonded to a silicon atom in the polysiloxane represented by formula (1) via a carbon atom, and X represents a hydrolyzable group), using an organic solvent and adding 0.2 to 30 molar equivalents of water relative to the total amount of hydrolyzable groups possessed by the organosilicon compound (hereinafter also referred to as the "hydrolysis step"). R is a group (R １ ~R ５ X is preferably an alkoxy group, a silyloxy group, or a halogen atom, and more preferably an alkoxy group or a silyloxy group.

[0081] In the hydrolysis step, it is preferable to carry out 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. Also, in the hydrolysis step, the hydrolysis and polycondensation reaction of the organosilicon compound and, if necessary, other silicon compounds is carried out to obtain an intermediate product, polysiloxane, and then the obtained intermediate product may be further subjected to hydrolysis and polycondensation reaction with the organosilicon compound, etc.

[0082] When obtaining an intermediate product as described above, after carrying out hydrolysis and polycondensation reactions of the organosilicon compound and, if necessary, other silicon compounds, the obtained intermediate product may be further subjected to hydrolysis and polycondensation reactions of the organosilicon compound in which m is 3 and k is 1. This makes it possible to suitably synthesize a polysiloxane whose terminal portions are blocked with structural units (e) derived from the organosilicon compound in which m is 3 and k is 1, thereby suppressing an increase in the viscosity of the polysiloxane and improving its storage stability.

[0083] The method for producing the polysiloxane represented by formula (1) preferably includes a distillation step in which a silicon compound is subjected to hydrolysis and polycondensation in the presence of a reaction solvent, and then the reaction solvent, by-products, residual monomers, water, and the like are distilled off from the reaction solution.

[0084] In the organosilicon compound that provides the structural unit (a) through hydrolysis and polycondensation, examples of the Q monomer where m=0 and k=4 include tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane.

[0085] In the organosilicon compound that provides the structural units (b) and (c) by hydrolysis and polycondensation, examples of the T monomer that provides the structural units (b) and (C) where m is 1 and k is 3 include (3-acryloyloxypropyl)trimethoxysilane, (3-acryloyloxypropyl)triethoxysilane and (8-acryloyloxyoctyl)trimethoxysilane, (3-acryloyloxypropyl)trichlorosilane, (3-methacryloyloxypropyl)trimethoxysilane, (3-methacryloyloxypropyl)triethoxysilane and (8-methacryloyloxyoctyl)trimethoxysilane, (3-methacryloyloxypropyl)triethoxysilane and (8-methacryloyloxyoctyl)trimethoxysilane, (1H,1H,2H,2H-trichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, octyltrimethoxysilane, trimethoxy(trifluoromethyl)silane, triethoxy(trifluoromethyl)silane, trimethoxy(3,3,3-trifluoropropyl)silane, trimethoxy(4,4,4-trifluorobutyl)silane, triethoxy-1H,1H,2H,2H-heptadecafluorodecylsilane, triethoxy-1H,1H,2H,2H-tridecafluoro-n-octylsilane, trimethoxy(1H,1H,2H,2H-nonafluorohexyl)silane, phenyltrimethoxysilane, phenyl Triethoxysilane, benzyltrimethoxysilane, cyclohexyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, p-styryltrimethoxysilane, ethynyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 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, 3-ethyl-3-[{3-(triethoxysilyl)propoxy}methyl]oxetane, (3-ethyl-3 oxetanylmethoxy)propyltrimethoxysilane, and the like.

[0086] In the organosilicon compound that provides the structural unit (d) through hydrolysis and polycondensation, examples of the D monomer where m is 2 and k is 2 include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldidiethoxysilane, diperfluoromethyldimethoxysilane, diperfluoroethyldiethoxysilane, propylmethyldimethoxysilane, octylmethyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, benzylmethyldimethoxysilane, cyclohexylmethyldimethoxysilane, vinylmethyl Examples of suitable silanes include dimethoxysilane, allylmethyldimethoxysilane, p-styrylmethyldimethoxysilane, ethynylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropylmethyldimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropylmethyldimethoxysilane hydrochloride, 3-ureidopropylmethyldialkoxysilane, 3-isocyanatopropylmethyldiethoxysilane, (3-acryloxypropyl)methyldimethoxysilane, and (3-methacryloxypropyl)methyldiethoxysilane.

[0087] In the organosilicon compound that provides the structural unit (e) through hydrolysis and polycondensation, examples of the compound where m is 3 and k is 1 include, as the M monomer, trimethylmethoxysilane, trimethylethoxysilane, tri(perfluoromethyl)methoxysilane, tri(perfluoroethyl)methoxysilane, trimethylchlorosilane, dimethylphenylmethoxysilane, methoxydimethylvinylsilane, ethoxydimethylvinylsilane, chlorodimethylvinylsilane, dimethylvinylsilanol, (3-acryloyloxypropyl)dimethylmethoxysilane, (3-methacryloyloxypropyl)dimethylmethoxysilane, p-styryldimethylmethoxysilane, and ethynyldimethylmethoxysilane. Furthermore, examples of M dimers that provide two structural units (e) through hydrolysis and polycondensation include hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-bis(p-styryl)tetramethyldisiloxane, 1,3-bis(3-acryloyloxypropyl)tetramethyldisiloxane, 1,3-bis(3-methacryloyloxypropyl)tetramethyldisiloxane, and hexa(perfluoromethyl)disiloxane.

[0088] Furthermore, examples of raw materials that provide the structural unit (d) include reactive silicone compounds having a siloxane bond-forming group represented by the following formula (3) or formula (4): By using such reactive silicone compounds, the silicone chain structure represented by formula (S) can be efficiently introduced into the silsesquioxane derivative represented by formula (1).

[0089]

[0090] Y in formula (3) and formula (4) １is a siloxane bond-forming group. The siloxane bond-forming group refers to an atom or atomic group capable of forming a siloxane bond with a silicon atom in a silane compound, and specific examples thereof include alkoxy groups such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, and t-butoxy groups, cycloalkoxy groups such as cyclohexyloxy, aryloxy groups such as phenyloxy, hydroxyl groups, and hydrogen atoms. In particular, siloxane bond-forming groups in which the hydroxyl group is the siloxane bond-forming group are preferred because they are easily available and the reaction with the silane compound is easily controlled.

[0091] The reactive silicone compound represented by formula (3) has two siloxane bond-forming groups in one molecule, and these may be the same or different groups. The reactive silicone compound represented by formula (4) has one siloxane bond-forming group in one molecule. In the present disclosure, either formula (3) or formula (4) may be used, but it is particularly preferable to use a reactive silicone compound represented by formula (3) having two siloxane bond-forming groups in one molecule.

[0092] R in formula (3) and formula (4) １１ and R １４ each independently represents an alkoxy group, an aryloxy group, an alkyl group, a cycloalkyl group, or an aryl group, and two R １１ and R １４ may be the same group or different groups. １１ and R １４ Specific examples of the alkyl group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, a t-butoxy group, a cyclohexyloxy group, a phenyloxy group, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, a cyclohexyl group, and a phenyl group.

[0093] R in formula (3) and formula (4) １２ , R １３ and R １５ each independently represents an alkyl group, a cycloalkyl group, or an aryl group, and a plurality of R ２and R ３ may be the same group or different groups. １２ , R １３ and R １５ Specific examples of R are methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, cyclohexyl, phenyl, etc. Reactive silicone compounds include those having a plurality of R groups present in one molecule. １２ and R １３ are methyl groups or ethyl groups, can be produced from inexpensive raw materials, and a cured product obtained using a curable resin obtained using the polysiloxane represented by formula (1) of the present disclosure is preferred from the viewpoints of durability, water repellency, antifouling properties, hardness, and surface smoothness, and those in which all are methyl groups are particularly preferred because these effects are significant.

[0094] The number of repeating units j in formula (3) and formula (4) represents a positive number. As for the reactive silicone compound, from the viewpoints of the transparency of the resulting polysiloxane, compatibility with other components of the curable composition, and the transparency, durability, water repellency, antifouling properties, hardness, and surface smoothness of the cured product of the curable composition, j is preferably a number from 1 to 300, more preferably a number from 2 to 100, even more preferably a number from 3 to 100, and particularly preferably a number from 4 to 50. Furthermore, as for the reactive silicone compound, j in formula (3) and formula (4) may be a single value or a mixture of compounds each having multiple values, and the average value J is a number of 1 or more, preferably 2 or more, more preferably 3 to 50, even more preferably 4 to 30, and particularly preferably 6 to 20, from the same viewpoints as above. The average value J can be calculated, for example, from the average molecular weight of the reactive silicone.

[0095] Among the reactive silicone compounds, R １１ and R １４is an alkoxy group or an aryloxy group, can be obtained, for example, by a dealcoholization reaction between a polysiloxane-α,ω-diol and a trialkoxysilane or triaryloxysilane, or by an elimination reaction of phenols. This reaction is preferably carried out in the absence of a catalyst under conditions in which the trialkoxysilane or triaryloxysilane is in excess, but it can also be carried out using a transesterification catalyst such as p-toluenesulfonic acid or trifluoroacetic acid.

[0096] Commercially available reactive silicone compounds that are raw materials for the structural unit (d) include dimethylpolysiloxane (X-21-5841, KF-9701, and XF-3905, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0097] In the hydrolysis step, the reaction solvent is not particularly limited, but it is preferable to use an alcohol as the organic solvent. The alcohol is an alcohol in the narrow sense, represented by the general formula R—OH, and is a compound having no functional groups 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.

[0098] The organic solvent used in the hydrolysis step may be alcohol alone, or may be a mixed solvent with at least one auxiliary solvent. The auxiliary solvent may be either a polar solvent or a non-polar solvent, or a combination of both. Examples of organic solvents other than alcohol include xylene, toluene, methyl ethyl ketone, methyl isobutyl ketone, and propylene glycol monomethyl ether.

[0099] The hydrolysis and condensation reactions in the hydrolysis step proceed in the presence of water. In the hydrolysis step, it is preferable to add 0.2 to 30 molar equivalents of water relative to the total amount of hydrolyzable groups possessed by the organosilicon compound to carry out hydrolysis and further condensation. Furthermore, in terms of the cure shrinkage, hardness, storage stability, and curl suppression properties during curing of the resulting polysiloxane, the amount of water added in the hydrolysis step is preferably 0.2 to 10 molar equivalents relative to the total amount of hydrolyzable groups possessed by the organosilicon compound, more preferably 0.3 to 7 molar equivalents, even more preferably 0.4 to 7 molar equivalents, particularly preferably 0.5 to 7 molar equivalents, and most preferably 0.6 to 6 molar equivalents.

[0100] The hydrolysis and polycondensation reaction of the silicon compound may be carried out without a catalyst or may be carried out using a catalyst. When a catalyst is used, acid catalysts exemplified by inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, and phosphoric acid; organic acids such as formic acid, acetic acid, oxalic acid, and paratoluenesulfonic acid; and base catalysts such as ammonia, tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate are preferably used, with acid catalysts being more preferred. The amount of 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%, relative to the total amount (mol) of silicon atoms contained in the silicon compound.

[0101] 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 the polysiloxane represented by formula (1), an auxiliary agent can be added to the reaction system.

[0102] By providing the above-described distillation step after the hydrolysis step in the production of the polysiloxane represented by formula (1), the stability of the resulting silsesquioxane derivative of the present disclosure can be improved. The distillation step can be carried out under normal pressure or reduced pressure, at room temperature or under heating, or under cooling.

[0103] The method for producing the polysiloxane represented by formula (1) may include a neutralization step of neutralizing the catalyst prior to the distillation step, and may also include a step of removing the salt produced by the neutralization by washing with water or the like.

[0104] Furthermore, the polysiloxane represented by formula (1) may contain, among the side-chain functional groups derived from the silicon compound used as a raw material in its production, a group formed by ring-opening due to the addition of an acid or the like to an oxetanyl group or an epoxy group, or may contain a hydroxyalkyl group formed by decomposition of an organic group having a (meth)acryloyl group, or a group formed by the addition of an acid or the like to an unsaturated hydrocarbon group, etc. Specific examples include those containing a structure represented by formula (A) and / or a structure represented by formula (B) below as part of formula (1). The content of these units is sufficient for implementing the present disclosure as long as it is 50 mol% or less relative to the amount corresponding to the original organic group having an oxetanyl group or an epoxy group, the original organic group having a (meth)acryloyl group, or the original organic group having an unsaturated hydrocarbon group derived from the silicon compound as a raw material, and is preferably 30 mol% or less, and more preferably 10 mol% or less. In both formulas (A) and (B), T units are exemplified, but similar D units, M units, etc. may also be used.

[0105]

[0106]

[0107] <Polysiloxane Represented by Formula (2)> From the viewpoints of durability, hardness, and storage stability, the curable composition of the present disclosure preferably further contains a polysiloxane represented by the following formula (2) in addition to the polysiloxane represented by formula (1).

[0108]

[0109] In formula (2), R ６ , R ７ and R ８ each independently represents at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a monovalent organic group having a polymerizable group; R ６ , R ７ and R ８ At least one of R is a monovalent organic group having a polymerizable group, ６ , R ７ and R ８ wherein the alkyl group, the aralkyl group, the aryl group, and the monovalent organic group having a polymerizable group may be substituted with a structure selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, an aryloxy group, an aralkyloxy group, and an oxy group, q represents a positive number, and p, r, and s each independently represent 0 or a positive number.

[0110] R ６ , R ７ and R ８ In addition to the above, preferred embodiments of the alkyl group having 1 to 10 carbon atoms, the aralkyl group having 7 to 10 carbon atoms, the aryl group having 6 to 10 carbon atoms, and the monovalent organic group having a polymerizable group in R １ These are the same as the preferred embodiments of the alkyl group having 1 to 10 carbon atoms, the aralkyl group having 7 to 10 carbon atoms, the aryl group having 6 to 10 carbon atoms, and the monovalent organic group having a polymerizable group in the above formula.

[0111] The constituent units in the polysiloxane represented by formula (2) are referred to as constituent units (g) to (j) below.

[0112]

[0113] In the polysiloxane represented by formula (2), q represents a positive number, and p, r, and s are each independently 0 or a positive number. In other words, the polysiloxane represented by formula (2) contains the structural unit (h) among the structural units (g) to (j) described above, and may contain at least one of the structural unit (g), the structural unit (i), and the structural unit (j) as necessary. Furthermore, because the polysiloxane represented by formula (2) contains at least the structural unit (h), it is sometimes referred to as silsesquioxane instead of polysiloxane.

[0114] The proportion of the structural unit (g) in the polysiloxane represented by formula (2) is not particularly limited. For example, from the viewpoint of viscosity, the molar ratio of the structural unit (g) to all structural units (p / (p+q+r+s)) is preferably 0.6 or less, more preferably 0.5 or less, even more preferably 0.3 or less, and even more preferably 0.1 or less.

[0115] The proportion of the structural unit (h) in the polysiloxane represented by formula (2) is not particularly limited. For example, the molar ratio of the structural unit (h) to all structural units (q / (p+q+r+s)) is preferably 0.3 to 1, more preferably 0.5 to 1, and particularly preferably 0.7 to 1, from the viewpoints of cure shrinkage, hardness, storage stability, UV curability, and viscosity.

[0116] The proportion of the structural unit (i) in the polysiloxane represented by formula (2) is not particularly limited. For example, the molar ratio of the structural unit (i) to all structural units (r / (p+q+r+s)) is preferably 0.5 or less, more preferably 0.3 or less, and even more preferably 0.1 or less, from the viewpoints of viscosity and hardness of the cured product.

[0117] The proportion of the structural unit (j) in the polysiloxane represented by formula (2) is not particularly limited. For example, from the viewpoints of viscosity and hardness of the cured product, the molar ratio of the structural unit (j) to all structural units (s / (p+q+r+s)) is preferably 0.5 or less, more preferably 0.3 or less, and even more preferably 0.1 or less.

[0118] (Weight-Average Molecular Weight of Polysiloxane Represented by Formula (2)) The Mw of the polysiloxane represented by Formula (2) 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.

[0119] (Viscosity of polysiloxane represented by formula (2)) The viscosity of the polysiloxane represented by formula (2) at 25°C is not particularly limited, and it may be a solid. The polysiloxane represented by formula (2) is preferably a liquid from the viewpoint of handling, and in this case, the viscosity is not particularly limited, but is preferably 10 mPa·s to 100,000 mPa·s, more preferably 100 mPa·s to 80,000 mPa·s, even more preferably 300 mPa·s to 60,000 mPa·s, and particularly preferably 500 mPa·s to 50,000 mPa·s. In the present disclosure, the viscosity at 25°C refers to a value measured using an E-type viscometer (a cone-plate viscometer, for example, a TVE22H viscometer manufactured by Toki Sangyo Co., Ltd.).

[0120] (Content of Polysiloxane Represented by Formula (2)) From the viewpoints of durability, hardness, and storage stability, the content of the polysiloxane represented by formula (2) is preferably 50% by mass to 99.9% by mass, more preferably 65% ​​by mass to 99.5% by mass, and particularly preferably 80% by mass to 99.5% by mass, relative to the total solid content of the curable composition.

[0121] The method for producing the polysiloxane represented by formula (2) is not particularly limited, and the polysiloxane can be produced by a known method, which is disclosed in detail as a method for producing polysiloxane in WO 2013 / 031798, etc. In addition, the method for producing the polysiloxane represented by formula (1) described above can also be referenced.

[0122] <Polymerization initiator> From the viewpoint of curability, the curable composition of the present disclosure preferably contains a polymerization initiator. The polymerization initiator is not particularly limited, and examples thereof include a photopolymerization initiator and a thermal polymerization initiator. Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator. Examples of the thermal polymerization initiator include a thermal radical polymerization initiator. Known compounds may be used as the photopolymerization initiator and the thermal polymerization initiator.

[0123] Examples of photoradical polymerization initiators include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and diethoxy Acetophenone compounds such as acetophenone, oligo[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-propan-1-one; benzophenone compounds such as benzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone and 4-benzoyl-4'-methyldiphenyl sulfide; methylbenzoyl formate, oxyphenyl acetate α-ketoester compounds such as 2-[2-oxo-2-phenylacetoxyethoxy]ethyl ester of oxyphenylacetic acid and 2-[2-hydroxyethoxy]ethyl ester of oxyphenylacetic acid; phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; benzoin, benzoin methyl ether, benzoin benzoin-based compounds such as benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; titanocene-based compounds; acetophenone / benzophenone hybrid photoinitiators such as 1-(4-(4-benzoylphenylsulfanyl)phenyl)-2-methyl-2-(4-methylphenylsulfinyl)propan-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.

[0124] Examples of the cationic photopolymerization initiator include onium salts such as iodonium salts, sulfonium salts, diazonium salts, selenium salts, pyridinium salts, ferrocenium salts, and phosphonium salts. Among these, iodonium salts or sulfonium salts are preferred. When the cationic photopolymerization initiator is an iodonium salt or a sulfonium salt, examples of the counter anion include a tetrafluoroboronium anion, a hexafluoroarsenium anion, a hexafluoroantimonium anion, and a hexafluorophosphonium anion.

[0125] Examples of the iodonium salt include (tricumyl)iodonium tetrakis(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis(pentafluorophenyl)borate, bis(dodecylphenyl)iodonium hexafluorophosphate, bis(dodecylphenyl)iodonium hexafluoroantimonate, and bis(dodecylphenyl)iodonium tetrafluoroborate.

[0033] Examples of iodonium tetrakis(pentafluorophenyl)borate include bis(dodecylphenyl)iodonium tetrakis(pentafluorophenyl)borate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluorophosphate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluoroantimonate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrafluoroborate, and 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrakis(pentafluorophenyl)borate. In addition, commercially available iodonium salts can also be used, and specific examples include "UV9380C" (trade name) manufactured by Momentive Performance Materials Japan, Inc., "BLUESIL PI 2074" (trade name) manufactured by Elkem Silicones, and "WPI-116" (trade name) and "WPI-113" (trade name) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0126] Examples of the sulfonium salts include bis[4-(diphenylsulfonio)phenyl]sulfide bishexafluorophosphate, bis[4-(diphenylsulfonio)phenyl]sulfide bishexafluoroantimonate, bis[4-(diphenylsulfonio)phenyl]sulfide bistetrafluoroborate, bis[4-(diphenylsulfonio)phenyl]sulfide tetrakis(pentafluorophenyl)borate, diphenyl-4-(phenylthio)phenylsulfonium hexafluorophosphate, diphenyl-4-(phenylthio)phenylsulfonium hexafluoroantimonate, diphenyl-4-(phenylthio)phenylsulfonium tetrafluoroborate, and diphenyl-4-(phenylthio)phenylsulfonium tetrakis(pentafluorophenyl)borate. phenyl)borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl]sulfide bishexafluorophosphate, bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl]sulfide bishexafluoroantimonate, bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl]sulfide bistetrafluoroborate, and bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl]sulfide tetrakis(pentafluorophenyl)borate.In addition, commercially available sulfonium salts can also be used, and specific examples include "CYRACURE UVI-6990" (trade name), "CYRACURE UVI-6992" (trade name), and "CYRACURE UVI-6974" manufactured by Dow Chemical Japan, "ADEKAOPTOMER SP-150" (trade name), "ADEKAOPTOMER SP-152" (trade name), "ADEKAOPTOMER SP-170" (trade name), and "ADEKAOPTOMER SP-172" (trade name) manufactured by ADEKA Corporation, and "WPAG-370" (trade name) and "WPAG-638" (trade name) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0127] Examples of the diazonium salt include benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, and benzenediazonium hexafluoroborate.

[0128] There are no particular limitations on the thermal radical polymerization initiator, and examples thereof include peroxides and azo-based initiators.

[0129] Examples of peroxides include hydrogen peroxide; inorganic peroxides such as sodium persulfate, ammonium persulfate, and potassium persulfate; 1,1-bis(t-butylperoxy)2-methylcyclohexane, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, and 2,2-bis(4,4-dibutyl peroxycyclohexyl)propane, 1,1-bis(t-butylperoxy)cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di(m-toluoylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxy Oxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxyacetate, 2,2-bis(t-butylperoxy)butane, t-butylperoxybenzoate, n-butyl-4,4-bis(t-butylperoxy)valerate, di-t-butylperoxyisophthalate, α,α'-bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl Examples of organic peroxides include diisopropyl benzene hydroperoxide, di-t-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, dilauroyl peroxide, and t-butyl hydroperoxide. These may be used alone or in combination of two or more.

[0130] Examples of azo initiators include azo compounds such as 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, azodi-t-octane, and azodi-t-butane. These may be used alone or in combination of two or more. A redox reaction can also be carried out by combining a peroxide with a redox polymerization initiation system that uses a reducing agent such as ascorbic acid, sodium ascorbate, sodium erythorbate, tartaric acid, citric acid, a metal salt of formaldehyde sulfoxylate, sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium metabisulfite, or ferric chloride.

[0131] In the curable composition of the present disclosure, the content of the polymerization initiator is preferably 0.01% by mass to 20% by mass, more preferably 0.1% by mass to 10% by mass, and even more preferably 1% by mass to 8% by mass, relative to the total solid content of the curable composition.

[0132] <Other Components> The other components are not particularly limited, and examples thereof include solvents, polymerizable compounds other than the polysiloxane represented by Formula (1) and the polysiloxane represented by Formula (2), resins, silicones, monomers, fillers, surfactants, antistatic agents (e.g., conductive polymers), leveling agents, photosensitizers, UV absorbers, antioxidants, heat resistance improvers, stabilizers, lubricants, pigments, dyes, plasticizers, suspending agents, adhesion promoters, nanoparticles, nanofibers, and nanosheets. Examples of fillers include silica particles (manufactured by JGC Catalysts and Chemicals Co., Ltd.: V-8804), silicon-modified silica (manufactured by BYK Corporation: NANOBYK-3650), and silicon-acrylic-modified silica (manufactured by BYK Corporation: BYK-UV3518). The curable composition of the present disclosure may also include silane-based reactive diluents such as tetraalkoxysilanes, trialkoxysilanes, dialkoxysilanes, monoalkoxysilanes, and disiloxanes.

[0133] The curable composition of the present disclosure may or may not contain a solvent, for example, 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.

[0134] The curable composition of the present disclosure may or may not contain a polymerizable compound other than the polysiloxane represented by formula (1) and the polysiloxane represented by formula (2) (hereinafter also referred to as "other polymerizable compounds"). The other polymerizable compound is not particularly limited as long as it is a compound capable of undergoing a polymerization reaction in the presence of the polysiloxane represented by formula (1), and optionally the polysiloxane represented by formula (2), and a polymerization initiator. Examples of the other polymerizable compound include polysiloxanes other than the polysiloxane represented by formula (1) and the polysiloxane represented by formula (2), (meth)acrylate compounds, compounds having an ethylenically unsaturated group, epoxy compounds (compounds having an epoxy group), compounds having an oxetanyl group (oxetanyl group-containing compounds), and compounds having a vinyl ether group (vinyl ether compounds).

[0135] Examples of polysiloxanes other than the polysiloxanes represented by formula (1) and formula (2) include polysiloxanes having polymerizable groups only in units other than T units.

[0136] The (meth)acrylate compound is not particularly limited, and examples thereof include a compound having one (meth)acryloyl group (hereinafter also referred to as a "monofunctional (meth)acrylate") and a compound having two or more (meth)acryloyl groups (hereinafter also referred to as a "polyfunctional (meth)acrylate").

[0137] 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-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and tricyclodecanemethylol (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 (meth)acrylate of phenol ethylene oxide adduct, (meth)acrylate of phenol propylene oxide adduct, (meth)acrylate of modified nonylphenol ethylene oxide adduct, (meth)acrylate of nonylphenol propylene oxide adduct, (meth)acrylate of alkylene oxide adduct of para-cumylphenol, orthophenylphenol (meth)acrylate, and (meth)acrylate of alkylene oxide adduct of orthophenylphenol; monofunctional (meth)acrylates having an alkoxyalkyl group such as 2-ethylhexyl carbitol (meth)acrylate; monofunctional (meth)acrylates having a heterocycle such as tetrahydrofurfuryl (meth)acrylate and N-(2-(meth)acryloxyethyl)hexahydrophthalimide; Hydroxylalkyl (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 carboxy group such as ω-carboxypolycaprolactone mono(meth)acrylate and monohydroxyethyl phthalate (meth)acrylate.

[0138] Examples of polyfunctional (meth)acrylates 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; Examples of the di(meth)acrylate include 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.

[0139] As the polyfunctional (meth)acrylate, a urethane (meth)acrylate can also be used. Examples of the urethane (meth)acrylate include a compound obtained by addition reaction of an organic polyisocyanate with a hydroxyl group-containing (meth)acrylate, and a compound obtained by addition reaction of an organic polyisocyanate with a polyol and a hydroxyl group-containing (meth)acrylate. The monofunctional (meth)acrylate, polyfunctional (meth)acrylate, etc. may be used alone or in combination of two or more types, or different types may be used in combination.

[0140] Here, examples of polyols include low-molecular-weight polyols, polyether polyols, polyester polyols, and polycarbonate polyols. Examples of low-molecular-weight polyols include ethylene glycol, propylene glycol, neopentyl glycol, cyclohexane dimethylol, and 3-methyl-1,5-pentanediol. Examples of polyether polyols include polypropylene glycol and polytetramethylene glycol. Examples of polyester polyols 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 anhydrides thereof. These may be used alone or in combination of two or more types, or different types may be used in combination.

[0141] Examples of organic polyisocyanates include tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Examples of hydroxyl group-containing (meth)acrylates include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; and hydroxyl group-containing polyfunctional (meth)acrylates such as pentaerythritol tri(meth)acrylate, di(meth)acrylate of an adduct of 3 moles 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.

[0142] When a (meth)acrylate compound is used in combination with the curable composition of the present disclosure, the blending ratio thereof is not particularly limited, and for example, the blending ratio of the (meth)acrylate compound is preferably 0% by mass to 50% by mass, more preferably 0% by mass to 25% by mass, and even more preferably 0% by mass to 10% by mass, relative to the total solid content of the curable composition. From the viewpoint of adhesion to the inorganic substance layer, a low blending ratio of the (meth)acrylate compound is preferred, and it is preferably not contained or its content is 10% by mass or less relative to the total solid content of the composition, more preferably not contained or its content is 5% by mass or less relative to the total solid content of the composition, even more preferably not contained or its content is 1% by mass or less relative to the total solid content of the composition, and it is particularly preferred that it is not contained.

[0143] 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 an ethylenically unsaturated group include (meth)acrylic acid, a Michael addition dimer of acrylic acid, N-(2-hydroxyethyl)citraconimide, N,N-dimethylacrylamide, acryloylmorpholine, N-vinylpyrrolidone, and N-vinylcaprolactam. These compounds may be used alone or in combination of two or more.

[0144] Examples of epoxy compounds include monofunctional epoxy compounds and polyfunctional epoxy compounds. Examples of oxetanyl group-containing compounds include monofunctional oxetane compounds and polyfunctional oxetane compounds. Examples of vinyl ether compounds include monofunctional vinyl ether compounds and polyfunctional vinyl ether compounds. For example, compounds described in JP 2011-42755 A may be used as these compounds. There are no particular limitations on the silicone, and known silicones can be used, such as polydimethylsilicone, polydiphenylsilicone, and polymethylphenylsilicone, with those having functional groups at their terminals and / or side chains being preferred. There are no particular limitations on the functional group, and examples include (meth)acryloyl groups, epoxy groups, oxetanyl groups, vinyl groups, hydroxyl groups, carboxy groups, amino groups, and thiol groups.

[0145] When the curable composition of the present disclosure contains other polymerizable compounds, the content of the other polymerizable compounds is preferably 0.01% by mass to 50% by mass, more preferably 0.1% by mass to 25 parts by mass, and even more preferably 1% by mass to 15% by mass, relative to the total solid content of the curable composition.

[0146] (Elastic Modulus of Cured Product) From the viewpoints of cure shrinkage, hardness, storage stability, and curl suppression during curing, the elastic modulus at 23°C of the cured product obtained by curing the curable composition of the present disclosure is preferably greater than 2.0 GPa, more preferably greater than 4.0 GPa, even more preferably greater than 4.0 GPa and not greater than 20.0 GPa, and particularly preferably 4.2 GPa or greater and not greater than 15.0 GPa.

[0147] In the present disclosure, the elastic modulus of a cured product at 23° C. is measured by the method for measuring the indentation elastic modulus described in the Examples. In the present disclosure, a curable composition capable of producing a cured product having excellent hardness means that the cured product obtained by curing the curable composition has an excellent elastic modulus.

[0148] [Cured Product] 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 by heating the curable composition of the present disclosure.

[0149] The curable composition of the present disclosure may be cured after being applied to a substrate. The curable composition of the present disclosure may or may not contain a solvent. When the curable composition contains a solvent, it is preferable to remove the solvent before curing.

[0150] When applying the curable composition of the present disclosure to a substrate, the application method of the curable composition is not particularly limited. Examples of application methods include common coating methods such as casting, spin coating, bar coating, dip coating, spray coating, roll coating, flow coating, and gravure coating. The thickness of the applied curable composition of the present disclosure is not particularly limited and may 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, fibers, and fabrics. 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, fluororesins such as polyimide resins, polyamideimide resins, and 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, acetylcellulose resins such as triacetylcellulose (TAC), composite resins such as polychloroprene, polyphenylene sulfide, polysulfone, polyethersulfone, polyetheretherketone, polyurethane resins, and glass epoxy resins, and various fiber-reinforced resins. Examples of fibers include natural fibers, recycled fibers, semi-synthetic fibers, metal fibers, glass fibers, carbon fibers, ceramic fibers, and known chemical fibers. The fabric may be woven or nonwoven and may be made, for example, using the fibers described above.These materials may be used alone, or two or more may be combined, mixed, or composited. The shape of the substrate is not particularly limited, and examples thereof include plate-like, sheet-like, film-like, rod-like, spherical, fibrous, powder-like, lens-like, and other regular or irregular shapes.

[0151] (Curing Method) In the present disclosure, the curing method and curing conditions are selected depending on whether the curable composition is active energy ray-curable and / or thermosetting. Furthermore, the curing conditions (e.g., the type of light source and the amount of light irradiation in the case of active energy ray-curable compositions, and the heating temperature and heating time in the case of thermosetting compositions) are appropriately selected depending on the type and amount of polymerization initiator contained in the composition and the types of other polymerizable compounds.

[0152] (1) Active Energy Ray Curing Method When the present composition is an active energy ray-curable composition, the curing method may involve irradiating active energy rays using a known active energy ray irradiation device or the like. Examples of active energy rays include electron beams, and light such as ultraviolet light, visible light, and X-rays. Light is preferred, and ultraviolet light is more preferred from the viewpoint of the use of inexpensive equipment. Examples of ultraviolet light irradiation devices include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, ultraviolet (UV) electrodeless lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, and light-emitting diodes (LEDs). The light irradiation intensity on a coating formed by applying the present composition may be selected depending on the purpose, application, etc., and the light irradiation intensity in the light wavelength range effective for activating an active energy ray polymerization initiator (referred to as a photopolymerization initiator in the case of photocurable compositions) (this varies depending on the type of photopolymerization initiator, but preferably light with a wavelength of 220 nm to 460 nm is used) is 0.1 mW / cm. ２ ~1000mW / cm ２ The irradiation energy should be appropriately set depending on the type of active energy ray, the formulation, etc. The light irradiation time of the coating may also be selected depending on the purpose, application, etc., and it is preferable that the integrated light amount, which is expressed as the product of the light irradiation intensity and the light irradiation time in the light wavelength range, is 10 mJ / cm. ２~7,000mJ / cm ２ It is preferable that the light irradiation time is set so that the integrated light amount is 200 mJ / cm ２ ~5,000mJ / cm ２ More preferably, 500 mJ / cm ２ ~4,000mJ / cm ２ When the integrated light amount is within the above range, the curing of the composition proceeds smoothly, and a uniform cured product can be easily obtained.

[0153] Furthermore, heat curing can be appropriately combined before and / or after photocuring. For example, a substrate having a shaded area when irradiated with light may be impregnated with the composition, and then the composition may be irradiated with light to first cure the composition in the area exposed to light, and then heat may be applied to cure the composition in the area not exposed to light, thereby performing two-stage curing. There are no particular limitations on such substrates, and examples include substrates with complex shapes such as fabric-like, fibrous, powder-like, porous, and uneven, and may also have a shape in which two or more of these shapes are combined.

[0154] (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 constant or may be increased. A combination of temperature increase and decrease may also be used. The curing time is appropriately selected depending on the type of thermal polymerization initiator and the content ratio of other components, and is preferably 10 minutes to 360 minutes, more preferably 30 minutes to 300 minutes, and even more preferably 60 minutes to 240 minutes. By curing the composition under the above-mentioned preferred conditions, a uniform cured film free of blistering, cracks, etc. can be formed.

[0155] (Applications of Curable Compositions, etc.) The cured product of the present disclosure has excellent hardness and can be applied to hard coats, optical components, and the like. Furthermore, a hard coat having excellent hardness can be obtained by curing a hard coat agent containing the curable composition of the present disclosure. The hard coat agent of the present disclosure may be provided on a substrate. For example, a substrate having a hard coat can be obtained by curing a hard coat agent applied to a substrate. The hard coat agent of the present disclosure may contain various components as needed. The cured product or hard coat of the present disclosure has excellent weather resistance. This is presumably due to the excellent durability, water repellency, and stain resistance of the curable composition of the present disclosure, which suppresses deterioration of the cured product even under harsh conditions. The curable composition of the present disclosure can be applied, for example, to adhesive applications, printing applications such as inkjet printing and 3D printing, coating applications, nanoprinting applications, and the like. The curable composition of the present disclosure may be used in combination with fillers, other polymerizable compounds, and the like.

[0156] The elastic modulus at 23°C of the cured product of the present disclosure or the hard coat of the present disclosure is preferably greater than 2.0 GPa, more preferably greater than 4.0 GPa, even more preferably greater than 4.0 GPa and not greater than 20.0 GPa, and particularly preferably 4.2 GPa or greater but not greater than 15.0 GPa.

[0157] Next, the present disclosure will be specifically described based on examples and comparative examples, but the present disclosure is not limited to the following examples.

[0158] Synthesis of Polysiloxane Represented by Formula (1) (Synthesis Example 1: Synthesis of Polysiloxane 1) 19.7 g of 3-acryloyloxypropyltrimethoxysilane (0.08 mol, manufactured by Shin-Etsu Chemical Co., Ltd.), 73.5 g of triethoxytridecafluoro-n-octylsilane (0.14 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), and 157 g of 2-propanol were weighed into a 500 mL four-neck flask equipped with a stirrer, a dropping funnel, and a Dimroth trap, and 12.4 g of a 2 mass % aqueous hydrochloric acid solution was added dropwise. After stirring for 1 hour, 1.12 g of dimethyldivinyldisiloxane (6 mmol, manufactured by Silicon Materials Development Co., Ltd.) was added dropwise and the mixture was stirred at room temperature overnight. The solvent was removed from the resulting solution under vacuum, yielding 73 g of Polysiloxane 1. １ H-NMR analysis confirmed that each structural unit was quantitatively introduced according to the ratio of the raw materials used.

[0159] Synthesis Example 2 Synthesis of Polysiloxane 2 62 g of Polysiloxane 2 was obtained in the same manner as in Synthesis Example 1, except that the amount of 3-acryloyloxypropyltrimethoxysilane was changed to 30.9 g (0.13 mol) and the amount of triethoxytridecafluoro-n-octylsilane was changed to 49 g (0.07 mol).

[0160] Synthesis Example 3 Synthesis of Polysiloxane 3 56 g of Polysiloxane 3 was obtained in the same manner as in Synthesis Example 1, except that the amount of 3-acryloyloxypropyltrimethoxysilane was changed to 36.5 g (0.16 mol) and the amount of triethoxytridecafluoro-n-octylsilane was changed to 36.7 g (0.1 mol).

[0161] Synthesis Example 4 Synthesis of Polysiloxane 4 56.7 g (0.24 mol, manufactured by Shin-Etsu Chemical Co., Ltd.) of 3-acryloyloxypropyltrimethoxysilane, 10 g of polydimethylsiloxane (X-21-5841 manufactured by Shin-Etsu Chemical Co., Ltd., both terminally silanol-modified, functional group equivalent: 500 g / mol), and 103 g of 2-propanol were weighed into a 500 mL four-neck flask equipped with a stirrer, a dropping funnel, and a Dimroth trap, and 0.9 g of a 25% by mass aqueous solution of tetramethylammonium hydroxide and 12.3 g of pure water were added dropwise thereto and stirred at room temperature for 4 hours. The resulting solution was concentrated under reduced pressure, dissolved in toluene, and washed with water using a separatory funnel. The solvent was removed from the organic layer by distillation under reduced pressure to obtain 50 g of polysiloxane 4.

[0162] Synthesis Example 5 Synthesis of Polysiloxane 5 50 g of Polysiloxane 5 was obtained in the same manner as in Synthesis Example 4, except that 57.7 g (0.23 mol) of 3-methacryloyloxypropyltrimethoxysilane was used instead of 3-acryloyloxypropyltrimethoxysilane.

[0163] Synthesis Example 6 Synthesis of Polysiloxane 6 50 g of Polysiloxane 6 was obtained in the same manner as in Synthesis Example 4, except that 3-acryloyloxypropyltrimethoxysilane was changed to 61 g (0.22 mol) of (3-ethyl-3-oxetanylmethoxy)propyltrimethoxysilane.

[0164] Synthesis Example 7 Synthesis of Polysiloxane 7 46.86 g (0.20 mol, manufactured by Shin-Etsu Chemical Co., Ltd.), 3.68 g of polydimethylsiloxane (X-21-5841 manufactured by Shin-Etsu Chemical Co., Ltd.), and 60 g of 2-propanol were weighed into a 500 mL four-neck flask equipped with a stirrer, a dropping funnel, and a Dimroth trap, and 1.5 g of a 10 mass % aqueous solution of tetramethylammonium hydroxide and 9.45 g of pure water were added dropwise thereto and stirred at room temperature for 8 hours. The resulting solution was concentrated under reduced pressure, then dissolved in toluene and washed with water using a separatory funnel. The solvent was distilled off under reduced pressure from the organic layer to obtain Polysiloxane 7.

[0165] Synthesis Example 8 Synthesis of Polysiloxane 8 210.8 g (0.90 mol, Shin-Etsu Chemical Co., Ltd.) of 3-acryloyloxypropyltrimethoxysilane, 148.7 g of polydimethylsiloxane (Shin-Etsu Chemical Co., Ltd.), and 582.4 g of 2-propanol were weighed into a 2 L four-neck flask equipped with a stirrer, a dropping funnel, and a Dimroth trap, and 0.9 g of a 25% by mass aqueous solution of tetramethylammonium hydroxide and 12.3 g of pure water were added dropwise thereto, followed by stirring at room temperature for 4 hours. The resulting solution was concentrated under reduced pressure, dissolved in toluene, and washed with water using a separatory funnel. The solvent was then removed from the organic layer by distillation under reduced pressure, yielding 297.4 g of polysiloxane 8.

[0166] Synthesis of Polysiloxane Represented by Formula (2) (Synthesis Example 9: Synthesis of Polysiloxane 9) In a 1 L four-neck round-bottom flask equipped with a thermometer, dropping funnel, and stirring blade, (3-acryloyloxy)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 placed in a water bath at approximately 30°C. Separately, an aqueous solution was prepared by mixing 35% hydrochloric acid (1.0 g, 9.6 mmol as hydrogen chloride) and pure water (150.7 g). The aqueous solution prepared in the mixture was added dropwise from the dropping funnel over approximately 1 hour while stirring the reaction solution, and then allowed to stand overnight at room temperature. The amount of water added was 2.8 times the molar amount of the total amount of hydrolyzable groups in the starting organosilicon compound. Thereafter, the reaction solution was heated to 60° C. while the solvent and other components in the reaction solution were distilled off under reduced pressure, yielding 170 g of Polysiloxane 9 as a colorless, transparent liquid. １ H-NMR analysis confirmed that each structural unit was quantitatively introduced according to the ratio of the raw materials used. The synthesized polysiloxane 9 had a viscosity of 6,270 mPa s at 25°C and a weight-average molecular weight (Mw) of 2,010.

[0167] Synthesis Example 10: Synthesis of Polysiloxane 10 According to the method of Example 1 of JP-A-11-029640, polysiloxane 10 having oxetanyl groups as polymerizable groups was synthesized as shown below. In a reactor equipped with a stirrer, a thermometer, and a cooler, 12.37 g (38.6 mmol) of 3-(3-ethyl-3-oxetanylmethoxy)propyltriethoxysilane, tetramethylammonium hydroxide (hereinafter referred to as "MeOH"), and 10 g of tetramethylammonium hydroxide (hereinafter referred to as "MeOH") were added. ４ 1.05 g of a 10% by weight aqueous solution of HCl (also referred to as "HCl" or "HCl"). ２ O; 52.5 mmol, Me ４ NOH (1.2 mmol), 1.14 g (63.3 mmol) of water, and 300 ml of 1,4-dioxane as a solvent were charged and heated to reflux for 16 hours while stirring. At this time, the pH of the reaction system was 12.1. After heating to reflux, 200 mL of solvent was distilled off to concentrate the reaction system, and the reaction was continued for an additional 6 hours. After completion of the reaction, the solvent and other components were distilled off under reduced pressure, and the solvent was replaced with 200 mL of toluene. The mixture was washed several times with water in a separatory funnel and dehydrated with anhydrous sodium sulfate, after which the toluene was distilled off under reduced pressure to obtain the target polysiloxane 10.

[0168] (Measurement of Molecular Weight) The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polysiloxane were determined by separation using a gel permeation chromatograph (HLC-8320GPC manufactured by Tosoh Corporation, hereinafter abbreviated as "GPC") in a tetrahydrofuran solvent at 40°C using a GPC column "TSK gel SuperMultiporeHZ-M" (manufactured by Tosoh Corporation), and the molecular weight in terms of standard polystyrene was calculated from the retention time.

[0169] (Measurement of Viscosity) The viscosity of the polysiloxane was measured at 25°C using a TVE22H viscometer manufactured by Toki Sangyo Co., Ltd.

[0170] The results are summarized in Table 1.

[0171]

[0172] In Table 1, the numerical values ​​a to f represent molar ratios. The following commercially available leveling agents were used in Comparative Examples 3 to 5. RS75A: DIC Corporation, leveling agent containing a (meth)acrylic group and a perfluoropolyether group, which does not have a silsesquioxane structure. RS57: DIC Corporation, leveling agent containing a (meth)acrylic group and a dimethylsilicone group, which does not have a silsesquioxane structure. F-44: DIC Corporation, leveling agent containing no polymerizable group and a fluorine group.

[0173] Examples 1 to 10 and Comparative Examples 1 to 8 (Preparation of Curable Compositions and Fabrication of Cured Films) 3 g of polysiloxane 9 or 10 as the compound represented by formula (2), 0.15 g of 2-hydroxy-2-methyl-1-phenylpropanone, 3 g of propylene glycol monobutyl ether, polysiloxanes 1 to 8 or a commercially available leveling agent as the compound represented by formula (1), and silica particles (V-8804, manufactured by JGC Catalysts and Chemicals Co., Ltd.) as a filler were weighed out, and the mixture was stirred and dissolved in a centrifugal mixer to prepare curable compositions (photocurable compositions). The amount of silica particles weighed out in Example 10 and Comparative Example 7 was 50% by mass relative to the total weight of the polysiloxane represented by formula (1) and the polysiloxane represented by formula (2). The photocurable compositions were placed on a polyethylene terephthalate (PET) film (A4360, manufactured by Toyobo Co., Ltd., thickness 50 μm) or an SPCC-SD steel plate (dull-finished cold-rolled steel plate), coated using a No. 8 bar coater, dried in a 60°C air-blowing oven for 5 minutes, and then irradiated with ultraviolet light under the following conditions to produce cured films (photocured films). The film thickness was approximately 5 μm in each case. -Ultraviolet Light Irradiation Conditions- Lamp: high-pressure mercury lamp Lamp height: 10 cm Conveyor speed: 5.75 m / min Integrated light intensity per pass: 360 mJ / cm ２ (UV-A) Atmosphere: Air Number of passes: 10

[0174] (Contact Angle Measurement) The contact angle of the photocured film formed on the SPCC-SD steel plate as described above with pure water at 23° C. was evaluated using OCA20 manufactured by Eiko Seiki Co., Ltd.

[0175] (Indentation Elastic Modulus Measurement) The photocured films prepared on the PET films as described above were subjected to indentation hardness measurement at 23°C and a strain rate of 0.05 / s using a nanoindenter (Agilent Technologies G200, using a Berkovich indenter). The modulus was calculated by averaging the modulus values ​​at indentation depths of 100 nm to 500 nm. Furthermore, for Examples 1 to 4, 6 to 10, Comparative Examples 2 to 4, and 6 to 8, the degree to which the modulus of elasticity of the cured product containing a leveling agent was reduced relative to the modulus of elasticity of the cured product containing no leveling agent in Comparative Example 1 was calculated as follows: Reduction (%) = {(Elastic modulus of cured product without leveling agent added - Elastic modulus of cured product with leveling agent added) / Elastic modulus of cured product without leveling agent added} × 100. In Example 5, the reduction rate of the elastic modulus was calculated relative to that of the cured product of Comparative Example 5 to which no leveling agent was added.

[0176] (Measurement of dynamic friction coefficient) The dynamic friction coefficient of the photocured film prepared on the SPCC-SD steel plate as described above was evaluated at 23°C using a Shinto Scientific Tripogear Type: 14FW in accordance with ISO 8295: 1995(E). A ball-type indenter was used, and measurements were taken three times at a distance of 3 cm with a load of 200 g, and the average value was taken as the dynamic friction coefficient.

[0177] (Pencil Hardness Test) The photocured film prepared on the SPCC-SD steel plate as described above was subjected to a test in accordance with JIS K5600-5-4. The scratch test was carried out three times using pencils of each hardness, and the highest value of the pencil type that did not cause any defects in the photocured film was recorded as the pencil hardness.

[0178] (Durability Evaluation) The photocured film prepared on the SPCC-SD steel plate as described above was subjected to 50 reciprocating abrasion tests with absorbent cotton soaked in acetone, absorbent cotton soaked in hexane, and steel wool #0000, each measuring 1 cm x 1 cm and under a load of 1 kg. The contact angle with pure water after abrasion was measured, and a rating of S was given to samples that showed no decrease compared to before the test, A to samples that showed a decrease of 5% or less, B to samples that showed a decrease of 10% or less, and C to samples that showed a decrease of more than that.

[0179] The evaluation results are shown in Table 2.

[0180]

[0181] As shown in Table 2, the cured films of Examples 1 to 10 were superior in durability, particularly durability against abrasion by steel wool, compared to the cured films of Comparative Examples 1 to 8. This means that the cured films of Examples 1 to 10 of the present invention were less susceptible to the leveling agent falling off or losing its function due to bleed-out. Furthermore, as shown in Table 2, the cured films of Examples 1 to 10 were also superior in suppressing a decrease in indentation modulus compared to the cured films of Comparative Examples 1 to 8.

[0182] The contact angle in Comparative Example 8 varied from 96° to 107°. The exact cause is unknown, but it is presumed to be related to clouding of the cured film.

[0183] The disclosure of Japanese Patent Application No. 2023-177806, filed on October 13, 2023, is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A curable composition comprising a polysiloxane represented by the following formula (1) in an amount of 0.1 mass % or more and less than 10 mass % based on the total solid content of the curable composition, and in which x / (v+w+x+y+z) is less than 0.6: In formula (1), R １ each independently represents at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a monovalent organic group having a polymerizable group; R １ At least one of R is a monovalent organic group having a polymerizable group. １ The alkyl group, the aralkyl group, the aryl group, and the monovalent organic group having a polymerizable group in the formula (I) may be substituted with a structure selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, an aryloxy group, an aralkyloxy group, and an oxy group; ２ each independently represents a hydrocarbon group having 1 to 20 carbon atoms substituted with a fluorine atom; R ３ , R ４ and R ５ each independently represents at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a monovalent organic group having a polymerizable group; R ３ , R ４ and R ５ the alkyl group, the aralkyl group, the aryl group, and the monovalent organic group having a polymerizable group may be substituted with a structure selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, an aryloxy group, an aralkyloxy group, and an oxy group; w represents a positive number; v, x, y, and z each independently represent 0 or a positive number, at least one of x and y represents a positive number, and when x is 0, the compound contains a structure represented by the following formula (S): n represents a number of 3 or more.

2. The curable composition according to claim 1, further comprising a polysiloxane represented by the following formula (2) in addition to the polysiloxane represented by the formula (1): In formula (2), R ６ , R ７ and R ８ each independently represents at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a monovalent organic group having a polymerizable group; R ６ , R ７ and R ８ At least one of R is a monovalent organic group having a polymerizable group. ６ , R ７ and R ８ the alkyl group, the aralkyl group, the aryl group, and the monovalent organic group having a polymerizable group may be substituted with a structure selected from the group consisting of a halogen atom, a hydroxy group, an alkoxy group, an aryloxy group, an aralkyloxy group, and an oxy group, q represents a positive number, and p, r, and s each independently represent 0 or a positive number.

3. R ​​in the above formula (1) １ 3. The curable composition according to claim 1, wherein the polymerizable group is at least one selected from the group consisting of an acryloyl group, a methacryloyl group, an epoxy group, an oxetanyl group, a vinyl group and an allyl group.

4. The curable composition according to claim 1 or 2, wherein the value of (x+y) / (v+w+x+y+z) in the formula (1) is 0.20 to 0.

80.

5. The curable composition according to claim 1 or 2, further comprising a polymerization initiator.

6. A cured product obtained by curing the curable composition according to claim 1 or 2.

7. A hard coat agent comprising the curable composition according to claim 1 or 2.

8. A hard coat obtained by curing the hard coat agent according to claim 7.

9. An article comprising the hard coat of claim 8.

10. A laminate comprising the hard coat according to claim 9 and a substrate.

11. The cured product according to claim 6, which has a pencil hardness of 5H or more and a dynamic friction coefficient of 0.35 or less when formed on a steel plate.

12. The cured product according to claim 6, in which the reduction in the contact angle with water before and after an abrasion test using absorbent cotton soaked in acetone, an abrasion test using absorbent cotton soaked in hexane, and an abrasion test using steel wool is 10% or less in all cases.

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