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

Abstract

Provided is a curable composition which contains an organopolysiloxane represented by formula (1) in an amount of not less than 0.1 mass% but less than 20 mass% with respect to the total solid content of the curable composition. In addition, formula (1) contains a component having a structure represented by formula (S). In formula (S), n represents an integer of 14 or more.

Description

Curable compositions, cured products, hard coating agents, hard coatings, articles, and laminates

[0001] This disclosure relates to curable compositions, cured products, hard coating agents, hard coatings, articles, and laminates.

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

[0003] However, these leveling agents are not chemically fixed to the base resin, leading to problems such as bleed-out, detachment due to repeated use, or loss of function. To address these issues, leveling agents containing polymerizable functional groups and fluorinated alkyl groups or silicone chains are now being used. Furthermore, from an environmental protection standpoint, it is desirable that these agents do not contain fluorinated resins.

[0004] Conventional leveling agents include those described in Patent Documents 1 to 4. Patent Document 1 discloses a hard coat layer forming composition comprising a polyorganosilsesquioxane having polymerizable epoxy groups and a nonionic fluorine-containing compound as a leveling agent. Patent Document 2 discloses a leveling agent having a fluorine atom, obtained by polymerizing a monomer having two or more groups having radical polymerizable double bonds and containing at least one nitrogen atom, and a composition comprising this and polyorganosilsesquioxane. Patent Document 3 discloses a hard coat composition comprising a polymer having at least one of a silicone group and a perfluoropolyether group and a reactive group as side chains, and polyorganosilsesquioxane having polymerizable groups as a leveling agent. Patent Document 4 discloses a hard coat layer forming composition comprising polysilsesquioxane having perfluoropolyether groups.

[0005] International Publication No. 2021 / 193173, International Publication No. 2019 / 235108, International Publication No. 2020 / 059726, International Publication No. 2021 / 193478

[0006] In particular, for displays that are directly touched, such as touch panels, it is desirable that the leveling agent unevenly distributed on the coating surface exhibits not only high stain resistance but also excellent hardness and weather resistance, from the viewpoint of physical strength and durability. Patent Document 1 discloses a hard coat composition in which a nonionic fluorine-containing compound is added as a leveling agent to a polyorganosilsesquioxane having polymerizable epoxy groups. However, in a hard coat cured from this composition, performance degradation occurs due to bleed-out of the leveling agent because there is no covalent bond between the main component, silsesquioxane, and the leveling agent. Patent Document 2 discloses a leveling agent having a fluorine atom, which is obtained by polymerizing a monomer having two or more groups having radical polymerizable double bonds and containing at least one nitrogen atom. However, in a hard coat cured from this composition, performance degradation occurs due to bleed-out of the leveling agent because there is no covalent bond between the main component, silsesquioxane, and the leveling agent. Furthermore, because the leveling agent molecule contains nitrogen atoms, there is a risk that deterioration may be accelerated during long-term use, such as hydrolysis of the hard coat obtained by curing the composition. Patent Document 3 discloses a hard coat composition in which a leveling agent having polymerizable functional groups and silicone or perfluoropolyether is added to a polysilsesquioxane derivative, but the crosslinking density of the leveling agent is low, and there is a risk that the hardness of the coating surface will decrease. Patent Document 4 discloses a hard coat layer forming composition containing polysilsesquioxane having perfluoropolyether groups, but it has not been possible to achieve both surface hardness and a low coefficient of dynamic friction (i.e., high surface smoothness). In addition, all of the leveling agents in Patent Documents 1 to 4 contain fluororesins.

[0007] This disclosure has been made in view of the above, and aims to provide a curable composition that has excellent water repellency, oil repellency, and slipperiness of the resulting cured product, as well as cured products, hard coat agents, hard coats, articles, and laminates using the curable composition.

[0008] The means for solving the above problem include the following embodiments: <1> A curable composition containing an organopolysiloxane represented by the average composition formula of the following formula (1) in an amount of 0.1% by mass or more and less than 20% by mass, based on the total solid content of the curable composition.

[0009] In formula (1), R １ Each of these independently represents 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, or a monovalent organic group having a polymerizable group, R １ At least one of them is a monovalent organic group having a polymerizable group, R １ 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 hydroxyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, and an oxy group, ２ and R ３ Each of these independently represents 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, or a monovalent organic group having a polymerizable group, R ２ and R ３ The alkyl group, aralkyl group, aryl group, and monovalent organic group having polymerizable groups in the above may be substituted with a structure selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, and an oxy group, where b and c represent positive numbers, a and d each represent 0 or a positive number, and the mixture contains a component with a structure represented by the following formula (S).

[0010] In equation (S), n represents an integer greater than or equal to 14.

[0011] <2> The curable composition according to <1>, wherein a contact angle of water on a surface of a cured product of the curable composition is 100° or more. <3> The curable composition according to <1> or <2>, wherein both the coefficient of static friction and coefficient of kinetic friction against a dust-free cloth on a surface of a cured product of the curable composition are 0.2 or less. <4> The curable composition according to any one of <1> to <3>, further comprising an organopolysiloxane represented by an average compositional formula of the following formula (2).

[0012] In formula (2), R ４ , R ５ and R ６ each independently represent 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, or a monovalent organic group having a polymerizable group, and R ４ , R ５ and R ６ at least one of them is a monovalent organic group having a polymerizable group, and R ４ , R ５ and R ６ the alkyl group, the aralkyl group, the aryl group, and the monovalent organic group having a polymerizable group in R, R and R may each 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.

[0013] <5> The curable composition according to any one of <1> to <4>, further comprising a filler. <6> The curable composition according to any one of <1> to <5>, wherein the polymerizable group in R １ of 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. <7> The curable composition according to any one of <1> to <6>, wherein the organopolysiloxane represented by formula (1) is obtained by reacting a silicon compound containing at least a silane monomer having three hydrolyzable groups and / or hydroxyl groups represented by the following formula (3) and a silicone represented by the following formula (4). R １ -SiX ３(3) In formula (3), R １ Each of these independently represents 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, or a monovalent organic group having a polymerizable group, R １ At least one of them is a monovalent organic group having a polymerizable group, R １ The alkyl group, the aralkyl group, the aryl group, and the monovalent organic group having a polymerizable group in the above may be substituted with a structure selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, and an oxy group, where X represents a hydrolyzable group and / or a hydroxyl group.

[0014] In formula (4), R ２ Each of these independently represents 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, or a monovalent organic group having a polymerizable group, R ２ and R ３ The alkyl group, aralkyl group, aryl group, and monovalent organic group having a polymerizable group in formula (4) may be substituted with a structure selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, and an oxy group, and A and B each independently represent a hydrolyzable group, a hydroxyl group, 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, or a monovalent organic group having a polymerizable group, and at least one of A and B is a hydrolyzable group or a hydroxyl group, m represents a positive integer, and the number-average molecular weight of the silicone represented by formula (4) is 1,100 or more and 150,000 or less.

[0015] <8> A curable composition according to any one of <1> to <7>, further comprising a polymerization initiator. <9> A curable composition according to any one of <1> to <8>, wherein the pencil hardness of the cured product of the curable composition formed on an SPCC-SD steel sheet is 6H or higher. <10> A cured product obtained by curing the curable composition according to any one of <1> to <9>. <11> A hard coat agent comprising the curable composition according to any one of <1> to <9>. <12> A hard coat obtained by curing the hard coat agent according to <11>. <13> An article having the hard coat according to <12>. <14> A laminate having the hard coat according to <13> and a substrate.

[0016] According to this disclosure, a curable composition is available that yields a highly hard cured product with excellent water repellency, oil repellency, and slipperiness, while being fluorine-free. The disclosure also provides cured products, hard coat agents, hard coats, articles, and laminates using the curable composition.

[0017] The embodiments for implementing this disclosure will be described in detail below. However, this disclosure is not limited to the embodiments described below. In the embodiments described below, the components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and they do not limit this disclosure. In this specification, numerical ranges indicated using "~" include the numerical values ​​before and after "~" as the minimum and maximum values, respectively. In numerical ranges described stepwise in this specification, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another stepwise numerical range. Also, in numerical ranges described in this specification, the upper or lower limit of that numerical range may be replaced with the values ​​shown in the examples. Furthermore, in this specification, a combination of two or more preferred embodiments is a more preferred embodiment.

[0018] In this specification, R in formula (1) １ ~R ３ Each of these may independently have part of its structure substituted with a substituent or halogen atom. For example, R １ ~R３ Each of these groups may independently have part of its structure substituted with an alkyl group, aryl group, aralkyl group, vinyl group, epoxy group, oxetanyl group, hydroxyl group, amino group, alkylamino group, arylamino group, aralkylamino group, ammonium group, sulfanyl group, isocyanurate group, ureido group, isocyanate group, carboxyl group, acid anhydride group, or halogen atom.

[0019] [Curable Composition] The curable composition according to this disclosure is a curable composition comprising an organopolysiloxane represented by the following formula (1) in an amount of 0.1% by mass or more and less than 20% by mass, based on the total solid content of the curable composition.

[0020] In formula (1), R １ Each of these independently represents 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, or a monovalent organic group having a polymerizable group, R １ At least one of them is a monovalent organic group having a polymerizable group, R １ 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 hydroxyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, and an oxy group, ２ and R ３ Each of these independently represents 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, or a monovalent organic group having a polymerizable group, R ２ and R ３ The alkyl group, aralkyl group, aryl group, and monovalent organic group having polymerizable groups in the above may be substituted with a structure selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, and an oxy group, where b and c represent positive numbers, a and d each represent 0 or a positive number, and the mixture contains a component with a structure represented by the following formula (S).

[0021] In equation (S), n represents an integer greater than or equal to 14.

[0022] As described above, cured products obtained by curing conventional curable compositions lacked sufficient water repellency and lubricity. As a result of diligent research by the present inventors, it has been found that by adopting the above configuration, it is possible to provide a curable composition that yields a highly hard cured product with excellent water repellency, oil repellency, and lubricity, while being fluorine-free. By including the organopolysiloxane represented by formula (1) in an amount of 0.1% by mass or more and less than 20% by mass relative to the total solid content of the curable composition, it is possible to obtain a resin mixture that does not contain fluorine-based resins and has a special structure after curing, and therefore it is estimated that it is possible to produce a cured product with excellent water repellency and lubricity.

[0023] <Organopolysiloxane represented by formula (1)> The curable composition according to this disclosure contains an organopolysiloxane represented by the average composition formula of formula (1), which is a silsesquioxane derivative.

[0024] Each constituent unit that may be included in the silsesquioxane derivative used in this disclosure is referred to as constituent units (a) to (d) below.

[0025]

[0026] In the organopolysiloxane represented by formula (1), b and c each independently represent a positive number, and a and d each independently represent 0 or a positive number. In other words, the organopolysiloxane represented by formula (1) includes component (b) and component (c) from the above-mentioned component units (a) to (d), and may optionally include at least one of component units (a) and component (d).

[0027] In formula (1), a to d represent the molar ratio of constituent units (a) to (d). In formula (1), a to d represent the relative molar ratio of constituent units (a) to (d) that the organopolysiloxane represented by formula (1) may contain. The molar ratio can be determined, for example, from the NMR (nuclear magnetic resonance) analysis value of the organopolysiloxane represented by formula (1). Alternatively, when the reaction rate of each raw material of the organopolysiloxane represented by formula (1) is known, or when the yield is 100%, it can be determined from the amount of raw material charged. For example, the molar ratio of each constituent unit of the organopolysiloxane represented by formula (1) can be determined from the amount of raw material charged when the sample is dissolved in deuterated chloroform, etc. １ Perform H-NMR analysis, and if necessary, further analysis will be conducted. ２９ The structure may also be calculated by performing Si-NMR analysis. Alternatively, the structure of the organopolysiloxane represented by the original formula (1) may be estimated from the ratio of the constituent units after decomposition into constituent units using alkali, etc. If necessary, the molar ratio of each constituent unit of the organopolysiloxane represented by formula (1) may be determined by combining known methods such as mass spectrometry and IR (infrared absorption spectroscopy) analysis.

[0028] Each of the constituent units (b) to (d) in formula (1) may be of only one type or of two or more types. Furthermore, the sequence in formula (1) indicates the composition of the constituent units and does not represent the sequence of the organopolysiloxane represented by formula (1). Therefore, the condensation form of the constituent units in the organopolysiloxane represented by formula (1) does not necessarily have to be in the same sequence as in formula (1).

[0029] The organopolysiloxane represented by formula (1) above may include, for example, a complete cage structure, an incomplete cage structure, a ladder structure, a random structure, and a linear structure, and may also include structures that are arbitrarily partially combined from these structures. Furthermore, it may be a mixture that arbitrarily contains these various structures. Therefore, the organopolysiloxane represented by formula (1) can be said to represent the average composition by determining the molar ratio of each constituent unit (a) to (d) as described above. The details of constituent units (a) to (d) and other constituent units (e) will be described below.

[0030] (Constituent unit (a)) Constituent unit (a) consists of one silicon atom and O ０．５ This is a Q unit that has four (two as oxygen atoms). Note that a Q unit is defined as having one silicon atom and four O ０．５ It means a unit that has four of these elements.

[0031] The proportion of constituent unit (a) in the organopolysiloxane represented by formula (1) is not particularly limited, but from the viewpoint of water repellency, oil repellency, and slipperiness, when expressed as the ratio of the total molar amount of all constituent units (a) to (d) of the organopolysiloxane represented by formula (1) as follows: a / (a ​​+ b + c + d) × 100 (mol%), it is preferably less than 50 mol%, more preferably less than 20 mol%, even more preferably less than 10 mol%, and it is particularly preferable that it does not contain constituent unit (a).

[0032] (Constituent unit (b)) Constituent unit (b) consists of one silicon atom and O ０．５ A T unit is a single-valent organic group (1.5 oxygen atoms) with three oxygen atoms (1.5 oxygen atoms) bonded to a silicon atom. ０．５ It means a unit that has three of these elements.

[0033] R in organopolysiloxane represented by formula (1) １ This may include one type alone or two or more types. １ From the viewpoint of reactivity and hardness, it is preferable that the material contains a monovalent organic group having a polymerizable group, more preferably a monovalent organic group having a radical polymerizable group or a cationic polymerizable group, and even more preferably a monovalent organic group having a radical polymerizable group. From the viewpoint of reactivity and hardness, an ethylenically unsaturated group is preferred as the radical polymerizable group, a (meth)acrylate group is more preferred, and an epoxy group or an oxetanyl group is preferred as the cationic polymerizable functional group. Here, (meth)acrylate means acrylate or methacrylate, and the same applies hereinafter. １If it contains a radical polymerizable group, from the viewpoint of reactivity and hardness, it is preferable that it contains a group represented by the following formula (R1-1), and more preferably that it is a group represented by the following formula (R1-1). Also, R １ If the material contains a cationic polymerizable group, it is preferable, from the viewpoint of reactivity and hardness, that it contains a group represented by the following formula (R1-2), and more preferably that it contains a group represented by the following formula (R1-2).

[0034]

[0035]

[0036] In equations (R1-1) and (R1-2), R ｂ L represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. １ * represents an alkylene group with 1 to 10 carbon atoms, a cycloalkylene group with 3 to 10 carbon atoms, an arylene group with 6 to 10 carbon atoms, or an aralkylene group with 7 to 12 carbon atoms, n represents 0 or 1, and * represents the bond position with the silicon atom.

[0037] L １ The atom is preferably an alkylene group having 1 to 10 carbon atoms or a cycloalkylene group having 3 to 10 carbon atoms, and more preferably an alkylene group having 1 to 10 carbon atoms. The alkylene group having 1 to 10 carbon atoms is preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, and even more preferably a propylene group. The alkylene group having 1 to 10 carbon atoms may be linear or branched. The cycloalkylene group having 3 to 10 carbon atoms is preferably a cycloalkylene group having 3 to 6 carbon atoms, and more preferably a cycloalkylene group having 4 to 6 carbon atoms. The cycloalkylene group having 3 to 10 carbon atoms may be branched. ｂ Examples of alkyl groups having 1 to 6 carbon atoms in formula (R1-1) include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups, with methyl and ethyl groups being preferred, methyl groups being more preferred in formula (R1-1), and ethyl groups being more preferred in formula (R1-2). n is preferably 1.

[0038] Also, R １ Preferably, the group is a hydrogen atom, a saturated or unsaturated chain hydrocarbon group having 1 to 20 carbon atoms, a saturated or unsaturated cyclic hydrocarbon group having 3 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.

[0039] A saturated or unsaturated chain hydrocarbon group having 1 to 20 carbon atoms may be linear or branched. Preferably, the saturated or unsaturated chain hydrocarbon group having 1 to 10 carbon atoms is a saturated or unsaturated chain hydrocarbon group having 1 to 10 carbon atoms, and more preferably a saturated chain hydrocarbon group having 1 to 10 carbon atoms.

[0040] Examples of saturated chain hydrocarbon groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. From the viewpoint of heat resistance and hardness of the cured product, methyl or ethyl groups are preferred, and methyl groups are more preferred.

[0041] Examples of unsaturated chain hydrocarbon groups having 1 to 10 carbon atoms include vinyl groups, 2-propenyl groups, and ethynyl groups.

[0042] A saturated or unsaturated cyclic hydrocarbon group having 3 to 8 carbon atoms may be branched. Preferably, the saturated or unsaturated cyclic hydrocarbon group having 4 to 6 carbon atoms is a saturated or unsaturated cyclic hydrocarbon group having 3 to 8 carbon atoms.

[0043] The aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 10 carbon atoms.

[0044] Examples of aryl groups having 6 to 20 carbon atoms include phenyl groups, groups in which one or more hydrogen atoms of a phenyl group are substituted with alkyl groups having 1 to 10 carbon atoms, and naphthyl groups. From the viewpoint of heat resistance and hardness of the cured product, phenyl groups are preferred.

[0045] The aralkyl group having 7 to 20 carbon atoms is preferably an aralkyl group having 7 to 10 carbon atoms.

[0046] Examples of aralkyl groups having 7 to 20 carbon atoms include groups in which one hydrogen atom of an alkyl group having 1 to 10 carbon atoms is substituted with an aryl group such as a phenyl group. Examples include benzyl groups and phenethyl groups, and from the viewpoint of heat resistance and hardness of the cured product, the benzyl group is preferred.

[0047] Also, R １ In the alkyl group, the aralkyl group, the aryl group, and the monovalent organic group having the polymerizable group, the substituents that may be present are preferably free of fluorine atoms. That is, the substituents are preferably structures selected from the group consisting of chlorine atoms, bromine atoms, iodine atoms, hydroxyl groups, alkoxy groups, aryloxy groups, aralkyloxy groups, and oxy groups. １ If a portion of the group in R is substituted with a substituent or halogen atom, １ Examples include 3-glycidoxypropyl group, 2-(3,4-epoxycyclohexyl)ethyl group, 3-(3-ethyloxetan-3-yl)methoxypropyl group, 3-hydroxypropyl group, 3-aminopropyl group, 3-dimethylaminopropyl group, 3-hydroxypropyl group, hydrochloride of 3-aminopropyl group, hydrochloride of 3-dimethylaminopropyl group, p-styryl group, N-2-(aminoethyl)-3-aminopropyl group, N-phenyl-3-aminopropyl group, hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyl group, 3-ureidopropyl group, 3-mercaptopropyl group, 3-isocyanatepropyl group, 3-carboxypropyl group, and 3-chloropropyl group.

[0048] The proportion of constituent unit (b) in the organopolysiloxane represented by formula (1) is not particularly limited, but from the viewpoint of water repellency, slipperiness, oil repellency, and hardness, when expressed as the ratio of the total molar amount of all constituent units (a) to (d) of the organopolysiloxane represented by formula (1) as follows: b / (a ​​+ b + c + d) × 100 (mol%), it is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 20 mol% or more, even more preferably 30 mol% to 90 mol%, and particularly preferably 40 mol% to 80 mol%.

[0049] Furthermore, from the viewpoint of water repellency, slipperiness, oil repellency, and hardness, the b / c value is preferably 0.1 or higher, more preferably 0.2 to 20, even more preferably 0.5 to 10, even more preferably 1.0 to 2.5, even more preferably greater than 1.0 and less than 2.4, and particularly preferably greater than 1.0 and less than 2.0.

[0050] (Constituent unit (c)) Constituent unit (c) consists of one silicon atom and O ０．５ It has two (one as an oxygen atom) and two R ２ This is a D unit in which O is bonded to a silicon atom. Note that a D unit is defined as one silicon atom bonded to one O ０．５ It means a unit that has two of these elements.

[0051] In the constituent unit (c), R ２ Each of these independently represents 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, or a monovalent organic group having a polymerizable group, preferably a saturated or unsaturated linear hydrocarbon group having 1 to 20 carbon atoms, a saturated or unsaturated cyclic hydrocarbon group having 3 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. In the constituent unit (c), there are multiple R ２ They may be the same or different from each other. ２ Preferred embodiments of the C1-C10 alkyl group, C7-C10 aralkyl group, C6-C10 aryl group, and monovalent organic group having a polymerizable group are R １The preferred embodiments are the same as those for the C1-C10 alkyl group, C7-C10 aralkyl group, C6-C10 aryl group, and monovalent organic group having a polymerizable group in the above.

[0052] Furthermore, the organopolysiloxane represented by formula (1) contains a component with the structure represented by the following formula (S) as a constituent unit (c).

[0053] In equation (S), n represents an integer greater than or equal to 14.

[0054] n is 14 or more, preferably 15 or more, more preferably 20 or more, even more preferably 30 or more, even more preferably 40 or more, and particularly preferably 50 or more, from the viewpoint of water repellency, oil repellency, and slipperiness. Furthermore, there is no particular upper limit to n, but for example it can be 2,000 or less, and from the viewpoint of water repellency, oil repellency, slipperiness, and hardness it is preferably 200 or less, more preferably 150 or less, and even more preferably 120 or less. In addition to water repellency, oil repellency, slipperiness, and hardness, from the viewpoint of the appearance of the resulting cured product it is preferably 110 or less, more preferably 100 or less, and even more preferably 90 or less.

[0055] In the organopolysiloxane represented by formula (1), the proportion of constituent unit (c) is preferably 10 mol% to 80 mol%, more preferably 20 mol% to 65 mol%, and particularly preferably 25 mol% to 50 mol%, as expressed by the following formula: c / (a ​​+ b + c + d) × 100 (mol%), relative to the total molar amount of all constituent units (a) to (d) of the organopolysiloxane represented by formula (1). Furthermore, from the viewpoint of water repellency, oil repellency, slipperiness, and hardness, the proportion of constituent unit (c) in the organopolysiloxane represented by formula (1) is preferably less than the proportion of constituent unit (b).

[0056] (Constituent unit (d)) Constituent unit (d) consists of one silicon atom and O ０．５ It has one (0.5 as an oxygen atom) and three R３ This is an M-unit in which O is bonded to a silicon atom. Note that an M-unit is defined as one silicon atom bonded to an O ０．５ It means a unit that has one of these elements.

[0057] In the constituent unit (d), R ３ Each of these independently represents 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, or a monovalent organic group having a polymerizable group, preferably a saturated or unsaturated linear hydrocarbon group having 1 to 20 carbon atoms, a saturated or unsaturated cyclic hydrocarbon group having 3 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. In the constituent unit (d), there are multiple R ３ They may be the same or different from each other. ３ A preferred embodiment is R in the constituent unit (c). ２ It is similar to that.

[0058] In the organopolysiloxane represented by formula (1), the proportion of constituent unit (d) is preferably 30 mol% or less, more preferably 20 mol% or less, and particularly preferably 10 mol% or less, when expressed as the ratio of the total molar amount of all constituent units (a) to (d) of the organopolysiloxane represented by formula (1) using the following formula: d / (a ​​+ b + c + d) × 100 (mol%), from the viewpoint of water repellency, oil repellency, slipperiness, and hardness.

[0059] (Other constituent units (e)) The organopolysiloxane represented by formula (1) can further be expressed as a Si-free constituent unit (R ７ O １／２ ) may include (hereinafter also referred to as constituent unit (e)). Here, R ７ 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 alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups.

[0060] The constituent unit (e) is an alkoxy group, which is a hydrolyzable group contained in the silicon compound described later, or an alkoxy group produced when an alcohol contained in the reaction solvent substitutes for a hydrolyzable group in the silicon compound, and may remain in the molecule without hydrolysis or polycondensation, or it may be a hydroxyl group that remains in the molecule after hydrolysis without polycondensation.

[0061] There are no particular restrictions on the content of constituent unit (e), but from the viewpoint of water repellency, oil repellency, slipperiness, and hardness, for example, if the ratio of the molar amount of constituent unit (e) to the total molar amount of all silicon atoms in the organopolysiloxane represented by formula (1), i.e., the total molar amount of all constituent units (a) to (d), is expressed as the following formula: e / (a ​​+ b + c + d) × 100 (mol%) (where e represents the molar ratio of constituent unit (e) contained in the organopolysiloxane represented by formula (1), similar to a, b, c, and d), then it is preferably, for example, 0 mol% to 100 mol%, more preferably 1 mol% to 70 mol%, preferably 1 mol% to 50 mol%, more preferably 1 mol% to 30 mol%, even more preferably 2 mol% to 20 mol%, and particularly preferably 3 mol% to 10 mol%.

[0062] The molar ratio of constituent units (e) is, for example, relative to a sample dissolved in deuterated chloroform, etc. １ Perform H-NMR analysis, and if necessary, further analysis will be conducted. ２９ The molar ratio of each constituent unit of the organopolysiloxane represented by formula (1) may also be calculated by performing Si-NMR analysis. If necessary, known methods such as mass spectrometry and IR (infrared absorption spectroscopy) analysis may be combined to determine the molar ratio of each constituent unit of the organopolysiloxane represented by formula (1). The "HO" present in the organopolysiloxane represented by formula (1) １／２ "That is, the product obtained by reacting silanol with a reaction reagent such as chlorotrimethylsilane, １ H-NMR, ２９ By subjecting the organopolysiloxane represented by formula (1) to known analyses such as Si-NMR and / or IR analysis, the "HO" present in the organopolysiloxane is identified. １／２The content of " may be calculated. It may also be calculated by performing thermal analysis such as thermogravimetric analysis or differential thermal analysis on the sample. Furthermore, the content of constituent unit (e) may be expressed as mass %, for example, as the ratio of the mass of constituent unit (e) to the total mass of all constituent units (a) to (e) of the organopolysiloxane represented by formula (1).

[0063] The weight-average molecular weight (hereinafter also referred to as "Mw") of the organopolysiloxane represented by formula (1) is not particularly limited, but is preferably 500 to 50,000, more preferably 1,000 to 30,000, even more preferably 1,000 to 10,000, and particularly preferably 1,000 to 6,000. In this disclosure, Mw refers to the value obtained by converting the molecular weight measured by GPC (gel permeation chromatography) using polystyrene as a standard substance. For example, the measurement conditions in the [Examples] described later can be used as the measurement conditions for Mw.

[0064] (Method for producing organopolysiloxane represented by formula (1)) The organopolysiloxane represented by formula (1) can also be called a silsesquioxane derivative and can be produced by known methods. Methods for producing silsesquioxane derivatives are disclosed in detail as methods for producing polysiloxanes in Japanese Patent Publication No. 11-116682, Japanese Patent Publication No. 2000-044689, International Publication No. 2004 / 076534, International Publication No. 2009 / 090916, International Publication No. 2009 / 131038, International Publication No. 2012 / 090707, International Publication No. 2013 / 031798, etc.

[0065] In particular, a method for producing the organopolysiloxane represented by formula (1) preferably includes a reaction step of reacting a silane monomer having at least three hydrolyzable groups and / or hydroxyl groups represented by formula (3) below with a silicon compound containing a silicone represented by formula (4) below. Furthermore, it is preferable that the polysiloxane represented by formula (1) is obtained by the reaction of a silane monomer having at least three hydrolyzable groups and / or hydroxyl groups represented by formula (3) below with a silicon compound containing a silicone represented by formula (4) below.

[0066] R １ -Six ３ (3) In formula (3), R １ Each of these independently represents 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, or a monovalent organic group having a polymerizable group, R １ At least one of them is a monovalent organic group having a polymerizable group, R １ The alkyl group, the aralkyl group, the aryl group, and the monovalent organic group having a polymerizable group in the above may be substituted with a structure selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, and an oxy group, where X represents a hydrolyzable group and / or a hydroxyl group.

[0067] In formula (4), R ２ Each of these independently represents 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, or a monovalent organic group having a polymerizable group, R ２ and R ３The alkyl group, aralkyl group, aryl group, and monovalent organic group having a polymerizable group in the formula (4) may be substituted with a structure selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, and an oxy group. A and B each independently represent a hydrolyzable group, a hydroxyl group, a C1-C10 alkyl group, a C7-C10 aralkyl group, a C6-C10 aryl group, or a monovalent organic group having a polymerizable group, and at least one of A and B is a hydrolyzable group or a hydroxyl group. m represents a positive integer, and the number-average molecular weight of the silicone represented by formula (4) is 1,100 or more and 150,000 or less. From the viewpoint of water repellency, oil repellency, and slipperiness, m is 14 or more, preferably 15 or more, more preferably 20 or more, even more preferably 30 or more, even more preferably 40 or more, and particularly preferably 50 or more. Furthermore, while there is no particular upper limit to m, it can be, for example, 2,000 or less. From the viewpoint of water repellency, oil repellency, slipperiness, and hardness, it is preferably 200 or less, more preferably 150 or less, and even more preferably 120 or less. In addition to water repellency, oil repellency, slipperiness, and hardness, from the viewpoint of the appearance of the resulting cured product, it is preferably 110 or less, more preferably 100 or less, and even more preferably 90 or less.

[0068] R in equations (3) and (4) １ and R ２ R in formula (1) is １ and R ２ This is synonymous with the above, and the preferred embodiments are similar. X is preferably a hydroxyl group, an alkoxy group, a silyloxy group, or a halogen atom (excluding a fluorine atom), with an alkoxy group or a silyloxy group being more preferred.

[0069] A method for producing organopolysiloxane 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, etc. are removed from the reaction solution.

[0070] Further, examples of compounds used in the method for producing the organopolysiloxane represented by formula (1) include the following compounds. R ｎ SiX ｐ (n represents an integer of 0 to 3, p represents an integer of 1 to 4, n+p=4, R represents any one of the aforementioned R １ to R ３ , and X represents a hydrolyzable group and / or a hydroxyl group.)

[0071] Examples of silicon compounds in which n is 0 and p is 4, which give the structural unit (a) by hydrolysis and polycondensation, include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and the like.

[0072] Among the organosilicon compounds, as compounds having n=1 and p=3, those having an acryloyl group include, for example, (3-acryloyloxypropyl)trimethoxysilane, (3-acryloyloxypropyl)triethoxysilane, (8-acryloyloxyoctyl)trimethoxysilane, and (3-acryloyloxypropyl)trichlorosilane.

[0073] Among the organosilicon compounds, as compounds having n=1 and p=3, those having a methacryloyl group include, for example, (3-methacryloyloxypropyl)trimethoxysilane, (3-methacryloyloxypropyl)triethoxysilane, (8-methacryloyloxyoctyl)trimethoxysilane, and (3-methacryloyloxypropyl)trichlorosilane.

[0074] Among the organosilicon compounds, as compounds having n=1 and p=3, those having an oxetanyl group include, for example, (3-ethyl-3-oxetanylmethoxypropyl)trimethoxysilane, (3-ethyl-3-oxetanylmethoxypropyl)triethoxysilane, (3-methyl-3-oxetanylmethoxypropyl)trimethoxysilane, (3-oxetanyloxypropyl)triethoxysilane, and (3-oxetanylmethoxypropyl)trichlorosilane.

[0075] Examples of the organosilicon compounds in which n is 1 and p is 3 include those having an epoxy group, such as 3-(glycidyloxypropyl)trimethoxysilane, (glycidyloxypropyl)triethoxysilane, 3-(glycidyloxyoctyl)trimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0076] Examples of the organosilicon compounds in which n is 1 and p is 3 include vinyltrimethoxysilane, vinyltrichlorosilane, and p-styryltrimethoxysilane as compounds having a vinyl group, and allyltrimethoxysilane as compounds having an allyl group.

[0077] Examples of the organosilicon compounds in which n is 1 and p is 3 include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, octyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane, cyclohexyltrimethoxysilane, ethinyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, and 3-aminopropyltrimethoxysilane. Examples include 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatetopropyltriethoxysilane, tris(trimethoxysilylpropyl)isocyanurate, and 3-mercaptopropyltrimethoxysilane.

[0078] Examples of the organosilicon compounds in which n is 2 and p is 2 include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldidiethoxysilane, propylmethyldimethoxysilane, octylmethyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, diphenyldimethoxysilane, benzylmethyldimethoxysilane, cyclohexylmethyldimethoxysilane, vinylmethyldimethoxysilane, allylmethyldimethoxysilane, p-styrylmethyldimethoxysilane, ethinylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and (3-ethyl-3-oxetanylmethoxypropyl)methyldimethoxysilane. Examples include (3-ethyl-3-oxetanylmethoxypropyl)methyldiethoxysilane, (3-methyl-3-oxetanylmethoxypropyl)methyldimethoxysilane, (3-oxetanyloxypropyl)methyldiethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropylmethyldimethoxysilane, hydrochloride salt of N-(vinylbenzyl)-2-aminoethyl-3-aminopropylmethyldimethoxysilane, 3-ureidopropylmethyldialkoxysilane, 3-isocyanatetopropylmethyldiethoxysilane, (3-acryloxypropyl)methyldimethoxysilane, and (3-methacryloxypropyl)methyldiethoxysilane.

[0079] Furthermore, the constituent unit represented by constituent unit (c) is preferably introduced as a compound of formula (1) by polycondensation of a silicone oligomer. Examples include polydimethylsiloxane with OH type at both ends, polydimethylsiloxane with OH type at one end, polydiphenylsiloxane with OH type at both ends, polydiphenylsiloxane with OH type at one end, polymethylphenylsiloxane with OH type at both ends, and polymethylphenylsiloxane with OH type at one end. There are no restrictions on the molecular weight of these compounds, but for example, their number average molecular weight is preferably 1,100 to 150,000, more preferably 1,500 to 20,000, even more preferably 2,000 to 15,000, and particularly preferably 2,500 to 10,000.

[0080] Examples of the organosilicon compounds in which n is 3 and p is 1 include hexamethyldisiloxane, trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane, 1,3-divinyltetramethyldisiloxane, dimethylphenylmethoxysilane, vinyldimethylmethoxysilane, vinyldimethylchlorosilane, (3-acryloxypropyl)dimethylmethoxysilane, (3-methacryloxypropyl)dimethylmethoxysilane, 2-(3,4-epoxycyclohexyl)ethyldimethylmethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, (3-ethyl-3-oxetanylmethoxypropyl)dimethylmethoxysilane, (3-ethyl-3-oxetanylmethoxypropyl)dimethylethoxysilane, (3-methyl-3-oxetanylmethoxypropyl)dimethylmethoxysilane, and (3-oxetanyloxypropyl)dimethylethoxysilane.

[0081] There are no particular limitations on the reaction solvent, but it is preferable to use an alcohol as the organic solvent. An alcohol is an alcohol in the narrow sense, represented by the general formula R-OH, and is a compound that has no functional groups other than an alcoholic hydroxyl group. There are no particular limitations on the alcohol, and examples 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. These alcohols may be used individually or in combination of two or more.

[0082] The organic solvent may be an alcohol alone, or it may be a mixed solvent with at least one auxiliary solvent. The auxiliary solvent may be a polar solvent, a nonpolar solvent, or a combination of both. Examples of organic solvents other than alcohols include xylene, toluene, methyl ethyl ketone, methyl isobutyl ketone, and propylene glycol monomethyl ether.

[0083] The hydrolysis and condensation reactions in the reaction process proceed in the presence of water. In the reaction process, it is preferable to add 0.5 to 30 molar equivalents of water relative to the total amount of hydrolyzable groups of the organosilicon compound to perform hydrolysis, and then to perform condensation. Furthermore, in the hydrolysis process, the amount of water added is preferably 0.6 molar equivalents or more, more preferably 0.7 molar equivalents or more, even more preferably 0.8 to 8 molar equivalents, particularly preferably 0.9 to 7 molar equivalents, and most preferably 1.0 to 6 molar equivalents, relative to the total amount of hydrolyzable groups of the organosilicon compound, from the viewpoint of the hardening shrinkage rate, hardness, and storage stability of the resulting organopolysiloxane represented by formula (1).

[0084] Furthermore, the hydrolysis and polycondensation reactions of silicon compounds may be carried out without a catalyst or with a catalyst. When a catalyst is used, acid catalysts such as inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, and phosphoric acid; organic acids such as formic acid, acetic acid, oxalic acid, and p-toluenesulfonic acid; and base catalysts such as ammonia, tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate are preferably used. The amount of catalyst used is preferably equivalent to 0.01 mol% to 20 mol%, and more preferably equivalent to 0.1 mol% to 10 mol%, based on the total amount (moles) of silicon atoms contained in the silicon compound.

[0085] The completion of hydrolysis and polycondensation reactions in the reaction process can be appropriately detected by methods described in various publications. In addition, in the hydrolysis step of the method for producing organopolysiloxane represented by formula (1), auxiliary agents may be added to the reaction system.

[0086] By including the aforementioned distillation step after the hydrolysis and polycondensation steps in the production of the organopolysiloxane represented by formula (1), the stability of the resulting silsesquioxane derivative of the present disclosure can be improved. Distillation can be carried out under atmospheric pressure or reduced pressure, at room temperature or under heating, or under cooling.

[0087] The method for producing organopolysiloxane represented by formula (1) may include a neutralization step to neutralize the catalyst before the distillation step. It may also include a step to remove the salt produced by neutralization by washing with water or the like.

[0088] Furthermore, the organopolysiloxane represented by formula (1) may contain side chain functional groups derived from the silicon compound used as a raw material in its production, specifically groups formed by the addition of an acid or the like to an oxetanyl group or epoxy group to open the ring, or it may contain a hydroxyalkyl group produced by the decomposition of an organic group having a (meth)acryloyl group, or it may contain a group formed by the addition of an acid or the like to an unsaturated hydrocarbon group. A specific example is that formula (1) may contain, for example, a structure represented by the following formula (A) and / or the structure represented by formula (B) as part of it. The content ratio is such that it is acceptable to implement this disclosure if it is 50 mol% or less relative to the amount equivalent to the original organic group having an oxetanyl group or epoxy group, the original organic group having a (meth)acryloyl group, or the original organic group having an unsaturated hydrocarbon group derived from the silicon compound used as a raw material, and is preferably 30 mol% or less, and more preferably 10 mol% or less. In formulas (A) and (B), T units are exemplified, but similar D units, M units, etc., may also be used. Here, (meth)acryloyl group means acryloyl group or metacloyl, and the same applies hereafter.

[0089]

[0090]

[0091] Furthermore, the content of organopolysiloxane represented by formula (1) in the curable composition according to this disclosure is 0.1% by mass or more and less than 20% by mass, relative to the total solid content of the curable composition, and is preferably 0.2% by mass to 15% by mass, more preferably 0.5% by mass to 10% by mass, and even more preferably 0.5% by mass to 5% by mass, from the viewpoint of water repellency, slipperiness, and oil repellency. In this disclosure, the term "solid content" means components excluding solvents, and liquid components such as low molecular weight components other than solvents are also included in "solid content" in this disclosure.

[0092] <Filler> The curable composition according to this disclosure preferably contains a filler from the viewpoint of hardness, low curing shrinkage, and heat resistance. As the filler, inorganic particles are preferred, and inorganic particles with an average particle size of less than 1 μm are more preferred.

[0093] In this disclosure, the average particle size is the median diameter based on volume unless otherwise specified. The average particle size of the inorganic particles is preferably 500 nm or less, more preferably 100 nm or less, and particularly preferably 5 nm or more and 50 nm or less. In this disclosure, the average particle size of the inorganic particles represents the particle size corresponding to a cumulative 50% by volume from the fine particle side in the volume-based particle size distribution of the inorganic material measured by a particle size distribution analyzer based on laser light diffraction scattering.

[0094] There are no particular restrictions on the material of the inorganic particles, and examples include glass, silica, alumina, mica, ceramics, silicone rubber powder, calcium carbonate, aluminum nitride, carbon powder, kaolin clay, dried clay minerals, and dried diatomaceous earth. Among these, silica particles are preferred as the inorganic particles, and colloidal silica is more preferred.

[0095] Furthermore, the inorganic particles may be surface-treated. For example, it is preferable that the surface is hydrophobic, that the inorganic particles have organic groups on the surface, and more preferably that the inorganic particles have polymerizable groups on the surface. There are no particular restrictions on the polymerizable groups on the surface of the inorganic particles, and examples include radical polymerizable groups and cationic polymerizable groups, with radical polymerizable groups being more preferred. As for non-polymerizable organic groups, examples include groups containing non-polymerizable organic groups such as alkyl groups, aryl groups, and aralkyl groups, with alkyl groups being more preferred. The organic groups may also be reactive groups such as sulfanyl groups, amino groups, ethylenically unsaturated groups, and hydroxyl groups. Examples of radical polymerizable groups include acryloyl groups, methacryloyl groups, and vinyl groups. As for cationic polymerizable groups, for example, cyclic ether groups are preferred, epoxy groups or oxetanyl groups are more preferred, and epoxy groups are particularly preferred. There are no particular restrictions on the surface treatment method for the inorganic particles, and known methods can be used. In addition, various commercially available inorganic fillers can be used. Examples of commercially available colloidal silica include Nissan Chemical Corporation's "MEK-EC-2130Y", "MEK-EC-2430Z", "PGM-AC-2140Y", "PGM-AC-3140Y", "PGM-AC-4130Y", "MIBK-SD-L", "MEK-AC-2140Z", "MEK-AC-4130Y", "MEK-AC-5340Z", "MEK-AC-5140Z", "MIBK-AC-2140Z", "PMA-ST", "TOL-ST", "EAC-ST", "MEK-ST-ZL", "MIBK-ST", and "CHO-ST-M", and JGC Catalysts & Chemicals Corporation's "ELCOM V-8804" and "ELCOM Examples include the "V-8802," and BYK Corporation's "NANOBYK-3650," "NANOBYK-3652," "BYK-UV 3518," and "BYK-UV 3519."

[0096] From the viewpoints of hardness, low curing shrinkage, and heat resistance, the mass ratio of the filler is preferably 5% by mass to 90% by mass, more preferably 15% by mass to 85% by mass, still more preferably 30% by mass to 80% by mass, and particularly preferably 50% by mass to 75% by mass, relative to the total solid content of the curable composition.

[0097] <Organopolysiloxane represented by Formula (2)> From the viewpoint of hardness, the curable composition according to the present disclosure preferably further contains an organopolysiloxane represented by formula (2). The organopolysiloxane represented by formula (2) is a compound different from the compound represented by formula (1).

[0098] In formula (2), R ４ , R ５ and R ６ each independently represent 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, or a monovalent organic group having a polymerizable group; at least one of R ４ , R ５ and R ６ is a monovalent organic group having a polymerizable group. The alkyl group, aralkyl group, aryl group and monovalent organic group having a polymerizable group in R ４ , R ５ and R ６ 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.

[0099] Each structural unit of the organopolysiloxane represented by formula (2), which is a silsesquioxane derivative, is referred to as structural units (p) to (s) respectively, according to the subscripts p to s at the lower right of the parentheses indicating each structural unit. Unless otherwise specified below, preferred embodiments of the structural units (p) to (s) are the same as the preferred embodiments of the aforementioned structural units (a) to (d), respectively. Unless otherwise specified below, preferred embodiments of R ４ to R ６ are also the same as the preferred embodiments of the aforementioned R １ to R ３These are similar to the preferred embodiments.

[0100] From the viewpoint of hardness and reactivity, the R ４ ~R ６ It is preferable that at least one of them has a monovalent organic group having a polymerizable group. ４ ~R ６ If the group is not a monovalent organic group having polymerizable groups, from the viewpoint of hardness and viscosity, it is preferably a saturated or unsaturated chain hydrocarbon group having 1 to 20 carbon atoms, a saturated or unsaturated cyclic hydrocarbon group having 3 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms; more preferably an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms; even more preferably a methyl group, an ethyl group, a propyl group, a phenyl group, or a benzyl group; and a methyl group is particularly preferred.

[0101] The proportion of constituent units (p) in the organopolysiloxane represented by formula (2) is not particularly limited, but from the viewpoint of hardness, reactivity, and viscosity, when expressed as the proportion of all constituent units (p) to (s) of the organopolysiloxane represented by formula (2) to the total moles, using the following formula: p / (p + q + r + s) × 100 (mol%), it is preferably 0 mol% to 80 mol%, more preferably 0 mol% to 70 mol%, even more preferably 0 mol% to 60 mol%, and particularly preferably 0 mol% to 50 mol%.

[0102] The proportion of constituent units (q) in the organopolysiloxane represented by formula (2) is not particularly limited, but from the viewpoint of hardness, reactivity, and viscosity, when expressed as the ratio of all constituent units (p) to (s) of the organopolysiloxane represented by formula (2) to the total moles, using the following formula: q / (p + q + r + s) × 100 (mol%), it is preferably 5 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, more preferably 50 mol% to 100 mol%, even more preferably 70 mol% to 100 mol%, particularly preferably 80 mol% to 100 mol%, and most preferably 100 mol%.

[0103] In the organopolysiloxane represented by formula (2), the proportion of constituent units (r) is preferably 50 mol% or less, more preferably 30 mol% or less, even more preferably 10 mol% or less, and particularly preferably r is 0, when expressed as the ratio of all constituent units (p) to (s) of the organopolysiloxane represented by formula (2) to the total moles of the organopolysiloxane represented by formula (2) using the following formula: r / (p+q+r+s) × 100 (mol%).

[0104] In the organopolysiloxane represented by formula (2), the proportion of constituent units (s) is preferably 30 mol% or less, more preferably 20 mol% or less, even more preferably 10 mol% or less, and particularly preferably 0 mol%, when expressed as the ratio of all constituent units (p) to (s) of the organopolysiloxane represented by formula (2) to the total moles, using the following formula: s / (p+q+r+s) × 100 (mol%). This is especially preferable from the viewpoint of hardness, reactivity, and viscosity.

[0105] (Other constituent units (t)) The organopolysiloxane represented by formula (2) further includes (R) as a constituent unit that does not contain Si. ８ O １／２ ) may include (hereinafter also referred to as the constituent unit (t)). Here, R ８ 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 alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups.

[0106] The constituent unit (t) is an alkoxy group, which is a hydrolyzable group contained in the silicon compound described later, or an alkoxy group produced when an alcohol contained in the reaction solvent substitutes for a hydrolyzable group in the silicon compound. This alkoxy group may remain in the molecule without hydrolysis or polycondensation, or it may be a hydroxyl group that remains in the molecule after hydrolysis without polycondensation.

[0107] There are no particular restrictions on the content of constituent unit (t), but from the viewpoint of hardness, for example, if the molar amount of constituent unit (t) is expressed as the ratio of the molar amount of constituent unit (t) to the total molar amount of all silicon atoms of the organopolysiloxane represented by formula (2), i.e., the total molar amount of all constituent units (p) to (s), then it is preferably 0 mol% to 100 mol%, more preferably 1 to 70 mol%, even more preferably 5 mol% to 70 mol%, even more preferably 10 to 70 mol%, and particularly preferably 40 to 70 mol%. The content of constituent unit (t) may also be calculated in the same manner as the content of constituent unit (e).

[0108] The weight-average molecular weight (hereinafter also referred to as "Mw") of the organopolysiloxane represented by formula (2) is not particularly limited and may be, for example, 300 to 50,000, 500 to 25,000, 700 to 20,000, or 1,000 to 15,000. In this disclosure, Mw refers to the value obtained by converting the molecular weight measured by GPC (gel permeation chromatography) using polystyrene as a standard substance. For example, the measurement conditions in the examples described later can be used as the measurement conditions for Mw.

[0109] (Method for producing organopolysiloxane represented by formula (2)) The organopolysiloxane represented by formula (2) can be produced by known methods, similar to the organopolysiloxane represented by formula (1).

[0110] The organopolysiloxane represented by formula (2) may include, for example, a complete cage structure, an incomplete cage structure, a ladder structure, a random structure, and a linear structure, and may also include structures that are arbitrarily partially combined from these structures. Furthermore, it may be a mixture that arbitrarily contains these various structures. Therefore, the organopolysiloxane represented by formula (2) can be said to represent the average composition by determining the molar ratios of the constituent units (p) to (s) as described above.

[0111] The mass ratio of the organopolysiloxane represented by formula (2) is not particularly limited, but from the viewpoint of hardness and reactivity, it is preferably 10% to 99% by mass, more preferably 20% to 90% by mass, and even more preferably 30% to 85% by mass, based on the total solid content of the curable composition.

[0112] <Polymerization Initiator> From the viewpoint of curability, the curable composition according to this disclosure preferably contains a polymerization initiator. The polymerization initiator is not particularly limited and includes, for example, photopolymerization initiators and thermal polymerization initiators. Examples of photopolymerization initiators include photoradical polymerization initiators and photocationic polymerization initiators. Examples of thermal polymerization initiators include thermal radical polymerization initiators and thermal cationic polymerization initiators. Known compounds may be used as photopolymerization initiators and thermal polymerization initiators.

[0113] Examples of photoradical polymerization initiators include 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrakis(pentafluorophenyl)borate, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenyl 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, and 2-benzyl- Acetophenone compounds such as 2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, diethoxyacetophenone, oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone] and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methyl-propan-1-one; benzophenone compounds such as benzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone and 4-benzoyl-4'-methyldiphenyl sulfide. Compounds; α-ketoester compounds such as methylbenzoyl formate, 2-[2-oxo-2-phenylacetoxyethoxy]ethyl oxyphenylacetic acid, and 2-[2-hydroxyethoxy]ethyl 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, benzo Examples include benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; titanocene compounds; acetophenone / benzophenone hybrid photoinitiators such as 1-(4-(4-benzoylphenylsulfanyl)phenyl)-2-methyl-2-(4-methylphenylsulfinyl)propan-1-one; oxime ester photopolymerization initiators such as 1-(4-phenylthiophenyl)-2-(O-benzoyloxime)-1,2-octanedione; and camphorquinone.These can be used individually or in combination of two or more.

[0114] There are no particular restrictions on the photocationic polymerization initiator; for example, onium salts such as iodonium salts, sulfonium salts, diazonium salts, selenium salts, pyridinium salts, ferrocenium salts, and phosphonium salts are used. Among these, iodonium salts and sulfonium salts are preferred. When the photocationic polymerization initiator is an iodonium salt or a sulfonium salt, the counter anion is, for example, BF ４ － AsF ６ － SbF ６ － , PF ６ － and B (C ６ F ５ ) ４ － These are some examples.

[0115] The iodonium salts mentioned above include (tricumyl)iodonium tetrakis(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis(pentafluorophenyl)borate, bis(dodecylphenyl)iodonium hexafluorophosphate, bis(dodecylphenyl)iodonium hexafluoroantimonate, bis(dodecylphenyl)iodonium tetrafluoroborate, 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- Examples include 4-(1-methylethyl)phenyliodonium tetrakis(pentafluorophenyl)borate. Furthermore, commercially available iodonium salts can also be used, specifically, for example, "UV-9380C" (product name) from GE Toshiba Silicone, "Bluesil PI2074" (product name) from Elkem Silicones, and "WPI-116" (product name) and "WPI-113" (product name) from Fujifilm Wako Pure Chemical Industries. These may be used individually or in combination of two or more.

[0116] 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, diphenyl-4-(phenylthio)phenylsulfonium tetrakis(pentafluorophenyl)borate, and tri Examples include phenylsulfonium 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. Furthermore, commercially available sulfonium salts can also be used. Specifically, examples include "Cyracure UVI-6990" (product name), "Cyracure UVI-6992" (product name), and "Cyracure UVI-6974" from Dow Chemical Japan, and "ADEKA Optomer SP-150" (product name), "ADEKA Optomer SP-152" (product name), "ADEKA Optomer SP-170" (product name), and "ADEKA Optomer SP-172" (product name) from ADEKA Corporation. These can be used individually or in combination of two or more.

[0117] Examples of the diazonium salts include benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, and benzenediazonium hexafluoroborate. These may be used individually or in combination of two or more.

[0118] There are no particular restrictions on the thermal radical polymerization initiator; examples include peroxides and azo-based initiators.

[0119] 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-dimethylcyclohexane. -Butyl 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-toluylperoxy)hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy2-ethylhexyl monocarbonate, t- Hexyl peroxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butyl peroxyacetate, 2,2-bis(t-butylperoxy)butane, t-butyl peroxybenzoate, 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)hexyl Examples of organic peroxides include t-butylcumyl peroxide, di-t-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyn-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, and t-butyl hydroperoxide. These may be used individually or in combination of two or more.

[0120] Examples of azo initiators include azo compounds such as 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitride), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, azodi-t-octane, and azodi-t-butane. These may be used individually or in combination of two or more. Furthermore, a redox reaction can be achieved by combining a peroxide with a reducing agent such as ascorbic acid, sodium ascorbate, sodium erythorbate, tartaric acid, citric acid, metal salts of formaldehyde sulfoxylate, sodium thiosulfite, sodium sulfite, sodium metabisulfite, or ferric chloride.

[0121] The thermal cationic polymerization initiator is not particularly limited and examples include sulfonium salts, phosphonium salts, and quaternary ammonium salts. Among these, sulfonium salts are preferred. As a counteranion in the thermal cationic polymerization initiator, for example, AsF ６ － SbF ６ － , PF ６ － , B (C ６ F ５ ) ４ － These are some examples.

[0122] Examples of the sulfonium salts include triphenylsulfonium boron tetrafluoride, triphenylsulfonium antimony hexafluoride, triphenylsulfonium arsenide hexafluoride, tri(4-methoxyphenyl)sulfonium arsenide hexafluoride, diphenyl(4-phenylthiophenyl)sulfonium arsenide hexafluoride, etc. Commercially available sulfonium salts can also be used, specifically, for example, "ADEKA Opton CP-66" (product name) and "ADEKA Opton CP-77" (product name) from ADEKA Corporation, and "San-Aid SI-60L" (product name), "San-Aid SI-80L" (product name), and "San-Aid SI-100L" (product name) from Sanshin Chemical Industry Co., Ltd. These may be used individually or in combination of two or more.

[0123] Examples of the phosphonium salt include ethyltriphenylphosphonium antimony hexafluoride and tetrabutylphosphonium antimony hexafluoride. Examples of the quaternary ammonium salt include N,N-dimethyl-N-benzylanilinium antimony hexafluoride, N,N-diethyl-N-benzylanilinium boron tetrafluoride, N,N-dimethyl-N-benzylpyridinium antimony hexafluoride, N,N-diethyl-N-benzylpyridinium trifluoromethanesulfonic acid, N,N-dimethyl-N-(4-methoxybenzyl)pyridinium antimony hexafluoride, N,N-diethyl-N-(4-methoxybenzyl)pyridinium antimony hexafluoride, N,N-diethyl-N-(4-methoxybenzyl)toluidinium antimony hexafluoride, and N,N-dimethyl-N-(4-methoxybenzyl)toluidinium antimony hexafluoride. These may be used individually or in combination of two or more.

[0124] The polymerization initiator may be used alone or in combination of two or more types. From the viewpoint of curability, the content of the polymerization initiator is preferably 0.1% to 20.0% by mass, more preferably 0.5% to 15.0% by mass, even more preferably 1.0% to 10.0% by mass, and particularly preferably 2.0% to 6.0% by mass, based on the total solid content of the curable composition.

[0125] (Other Polymerizable Compounds) The curable composition according to this disclosure may contain polymerizable compounds other than those described above (hereinafter also referred to as "other polymerizable compounds"). Other polymerizable compounds are not particularly limited as long as they are compounds that can undergo polymerization reactions in the presence of a polymerization initiator. Examples of other polymerizable compounds include organopolysiloxanes represented by formula (1) and silsesquioxane derivatives other than organopolysiloxanes represented by formula (2), (meth)acrylate compounds, compounds having ethylenically unsaturated groups, epoxy compounds, compounds having oxetanyl groups, and compounds having vinyl ether groups.

[0126] There are no particular restrictions on (meth)acrylate compounds, and examples include compounds having one (meth)acryloyl group (hereinafter also referred to as "monofunctional (meth)acrylate") and compounds having two or more (meth)acryloyl groups (hereinafter also referred to as "polyfunctional (meth)acrylate").

[0127] Examples of monofunctional (meth)acrylates include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; monofunctional (meth)acrylates having alicyclic groups such as cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and tricyclodecanemethylol (meth)acrylate; monofunctional (meth)acrylates having aromatic groups such as benzyl (meth)acrylate and phenyl (meth)acrylate; (meth)acrylates of alkylene oxide adducts of phenol derivatives such as phenolethylene oxide adducts, phenolpropylene oxide adducts, modified nonylphenolethylene oxide adducts, and nonylphenolpropylene oxide adducts; (meth)acrylates of alkylene oxide adducts of paracumylphenol, orthophenylphenol (meth)acrylate, and orthophenylphenol (meth)acrylate; monofunctional (meth)acrylates having alkoxyalkyl groups such as 2-ethylhexylcarbitol (meth)acrylate; monofunctional (meth)acrylates having heterocyclic groups 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 hydroxyl and aromatic groups 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;Examples include monofunctional (meth)acrylates having a carboxyl group, such as ω-carboxypolycaprolactone mono(meth)acrylate and monohydroxyethyl phthalate (meth)acrylate.

[0128] 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; and polypropylene glycol di(meth)acrylates such as dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and tetrapropylene glycol di(meth)acrylate. Examples 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, trimethylolpropaneallyl 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.

[0129] Polyfunctional (meth)acrylates can also be used, such as urethane (meth)acrylates. Examples of urethane (meth)acrylates include compounds obtained by addition reaction between an organic polyisocyanate and a hydroxyl group-containing (meth)acrylate, and compounds obtained by addition reaction between an organic polyisocyanate, a polyol, and a hydroxyl group-containing (meth)acrylate. Monofunctional (meth)acrylates, polyfunctional (meth)acrylates, etc., may be used individually, or two or more may be used in combination, and different types may also be used in combination.

[0130] 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, cyclohexanedimethylol, 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 acid components such as dibasic acids such as adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid, and terephthalic acid, or their anhydrides. These may be used individually, in combination of two or more, or in combination of different types.

[0131] Examples of organic polyisocyanates include tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene 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 a 3-mol alkylene oxide adduct of isocyanuric acid, and dipentaerythritol penta(meth)acrylate. These may be used individually, in combination of two or more, or different types may be used in combination.

[0132] Compounds 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. Here, (meth)acrylic means acrylic or methacrylic, and the same applies hereafter. Specific examples of compounds having the ethylenically unsaturated group include (meth)acrylic acid, Michael-added dimers of acrylic acid, N-(2-hydroxyethyl)citraconimide, N,N-dimethylacrylamide, acryloylmorpholine, N-vinylpyrrolidone, and N-vinylcaprolactam. These may be used individually or in combination of two or more.

[0133] 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. As these compounds, for example, compounds described in Japanese Patent Application Publication No. 2011-42755 may be used. There are no particular restrictions on silicones, and known ones can be used, for example, polydimethyl silicone, polydiphenyl silicone and polymethylphenyl silicone, and those having functional groups at their terminals and / or side chains are preferred. There are no particular restrictions on the functional groups, for example, (meth)acryloyl groups, epoxy groups, oxetanyl groups, vinyl groups, hydroxyl groups, carboxyl groups, amino groups and thiol groups.

[0134] From the viewpoint of hardness, the mass ratio of the other polymerizable compounds is preferably 0% to 50% by mass, more preferably 0% to 30% by mass, and even more preferably 0% to 20% by mass, based on the total solid content of the curable composition.

[0135] (Other Components) The curable composition according to this disclosure may further contain other components other than the organopolysiloxane represented by formula (1), fillers, the organopolysiloxane represented by formula (2), polymerization initiators, and other polymerizable compounds. Other components are not particularly limited and include, for example, solvents, resins, monomers, surfactants, antistatic agents (e.g., conductive polymers), leveling agents, photosensitizers, ultraviolet absorbers, antioxidants, heat resistance improvers, stabilizers, lubricants, pigments, dyes, plasticizers, suspending agents, adhesion promoters, nanoparticles, nanofibers, nanosheets, etc. The curable composition according to this disclosure may also contain silane-based reactive diluents such as tetraalkoxysilanes, trialkoxysilanes, dialkoxysilanes, monoalkoxysilanes, and disiloxanes.

[0136] The curable composition according to this disclosure may or may not contain a solvent. Examples of solvents include various organic solvents such as aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, chlorinated hydrocarbon solvents, alcohol solvents, ether solvents, amide solvents, ketone solvents, ester solvents, and cellosolve solvents.

[0137] <Contact Angle> From the viewpoint of water repellency, the water contact angle of the cured surface of the curable composition is preferably 100° or more. Furthermore, the water contact angle of the cured surface of the curable composition is preferably 115° or less. Furthermore, from the viewpoint of oil repellency, the oleic acid contact angle of the cured surface of the curable composition is preferably 40° or more, more preferably 50° or more, and even more preferably 53° or more. Furthermore, the oleic acid contact angle of the cured surface of the curable composition is preferably 70° or less.

[0138] The method for measuring the contact angle in this disclosure is as follows. The curable composition was placed on an SPCC-SD steel sheet (dull-finished cold-rolled steel sheet) and a triacetylcellulose (TAC) film (Fujitac TD80UL, manufactured by Fujifilm Corporation, 80 μm thick), respectively, and coated using a No. 8 bar coater. After drying in a 60°C forced-air oven for 5 minutes, a cured film (photocured film) was prepared by ultraviolet irradiation under the following conditions. The film thickness in both cases was approximately 5 μm. - Ultraviolet curing 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: Nitrogen Number of passes: 10

[0139] The contact angle of the hardened film prepared on the SPCC-SD steel sheet as described above with pure water or oleic acid at 23°C is evaluated using DMo-502 manufactured by Kyowa Interface Science Co., Ltd.

[0140] <Coefficient of Friction> The static friction coefficient and dynamic friction coefficient of the cured surface of the curable composition with respect to the dust-free cloth are preferably 0.2 or less, more preferably 0.15 or less, and even more preferably 0.1 or less. Furthermore, the static friction coefficient and dynamic friction coefficient of the cured surface of the curable composition with respect to the dust-free cloth are preferably 0 or more.

[0141] The method for measuring the coefficient of friction in this disclosure is as follows: A hardened film is prepared in the same manner as the method for measuring the contact angle described above. The hardened film prepared on the SPCC-SD steel plate as described above is evaluated at 23°C using a Shinto Kagaku Tripogear TYPE:14FW in accordance with ISO 8295:1995(E). A dust-free cloth indenter (Asahi Kasei Corporation's Bencot M-3 II) is used, the load is 200g, the speed is 100mm / min, and the average value of three measurements taken at a distance of 3cm is taken as the coefficient of static friction and the coefficient of dynamic friction.

[0142] <Pencil Hardness> From the viewpoint of hardness, the pencil hardness of the cured product of the curable composition formed on the SPCC-SD steel sheet is preferably 6H or higher, more preferably 8H or higher, even more preferably 9H or higher, and particularly preferably 10H. Furthermore, from the viewpoint of hardness, the pencil hardness of the cured product of the curable composition formed on the triacetylcellulose (TAC) film is preferably 4H or higher.

[0143] The method for measuring pencil hardness in this disclosure is as follows: A hardened film is prepared on an SPCC-SD steel plate or TAC film in the same manner as the contact angle measurement method described above. The hardened film prepared on the SPCC-SD steel plate or TAC film as described above is tested in accordance with JIS K5600-5-4 (extending pencil hardness up to 10H). A scratch test is performed three times for each hardness pencil, and the highest value of the pencil type in which no defects occurred in the hardened film is defined as the pencil hardness.

[0144] [Cured products, hard coat agents, hard coats, articles, and laminates] The cured products according to this disclosure are obtained by curing the curable composition according to this disclosure. For example, the cured products according to this disclosure can be obtained by irradiating the curable composition according to this disclosure with active energy rays or by heating the curing composition according to this disclosure. The hard coat agent according to this disclosure includes the curable composition according to this disclosure. The hard coat according to this disclosure is obtained by curing the hard coat agent according to this disclosure. The articles according to this disclosure are equipped with the hard coat according to this disclosure. The laminate according to this disclosure comprises the hard coat according to this disclosure and a substrate.

[0145] When curing the curable composition according to this disclosure, the curable composition according to this disclosure may be applied to a substrate before curing. The curable composition according to this disclosure may or may not contain a solvent. If it contains a solvent, it is preferable to remove the solvent before curing.

[0146] When applying the curable composition according to this disclosure to a substrate, the method of application of the curable composition is not particularly limited. Examples of application methods include known coating methods such as inkjet, cast, spin coat, bar coat, dip coat, spray coat, roll coat, flow coat, and gravure coat. There are no particular limitations on the thickness to which the curable composition according to this disclosure is applied, and it can be appropriately set according to the purpose. There are no particular limitations on the substrate to which the curable composition according to this disclosure is applied, and examples 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 (PET), polyvinyl chloride resin, polycarbonate resin, epoxy resin, polyamide resins such as nylon and aramid, polyimide resin, polyamide-imide resin, fluororesins such as tetrafluoroethylene resin, polyolefin resins such as crosslinked polyethylene resin, vinylidene chloride resin, acrylonitrile-butadiene-styrene (ABS) resin, polystyrene resin, polyacrylonitrile resin, cycloolefin polymer (COP), cycloolefin copolymer (COC), acetate resin, polyarylate, cellophane, norbornene resin, acetylcellulose resin such as triacetylcellulose (TAC), polychloroprene, polyphenylene sulfide, polysulfone, polyethersulfone, polyetheretherketone, polyurethane resin, glass epoxy resin, and other composite resins, as well as various fiber-reinforced resins. Examples of fibers include natural fibers, regenerated fibers, semi-synthetic fibers, metal fibers, glass fibers, carbon fibers, ceramic fibers, and known chemical fibers. The fabric may be woven or nonwoven, and can be made using, for example, the aforementioned fibers.These materials may be used individually, or two or more may be combined, mixed, or compounded. There are no particular restrictions on the shape of the substrate; examples include plate-like, sheet-like, film-like, rod-like, spherical, fibrous, powder-like, lens-like, and other regular or irregular shapes.

[0147] (Curing Method) In this disclosure, the curing method and curing conditions are selected depending on whether the curable composition is active energy ray curable and / or thermosetting. The curing conditions (for example, the type of light source and the amount of light irradiation in the case of active energy ray curable, and the heating temperature and heating time in the case of thermosetting) are appropriately selected depending on the type and amount of polymerization initiator and the types of other polymerizable compounds contained in the curable composition.

[0148] (1) Active Energy Ray Curing Method If the curable composition according to this disclosure is an active energy ray curable composition, the curing method may be to irradiate it with active energy rays using a known active energy ray irradiation device. Examples of active energy rays include electron beams, ultraviolet rays, visible light, and X-rays, with light being preferred and ultraviolet rays being more preferred from the viewpoint of being able to use inexpensive equipment. Examples of ultraviolet irradiation devices include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, ultraviolet (UV) electrodeless lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, and light-emitting diodes (LEDs). The light irradiation intensity on a film coated with the curable composition according to this disclosure can be selected according to the purpose, application, etc. The light irradiation intensity in the wavelength range effective for activating the active energy ray polymerization initiator (referred to as the photopolymerization initiator in the case of photocurable) (which 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 / cm². ２ ~1000mW / cm ２It is preferable that this is the case. Furthermore, the irradiation energy should be appropriately set according to the type of active energy ray, the composition of the mixture, etc. The light irradiation time to the coating may also be selected according to the purpose, application, etc., and the integrated light amount, expressed as the product of the light irradiation intensity and light irradiation time in the light wavelength range, should be 10 mJ / cm. ２ ~7,000mJ / cm ２ It is preferable to set the light irradiation time so that the result is as follows. The integrated light intensity is 200 mJ / cm². ２ ~5,000mJ / cm ２ More preferably, 500 mJ / cm ２ ~4,000mJ / cm ２ This is even more preferable. If the cumulative light intensity is within the above range, the curing of the composition proceeds smoothly, and a uniform cured product can be easily obtained.

[0149] Furthermore, heat curing can be appropriately combined before and / or after active energy ray curing. For example, a two-stage curing process can be performed in which a curable composition is impregnated into a substrate that has areas that are shaded when irradiated with active energy rays, and then the active energy rays are irradiated to first cure the curable composition in the areas that are hit by the active energy rays, and then heat is applied to cure the parts of the composition that are not hit by the active energy rays. There are no particular restrictions on such substrates, and examples include substrates with complex shapes such as fabric, fibers, powder, porous, and uneven surfaces, and may also be shapes that combine two or more of these shapes.

[0150] The cured product according to this disclosure may be further heated before or after active energy ray curing. Additional heating improves hardness. The heating temperature of the cured product is preferably 60°C to 300°C, more preferably 80°C to 270°C, and even more preferably 100°C to 250°C. The curing temperature may be kept constant or increased. A combination of increasing and decreasing temperature may also be used. The heating time of the cured product is preferably 1 minute to 360 minutes, more preferably 5 minutes to 120 minutes, and even more preferably 5 minutes to 60 minutes.

[0151] (2) Thermosetting Method When the curing composition according to this disclosure is a thermosetting composition, the curing method and curing conditions are not particularly limited. The curing temperature is preferably 80°C to 200°C, more preferably 100°C to 180°C, and even more preferably 110°C to 150°C. The curing temperature may be kept constant or increased. A combination of increasing and decreasing temperature 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 preferred conditions, a uniform cured film without blistering, cracking, etc., can be formed.

[0152] (Uses of Cured Products, etc.) The curable composition according to this disclosure can be used in various coating agents, molding agents, 3D printer compositions, etc. Because the cured product has excellent hardness, it can be applied to hard coat films, and because it can impart antifouling properties, it can be suitably applied to high-hardness antifouling coating agents. For example, it can be suitably used as a hard coat agent for displays and lenses. Furthermore, the curable composition according to this disclosure can be used in anti-reflective coatings, antifouling coatings, molding materials for 3D printers, resists, imprint materials, filler materials, planarization materials, etc. Furthermore, because it contains polysiloxane and can optionally contain inorganic fillers, it can be used as a gas barrier material, waterproof material, sealing material, corrosion-resistant material, weather-resistant material, heat-resistant material, etc. Examples of applications include works of art and crafts, sanitary ware products such as toilets, painted parts such as the bodies of automobiles and railway vehicles, home appliances, and housing products, and these can be given abrasion resistance and durability by coating.

[0153] Next, the present disclosure will be described in detail based on examples and comparative examples. The present disclosure is not limited to the following examples.

[0154] <Synthesis of Polysiloxane 1> 56.7 g (0.24 mol) of 3-acryloyloxypropyltrimethoxysilane, 10 g of polydimethylsiloxane (silanol-modified at both ends, functional group equivalent 500 g / mol), and 103 g of 2-propanol were weighed into a 500 mL four-necked flask fitted with a stirrer, dropping funnel, and condensate. A mixture of 0.9 g of 25% by mass aqueous solution of tetramethylammonium hydroxide and 12.3 g of pure water was added dropwise, and the mixture was stirred at room temperature for 4 hours. The resulting solution was concentrated under reduced pressure, dissolved in toluene, washed with water using a separatory funnel, and the solvent was removed from the organic layer under reduced pressure to obtain 50 g of polysiloxane 1. １ The 1H-NMR spectrum was measured to confirm that T and D units were introduced according to the raw material ratio. Furthermore, the product... ２９ Si-NMR spectroscopy was measured to confirm that the silicone had been successfully introduced. The maximum molecular weight in polystyrene equivalent detected by GPC was 27,700, and the weight-average molecular weight (Mw) was 4,870.

[0155] <Synthesis of Polysiloxane 2> Except for replacing 3-acryloyloxypropyltrimethoxysilane with 57.7 g (0.23 mol) of 3-methacryloyloxypropyltrimethoxysilane, 50 g of polysiloxane 2 was obtained in the same manner as in Synthesis Example 1. １ The 1H-NMR spectrum was measured to confirm that T and D units were introduced according to the raw material ratio. Furthermore, the product... ２９ Si-NMR spectra were measured to confirm that the silicon had been successfully introduced.

[0156] <Synthesis of Polysiloxane 3> 57.7 g (0.23 mol) of 3-methacryloyloxypropyltrimethoxysilane, 10 g of polydimethylsiloxane (silanol-modified at both ends, functional group equivalent 1500 g / mol), and 103 g of 2-propanol were weighed into a 500 mL four-necked flask fitted with a stirrer, dropping funnel, and condensate. 0.9 g of 25% by mass aqueous solution of tetramethylammonium hydroxide and 12.3 g of pure water were added dropwise, and the mixture was stirred at 40°C for 4 hours. The resulting solution was concentrated under reduced pressure, dissolved in toluene, washed with water using a separatory funnel, and the solvent was removed from the organic layer under reduced pressure to obtain 50 g of polysiloxane 3. １ The 1H-NMR spectrum was measured to confirm that T and D units were introduced according to the raw material ratio. Furthermore, the product... ２９ Si-NMR spectra were measured to confirm that the silicon had been successfully introduced.

[0157] <Synthesis of Polysiloxane 4> Except for changing polydimethylsiloxane to polydimethylsiloxane (silanol-modified type at both ends, functional group equivalent 2100 g / mol), 50 g of polysiloxane 4 was obtained in the same manner as in Synthesis Example 1. １ The 1H-NMR spectrum was measured to confirm that T and D units were introduced according to the raw material ratio. Furthermore, the product... ２９ Si-NMR spectra were measured to confirm that the silicon had been successfully introduced.

[0158] <Synthesis of Polysiloxane 5> Except for changing polydimethylsiloxane to polydimethylsiloxane (silanol-modified type at both ends, functional group equivalent 4300 g / mol), 50 g of polysiloxane 5 was obtained in the same manner as in Synthesis Example 1. １ The 1H-NMR spectrum was measured to confirm that T and D units were introduced according to the raw material ratio. Furthermore, the product... ２９ Si-NMR spectra were measured to confirm that the silicon had been successfully introduced.

[0159] <Synthesis of Polysiloxane 6> Except for changing the ratio of raw materials used, 50 g of polysiloxane 5 was obtained in the same manner as in Synthesis Example 4.１ The 1H-NMR spectrum was measured to confirm that T and D units were introduced according to the raw material ratio. Furthermore, the product... ２９ Si-NMR spectra were measured to confirm that the silicon had been successfully introduced.

[0160] The synthesis results for synthesis examples 1 to 6 are summarized in Table 1.

[0161] <Synthesis of Polysiloxane 7 (Organopolysiloxane represented by formula (2))> 140.6 g (0.6 mol) of 3-acryloyloxypropyltrimethoxysilane, 99.3 g (0.4 mol) of 3-methacryloyloxypropyltrimethoxysilane, 64.6 g of 2-propanol, and 0.085 g of hydroquinone were weighed into a 500 mL four-necked flask fitted with a stirrer, dropping funnel, and condenser, and the mixture was thoroughly stirred in a water bath at 30°C. Separately, 1.0 g of 35% hydrochloric acid (9.6 mmol as hydrogen chloride) and 150.7 g of pure water were mixed to prepare an aqueous solution. The prepared aqueous solution was added to the mixture dropwise from the dropping funnel over approximately 1 hour while stirring the reaction mixture, and then left 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 of the starting organosilicon compounds. Subsequently, the reaction mixture was heated to 60°C while the solvent and other substances in the reaction mixture were removed by reduced pressure distillation to obtain 170 g of colorless, transparent polysiloxane X. １ ¹H-NMR analysis confirmed that each constituent unit was quantitatively introduced according to the raw material ratio. The synthesized polysiloxane 7 had a viscosity of 620 mPa·s at 25°C and a weight-average molecular weight (Mw) of 2,010.

[0162] <Measurement of Molecular Weight> The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of polysiloxane, and the maximum molecular weight of the components contained therein, were determined by gel permeation chromatography (HLC-8320GPC, manufactured by Tosoh Corporation; hereinafter abbreviated as "GPC") in tetrahydrofuran solvent at 40°C, using a GPC column "TSK gel SuperMultiporeHZ-M" (manufactured by Tosoh Corporation). The molecular weight in terms of standard polystyrene was calculated from the retention time.

[0163] <Viscosity Measurement> The viscosity of polysiloxane was measured at 25°C using a TVE22H viscometer manufactured by Toki Sangyo Co., Ltd.

[0164]

[0165] (Examples 1-8 and Comparative Examples 1-3) <Preparation of curable composition and production of cured film> As an organopolysiloxane represented by formula (2), 1.49 g of polysiloxane 7 was weighed, along with 0.15 g of 2-hydroxy-2-methyl-1-phenylpropanone, 0.77 g of propylene glycol monobutyl ether, as a polysiloxane represented by formula (1), polysiloxanes 1-6 listed in Table 2 in the mass ratios listed in Table 2, and 3.71 g of silica particles (V-8804 manufactured by JGC Catalysts & Chemicals Co., Ltd., silica particles surface-modified with functional groups having ethylenically unsaturated groups, effective concentration 40% by mass) as a filler. These were then mixed in a rotating / revolving mixer to prepare a curable composition (photocurable composition) with the composition shown in Table 2.

[0166] Each curable composition was placed on either an SPCC-SD steel sheet (dull-finished cold-rolled steel sheet) or a triacetylcellulose (TAC) film (Fujitac TD80UL, manufactured by Fujifilm Corporation, 80 μm thick), coated using a No. 8 bar coater, dried in a 60°C forced-air oven for 5 minutes, and then irradiated with ultraviolet light under the following conditions to produce a cured film (photocured film). The film thickness in both cases was approximately 5 μm. -Ultraviolet curing conditions- Lamp: High-pressure mercury lamp Lamp height: 10 cm Conveyor speed: 5.75 m / min Cumulative light intensity per pass: 360 mJ / cm ２ (UV-A) Atmosphere: Nitrogen Number of passes: 10

[0167] <Contact Angle Measurement> The contact angle of the hardened film prepared on the SPCC-SD steel sheet as described above was evaluated with respect to pure water or oleic acid at 23°C using DMo-502 manufactured by Kyowa Interface Science Co., Ltd.

[0168] <Measurement of Friction Coefficient> The hardened film prepared on the SPCC-SD steel plate as described above was evaluated at 23°C using a Shinto Kagaku Tripogear TYPE:14FW in accordance with ISO 8295:1995(E). A dust-free cloth indenter (Asahi Kasei Corporation's Bencot M-3 II) was used, with a load of 200g and a speed of 100mm / min. The average values ​​of three measurements taken at a distance of 3cm were used as the static and dynamic friction coefficients.

[0169] <Pencil Hardness Evaluation> The hardened film prepared on the SPCC-SD steel plate or TAC film as described above was tested in accordance with JIS K5600-5-4 (extending pencil hardness up to 10H). Scratch tests were performed three times for each hardness pencil, and the highest value for the pencil type in which no defects occurred in the hardened film was defined as the pencil hardness.

[0170] <Visual Evaluation> The hardened film prepared on the SPCC-SD steel sheet as described above was visually observed and evaluated for its surface appearance.

[0171] The evaluation results are summarized in Table 2.

[0172]

[0173] As shown in Table 2, the curable compositions of Examples 1 to 8, compared to Comparative Examples 1 to 3, were fluorine-free, yet the resulting cured products exhibited superior water repellency, oil repellency, and slipperiness, as well as high hardness. Furthermore, the curable compositions of Examples 1, 2, and 4 to 8 also exhibited superior appearance in the resulting cured products. Depending on the application, a composition with a more suitable appearance can be arbitrarily selected.

[0174] The disclosure of Japanese Patent Application No. 2025-50666, filed on 25 March 2025, 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 were specifically and individually noted to be incorporated by reference.

Claims

1. A curable composition containing an organopolysiloxane represented by the average composition formula of the following formula (1) in an amount of 0.1% by mass or more and less than 20% by mass, based on the total solid content of the curable composition. In formula (1), R １ Each of these independently represents 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, or a monovalent organic group having a polymerizable group, R １ At least one of them is a monovalent organic group having a polymerizable group, R １ 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 hydroxyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, and an oxy group, ２ and R ３ Each of these independently represents 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, or a monovalent organic group having a polymerizable group, R ２ and R ３ The alkyl group, aralkyl group, aryl group, and monovalent organic group having polymerizable groups in the above may be substituted with a structure selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, and an oxy group, where b and c represent positive numbers, a and d each represent 0 or a positive number, and the mixture contains a component with a structure represented by the following formula (S). In equation (S), n represents an integer greater than or equal to 14.

2. The curable composition according to claim 1, wherein the water contact angle on the surface of the cured product of the curable composition is 100° or more.

3. The curable composition according to claim 1, wherein the static friction coefficient and the dynamic friction coefficient on the surface of the cured product of the curable composition with respect to a dust-free cloth are both 0.2 or less.

4. The curable composition according to claim 1, further comprising an organopolysiloxane represented by an average composition formula of the following formula (2). In formula (2), R ４ , R ５ and R ６ each independently represent 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, or a monovalent organic group having a polymerizable group, and R ４ , R ５ and R ６ at least one of which is a monovalent organic group having a polymerizable group, and R ４ , R ５ and R ６ wherein the alkyl group, the aralkyl group, the aryl group, and the monovalent organic group having a polymerizable group may each 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.

5. The curable composition according to claim 1, further comprising a filler.

6. R in formula (1) １ The curable composition according to claim 1, wherein the polymerizable group in 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.

7. The curable composition according to claim 1, wherein the organopolysiloxane represented by formula (1) is obtained by the reaction of a silicon compound containing at least three hydrolyzable groups and / or hydroxyl groups represented by the following formula (3) and a silicone represented by the following formula (4). １ -Six ３ (3) In formula (3), R １ Each of these independently represents 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, or a monovalent organic group having a polymerizable group, R １ At least one of them is a monovalent organic group having a polymerizable group, R １ The alkyl group, the aralkyl group, the aryl group, and the monovalent organic group having a polymerizable group in the above may be substituted with a structure selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, and an oxy group, where X represents a hydrolyzable group and / or a hydroxyl group. In formula (4), R ２ Each of these independently represents 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, or a monovalent organic group having a polymerizable group, R ２ and R ３ The alkyl group, aralkyl group, aryl group, and monovalent organic group having a polymerizable group in formula (4) may be substituted with a structure selected from the group consisting of a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, and an oxy group, and A and B each independently represent a hydrolyzable group, a hydroxyl group, 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, or a monovalent organic group having a polymerizable group, and at least one of A and B is a hydrolyzable group or a hydroxyl group, m represents a positive integer, and the number-average molecular weight of the silicone represented by formula (4) is 1,100 or more and 150,000 or less.

8. The curable composition according to claim 1, further comprising a polymerization initiator.

9. The curable composition according to claim 1, wherein the pencil hardness of the cured product of the curable composition formed on an SPCC-SD steel sheet is 6H or higher.

10. A cured product obtained by curing the curable composition according to any one of claims 1 to 9.

11. A hard coat agent comprising the curable composition according to any one of claims 1 to 9.

12. A hard coat obtained by curing the hard coat agent described in claim 11.

13. An article having the hard coat described in claim 12.

14. A laminate having the hard coat described in claim 13 and a substrate.

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