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

Abstract

A curable composition, a cured product obtained by curing the curable composition, a hard coat agent using the curable composition, a hard coat layer, an article, and a laminate, the curable composition comprising a polysiloxane represented by formula (1), the content of the polysiloxane being less than or equal to 10% relative to the total solid content of the curable composition, and the content of the cured product being less than or equal to 10% relative to the total solid content of the curable composition. The content of the curable composition is at least 0.1 mass% and less than 10 mass%. In the formula, at least one of R1 is a monovalent organic group having a polymerizable group, R2 independently represents a C1-20 hydrocarbon group substituted by a fluorine atom, w represents a positive number, v, x, y and z independently represent 0 or a positive number, at least one of x and y represents a positive number, when x is 0, a structure represented by formula (S) is contained, and n represents a number of 3 or more.

Description

Technical Field

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

[0002] The displays of various devices that display images are provided with a transparent coating that is highly scratch-resistant and has excellent hardness as a surface protective layer. To prevent decreased visibility associated with contamination of the display surface, the coating preferably has anti-fouling properties. This is especially important for displays with touch panel functionality, where it is desirable to prevent sebum adhesion and to allow for easy removal. Therefore, leveling agents, which are substances with low surface free energy, are added to the coatings on the surfaces of many displays to improve surface smoothness and impart stain resistance. Fluoropolymer resins and silicone resins have been used as leveling agents in the past.

[0003] However, these leveling agents are not chemically fixed with the resin used as the substrate, resulting in issues such as exudation, peeling due to repeated use, or loss of function. To address this issue, leveling agents with polymerizable functional groups and fluorinated alkyl or silicon chains are used. As conventional leveling agents, the leveling agents described in Patent Documents 1-4 can be cited as examples.

[0004] Patent Document 1 discloses a hard coating forming composition that contains a nonionic fluorinated compound as a leveling agent in a polymerizable epoxy-based polyorganosilsesquioxane.

[0005] Patent Document 2 discloses a leveling agent that is polymerized from a monomer having two or more groups with free radical polymerizability double bonds and containing at least one nitrogen atom, and having fluorine atoms; and discloses a composition comprising the leveling agent and a polyorganosilsesquioxane.

[0006] Patent document 3 discloses a hard coating composition comprising: a polymer having at least one of a silicon group and a perfluoropolyether group and a reactive group in its side chain as a leveling agent; and a polyorganosilsesquioxane having polymerizable groups.

[0007] Patent document 4 discloses a hard coating forming composition comprising a polysilsesquioxane having a perfluoropolyether group. Existing technical documents Patent documents

[0008] Patent Document 1: International Publication No. 2021 / 193173 Patent Document 2: International Publication No. 2019 / 235108 Patent Document 3: International Publication No. 2020 / 059726 Patent Document 4: International Publication No. 2021 / 193478 Summary of the Invention The problem that the invention aims to solve

[0009] Especially in displays that come into direct contact with the user, such as touch panels, from the perspective of physical strength and durability, In addition to high antifouling properties, leveling agents that are unevenly distributed on the coating surface are expected to have excellent hardness and weather resistance.

[0010] Patent Document 1 discloses a hard coating composition in which a nonionic fluorinated compound is added as a leveling agent to a polyorganosilsesquioxane with polymerizable epoxy groups. However, in the hard coating formed by curing the composition, there is no covalent bond between the silsesquioxane as the main agent and the leveling agent, which leads to a decrease in performance due to the seepage of the leveling agent.

[0011] Patent Document 2 discloses a leveling agent that is polymerized from a monomer having two or more groups with free radical polymerizable double bonds and containing at least one nitrogen atom, and also contains fluorine atoms. However, in the hard coating formed by curing the composition, there is no covalent bond between the silsesquioxane as the main agent and the leveling agent, which leads to a decrease in performance due to the exudation of the leveling agent. Furthermore, since the leveling agent molecule contains nitrogen atoms, according to the viewpoint of hydrolysis of the hard coating obtained by curing the composition, long-term use may lead to further deterioration.

[0012] Patent document 3 discloses a hard coating composition in which a leveling agent having polymerizable functional groups and silicon or perfluoropolyether is added to a polysilsesquioxane derivative. However, the leveling agent has a low crosslinking density, which may reduce the hardness of the coating surface.

[0013] Patent document 4 discloses a composition for forming a hard coating. This composition for forming a hard coating contains a polysilsesquioxane having a perfluoropolyether group, but fails to simultaneously achieve surface hardness and a low coefficient of dynamic friction (i.e., high surface smoothness).

[0014] This disclosure is made in view of the above-mentioned problems, and its object is to provide a curable composition that yields a cured product with excellent durability and excellent inhibition of indentation elastic modulus reduction, as well as a cured product obtained by curing the curable composition, a hard coating comprising the curable composition, a hard coating obtained by curing the hard coating, an article having the hard coating, and a laminate. Technical means for solving the problem

[0015] The technical means used to solve the problem include the following solutions. <1> A curable composition comprising a polysiloxane represented by formula (1), wherein the polysiloxane content is 0.1% by mass or more and less than 10% by mass relative to the total solids content of the curable composition, and x / (v + w + x + y + z) is less than 0.6.

[0016] [Chemical Formula 1]

[0017] In equation (1), R 1 Each of the following groups independently represents at least one group selected from the group consisting of alkyl groups having 1-10 carbon atoms, aralkyl groups having 7-10 carbon atoms, aryl groups having 6-10 carbon atoms, and monovalent organic groups having polymerizable groups, R 1 At least one of them is a monovalent organic group with a polymerizable group, R 1 The alkyl group, the aralkyl group, the aryl group, and the monovalent organic group having a polymerizable group can be substituted by structures selected from the group consisting of halogen atoms, hydroxyl groups, alkoxy groups, aryloxy groups, arylalkoxy groups, and oxygen groups, R 2 R represents, independently, a hydrocarbon group consisting of 1-20 carbon atoms substituted by a fluorine atom. 3 R 4 and R 5 Each of the following groups independently represents at least one group selected from the group consisting of alkyl groups having 1-10 carbon atoms, aralkyl groups having 7-10 carbon atoms, aryl groups having 6-10 carbon atoms, and monovalent organic groups having polymerizable groups, R 3 R 4 and R 5 The alkyl, aralkyl, aryl, and monovalent organic groups having polymerizable groups can be substituted by structures selected from the group consisting of halogen atoms, hydroxyl groups, alkoxy groups, aryloxy groups, arylalkoxy groups, and oxygen groups. w represents a positive number, and v, x, y, and z independently represent 0 or positive numbers, with at least one of x and y representing a positive number. When x is 0, the structure contains the structure represented by the following formula (S).

[0018] [Chemical Formula 2]

[0019] n represents a number greater than or equal to 3.

[0020] <2> according to <1> The curable composition, in addition to containing the polysiloxane represented by the formula (1), also contains the polysiloxane represented by the formula (2).

[0021] [Chemical Formula 3]

[0022] In equation (2), R 6 R 7 and R 8 Each of the following groups independently represents at least one group selected from the group consisting of alkyl groups having 1-10 carbon atoms, aralkyl groups having 7-10 carbon atoms, aryl groups having 6-10 carbon atoms, and monovalent organic groups having polymerizable groups, R 6 R 7 and R 8 At least one of them is a monovalent organic group with a polymerizable group, R 6 R 7 and R 8 The alkyl, aralkyl, aryl, and monovalent organic groups having polymerizable groups can be substituted by structures selected from the group consisting of halogen atoms, hydroxyl groups, alkoxy groups, aryloxy groups, arylalkoxy groups, and oxy groups, where q represents a positive number, and p, r, and s independently represent 0 or a positive number, respectively.

[0023] <3> according to <1> or <2> The curable composition, wherein R in formula (1) 1 The polymerizable group is selected from at least one of the group consisting of acryloyl, methacryloyl, epoxy, oxetyl, vinyl, and allyl. <4> according to <1> - <3> The curable composition according to any one of the formulas, wherein the value of (x + y) / (v + w + x + y + z) in the formula (1) is 0.20-0.80. <5> according to <1> - <4> The curable composition described in any one of the above, further comprising a polymerization initiator. <6> A solidified substance, which is to make <1> - <5> It is formed by curing any of the curable compositions described in the above. <7> A hard coating comprising <1> - <5> The curable composition described in any one of the above. <8> A hard coating, which is to make <7> It is formed by curing the aforementioned hard coating agent. <9> An item that possesses <8> The aforementioned hard coating. <10> A layered body having <9> The aforementioned hard coating and substrate. <11> according to <6> The cured material, wherein the cured material obtained on the steel plate has a pencil hardness of 5H or higher and a coefficient of dynamic friction of 0.35 or lower. <12> according to <6> or <11> The solidified material, wherein the decrease rate of the water contact angle before and after the wear test using acetone-impregnated degreased cotton, the wear test using hexane-impregnated degreased cotton, and the wear test using steel wool is all less than 10%. Invention Effects

[0024] According to this disclosure, a curable composition that produces a cured product with excellent durability and excellent inhibition of the decrease in indentation elastic modulus of the cured product, a cured product obtained by curing the curable composition, a hard coating comprising the curable composition and a hard coating obtained by curing the hard coating, an article having the hard coating, and a laminate are provided. Detailed Implementation

[0025] The following describes specific embodiments of this disclosure in detail. However, this disclosure is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps) are not essential unless specifically stated otherwise. The same applies to numerical values ​​and their ranges, which do not limit this disclosure. The numerical range indicated by "-" in this specification includes the values ​​before and after "-", which are respectively the minimum and maximum values. In this specification, the numerical ranges described in a stepwise manner, where the upper or lower limit of one numerical range can be replaced with the upper or lower limit of other numerical ranges described in a stepwise manner. Furthermore, the upper or lower limit of a numerical range described in this specification can be replaced with the values ​​shown in the embodiments. In this specification, total solids content refers to the total mass of the components after removing the solvent from the total components of the composition. Furthermore, in this specification, a combination of two or more preferred solutions is a more preferred solution.

[0026] In this specification, R in formula (1) or formula (2) 1 -R 8 It can be independently replaced by substituents or halogen atoms, partially replacing its structure. For example, R 1 -R 8It can be independently replaced by alkyl, aryl, aralkyl, vinyl, epoxy, oxetyl, hydroxyl, amino, alkylamino, arylamino, aralkylamino, ammonium, thiol, isocyanurate, urea, isocyanate, carboxyl, anhydride, or halogen atom. R in equation (1) or equation (2) 1 -R 8 They can be considered as unsubstituted independently.

[0027] [Curing composition] The curable composition disclosed herein comprises a polysiloxane represented by formula (1), wherein the content of the polysiloxane is 0.1% by mass or more and less than 10% by mass relative to the total solids content of the curable composition, and x / (v + w + x + y + z) is less than 0.6.

[0028] [Chemical Formula 4]

[0029] In equation (1), R 1 Each of the following groups independently represents at least one group selected from the group consisting of alkyl groups having 1-10 carbon atoms, aralkyl groups having 7-10 carbon atoms, aryl groups having 6-10 carbon atoms, and monovalent organic groups having polymerizable groups, R 1 At least one of them is a monovalent organic group with a polymerizable group, R 1 The alkyl group, the aralkyl group, the aryl group, and the monovalent organic group having a polymerizable group can be substituted by structures selected from the group consisting of halogen atoms, hydroxyl groups, alkoxy groups, aryloxy groups, arylalkoxy groups, and oxygen groups, R 2 R represents, independently, a hydrocarbon group consisting of 1-20 carbon atoms substituted by a fluorine atom. 3 R 4 and R 5 Each of the following groups independently represents at least one group selected from the group consisting of alkyl groups having 1-10 carbon atoms, aralkyl groups having 7-10 carbon atoms, aryl groups having 6-10 carbon atoms, and monovalent organic groups having polymerizable groups, R 3 R 4 and R 5 The alkyl, aralkyl, aryl, and monovalent organic groups having polymerizable groups can be substituted by structures selected from the group consisting of halogen atoms, hydroxyl groups, alkoxy groups, aryloxy groups, arylalkoxy groups, and oxygen groups. w represents a positive number, and v, x, y, and z independently represent 0 or positive numbers, with at least one of x and y representing a positive number. When x is 0, the structure contains the structure represented by the following formula (S).

[0030] [Chemical Formula 5]

[0031] n represents a number greater than or equal to 3.

[0032] As mentioned above, the durability of the cured products obtained from conventional curing compositions is insufficient. The inventors have conducted in-depth research and discovered that by employing the aforementioned structure, it is possible to provide a curable composition with excellent durability of the resulting cured film. The curable composition contains 0.1% by mass and less than 10% by mass of a polysiloxane relative to the total solids content. The polysiloxane has a hydrocarbon group with 1-20 carbon atoms substituted by fluorine atoms and / or a silicon chain, and has a sesquioxane structure containing polymerizable groups, thereby enabling the formation of a suitable crosslinked structure after curing. In addition, the polysiloxane represented by formula (1) is unevenly distributed on the surface, thereby enabling the formation of a cured product with excellent solvent resistance and abrasion resistance. It is speculated that this will enable the formation of a cured product with excellent durability. Furthermore, by using the polysiloxane represented by formula (1), the decrease in the indentation elastic modulus of the obtained cured product is suppressed compared with conventional leveling agents.

[0033] Furthermore, the cured composition disclosed herein exhibits excellent hardness, surface smoothness, hydrophobicity, and antifouling properties.

[0034] The curable compositions disclosed herein preferably further comprise a polysiloxane represented by formula (2) described later. In addition, the curable composition disclosed herein preferably further comprises a polymerization initiator described later. The curable compositions disclosed herein may also contain various other components (hereinafter referred to as "other components") as needed. The curable compositions disclosed herein can be suitably used as hard coatings.

[0035] <Polysiloxane represented by formula (1)> The curable compositions disclosed herein comprise polysiloxanes represented by formula (1). Each constituent unit in the polysiloxane represented by formula (1) is referred to as constituent unit (a)-(e) as follows.

[0036] [Chemical Formula 6]

[0037] In the polysiloxane represented by equation (1), w represents a positive number, and v, x, y and z independently represent 0 or a positive number, with at least one of x and y being a positive number. That is, the polysiloxane represented by equation (1) may include at least one of the constituent units (b), (c) and (d) in the constituent units (a)-(e) above, and may include at least one of the constituent units (a) and (e) as needed. In addition, since the polysiloxane represented by formula (1) contains at least the constituent unit (b), there are cases where it is not called polysiloxane but sesquisiloxane.

[0038] In Equation (1), v, w, x, y, and z represent the molar ratio of constituent units (a)-(e). Furthermore, in Equation (1), v, w, x, y, and z represent the relative molar ratios of constituent units (a)-(e) that may be contained in the polysiloxane represented by Equation (1). The molar ratio can be determined, for example, from the NMR (nuclear magnetic resonance) analysis value of the polysiloxane represented by Equation (1). Additionally, when the reaction rates of each raw material of the polysiloxane represented by Equation (1) are known, or when the yield is 100%, it can be determined from the amount of that raw material input. For example, the molar ratio of each constituent unit of the polysiloxane represented by formula (1) can be calculated as follows: A sample dissolved in deuterated chloroform, etc., is subjected to... 1 H-NMR analysis, and further analysis as needed. 29 Si-NMR analysis. The original structure of the polysiloxane represented by equation (1) can be inferred from the ratio of the constituent units by decomposing it into constituent units using alkalis, etc. Alternatively, known methods such as mass spectrometry and IR (infrared absorption spectroscopy) analysis can be combined as needed to determine the molar ratio of each constituent unit of polysiloxane represented by equation (1).

[0039] Regarding each of the constituent units (b)-(e) in formula (1), there may be only one type or more types. Furthermore, the arrangement order of the constituent units in formula (1) indicates the composition of the constituent units, but does not mean that the condensation mode of the constituent units in the polysiloxane represented by formula (1) is limited to this arrangement order. Therefore, in the curable composition disclosed herein, the condensation mode of the constituent units in the polysiloxane represented by formula (1) does not necessarily have to be the same as the arrangement order in formula (1). The following describes the details of the constituent units (a)-(e).

[0040] (Constructing Unit (a)) The constituent unit (a) has four oxygen atoms relative to one silicon atom. 1 / 2The Q unit (consisting of two oxygen atoms). Furthermore, the Q unit refers to a unit with four oxygen atoms compared to one silicon atom. 1 / 2 The unit.

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

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

[0043] (Constructing Unit (b)) The constituent unit (b) has 3 (or 1.5 as oxygen atoms) O atoms relative to 1 silicon atom. 1 / 2 R 1 T-units are bonded to silicon atoms. Furthermore, a T-unit refers to a unit with three oxygen atoms relative to one silicon atom. 1 / 2 The unit.

[0044] In constituent unit (b), R 1 Each of the following groups independently represents at least one group selected from the group consisting of alkyl groups with 1-10 carbon atoms, aralkyl groups with 7-10 carbon atoms, aryl groups with 6-10 carbon atoms, and monovalent organic groups having polymerizable groups, R 1 At least one of them is a monovalent organic group with a polymerizable group, R 1 The alkyl, aralkyl, aryl, and monovalent organic groups having polymerizable groups may be substituted by structures selected from the group consisting of halogen atoms, hydroxyl groups, alkoxy groups, aryloxy groups, arylalkoxy groups, and oxy groups.

[0045] Alkyl groups with 1-10 carbon atoms can be either straight-chain or branched. Examples of alkyl groups having 1-10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. From the viewpoint of heat resistance and the hardness of the cured product, methyl or ethyl is preferred, and methyl is more preferred.

[0046] Examples of aryl groups with 6-10 carbon atoms include phenyl, groups in which one or more hydrogen atoms of a phenyl group are replaced by alkyl groups with 1-4 carbon atoms, and naphthyl groups. Phenyl is preferred from the viewpoint of heat resistance and the hardness of the cured product.

[0047] Aryl groups having 7-10 carbon atoms include, for example, alkyl groups having 1-4 carbon atoms in which one hydrogen atom is replaced by an aryl group such as a phenyl group. Examples include benzyl and phenethyl groups, and benzyl is preferred from the viewpoint of heat resistance and the hardness of the cured product.

[0048] Examples of polymerizable monovalent organic groups include vinyl unsaturated groups, alkynyl groups, and cyclic ether groups. Furthermore, based on the viewpoints of reactivity and hardness, R 1 The polymerizable group is preferably at least one selected from the group consisting of acryloyl, methacryloyl, epoxy, oxetyl, vinyl, and allyl, more preferably at least one selected from the group consisting of acryloyl, methacryloyl, and oxetyl, and particularly preferably at least one selected from the group consisting of acryloyl and methacryloyl. As a monovalent organic group with polymerizable groups, it is preferably a monovalent organic group with 2-12 carbon atoms having an ethylene unsaturated group, an alkynyl group or a cyclic ether group, more preferably a monovalent organic group with 2-12 carbon atoms having an ethylene unsaturated group or a cyclic ether group, and particularly preferably a monovalent organic group with 2-12 carbon atoms having an ethylene unsaturated group.

[0049] Examples of vinyl unsaturated groups include vinyl, allyl, styryl, (meth)acryloyloxy, and (meth)acrylamido. Among these, vinyl or (meth)acryloyloxy is preferred from the viewpoint of curability. Examples of organic groups having 2-12 carbon atoms and an vinyl unsaturated group include, for example, vinyl, o-styrene, m-styrene, p-styrene, acryloyloxymethyl, methacryloyloxymethyl, 2-acryloyloxyethyl, 2-methacryloyloxyethyl, 3-acryloyloxypropyl, 3-methacryloyloxypropyl, 8-acryloyloxyoctyl, 8-methacryloyloxyoctyl, 1-propenyl, 2-propenyl (allyl), 1-methylvinyl, 1-butenyl, 3-butenyl, 1-pentenyl, 4-pentenyl, 3-methyl-1-butenyl, 1-phenylvinyl, 2-phenylvinyl, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 3-butynyl, 1-pentynyl, 4-pentynyl, 3-methyl-1-butynyl, and phenylbutynyl. From the viewpoint of curability, alkyl, vinyl, or allyl groups having (meth)acryloyloxy groups are preferred, 3-(meth)acryloyloxypropyl, vinyl, or allyl groups are more preferred, and 3-(meth)acryloyloxypropyl groups are particularly preferred.

[0050] Examples of cyclic ether groups include epoxy group and oxetyl group. Among them, oxetyl group is preferred from the viewpoint of reactivity and storage stability. Examples of organic groups having 2-12 carbon atoms and a cyclic ether group include, for example, 3-(3-ethyl-3-oxecyclobutylmethoxy)propyl.

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

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

[0053] (Constructing Unit (c)) The constituent unit (c) has 3 O atoms (1.5 as oxygen atoms) relative to 1 silicon atom. 1 / 2 R 2 T-units bonded to silicon atoms.

[0054] In the constituent unit (c), R 2 Each of the 1 to 20 hydrocarbon groups, which are replaced by fluorine atoms, represents a hydrocarbon group. R 2 There is no particular limitation on the number of fluorine atoms present, and one or more is sufficient. However, from the viewpoints of surface smoothness, durability, hydrophobicity, and antifouling properties, it is preferable to have three or more fluorine atoms, and more preferably five or more. Furthermore, based on the considerations of durability, hydrophobicity, antifouling properties, and the transparency of the cured film obtained by curing the resulting polysiloxane and curable composition, fluorine atoms R... 2 The fluorine atom content is preferably 3-50, more preferably 5-40, even more preferably 7-30, and particularly preferably 9-21. Additionally, R 2 There is no particular limitation on the number of carbon atoms, and it is acceptable to have one or more. From the viewpoints of durability, hydrophobicity and antifouling, it is preferable to have a fluoroalkyl hydrocarbon group with two or more carbon atoms, and more preferably a fluoroalkyl hydrocarbon group with four or more carbon atoms. Furthermore, based on the viewpoints of durability, hydrophobicity, antifouling properties, and the transparency of the cured film obtained by curing the resulting polysiloxane and curable composition, R 2 Preferably, it is a fluoroalkyl group with 2-30 carbon atoms, more preferably a fluoroalkyl group with 4-20 carbon atoms, even more preferably a fluoroalkyl group with 5-16 carbon atoms, and particularly preferably a fluoroalkyl group with 6-12 carbon atoms. Furthermore, based on the viewpoint of availability, R 2 Preferably, it is a group formed by the bonding of alkylene and fluoroalkyl groups. The alkylene group is preferably composed of 1-10 carbon atoms, more preferably 2-4 carbon atoms, and particularly preferably ethylene.

[0055] The molar ratio (x / (v + w + x + y + z)) of the polysiloxane represented by formula (1) to the total number of constituent units (c) is less than 0.6. From the viewpoints of durability, hydrophobicity, antifouling, hardness and surface smoothness, it is preferably 0.05 or more and less than 0.6, more preferably 0.10-0.55, even more preferably 0.20-0.50, and particularly preferably 0.25-0.45. The molar ratio of constituent unit (c) to all constituent units can also be 0, but in this case, y is a positive number, that is, the molar ratio of constituent unit (d) is a number greater than 0.

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

[0057] (Constructing unit (d)) The constituent unit (d) has two O atoms relative to one silicon atom (one as an oxygen atom). 1 / 2 2 R 3 D-units are bondsed to silicon atoms. Furthermore, a D-unit refers to a unit with two oxygen atoms relative to one silicon atom. 1 / 2 The unit.

[0058] In the constituent unit (d), R 3 Each of the following groups independently represents at least one group selected from the group consisting of alkyl groups having 1-10 carbon atoms, aralkyl groups having 7-10 carbon atoms, aryl groups having 6-10 carbon atoms, and monovalent organic groups having polymerizable groups, R 3 The alkyl, aralkyl, aryl, and monovalent organic groups having polymerizable groups mentioned herein may be substituted by structures selected from the group consisting of halogen atoms, hydroxyl groups, alkoxy groups, aryloxy groups, arylalkoxy groups, and oxygen groups. R 3 Preferably, each group is independently selected from at least one group selected from the group consisting of alkyl with 1-10 carbon atoms, aralkyl with 7-10 carbon atoms, and aryl with 6-10 carbon atoms; more preferably, it is an alkyl or phenyl group with 1-10 carbon atoms; even more preferably, it is methyl or phenyl; and particularly preferably, it is methyl. R 3 Preferred schemes and R include alkyl groups with 1-10 carbon atoms, aralkyl groups with 7-10 carbon atoms, aryl groups with 6-10 carbon atoms, and monovalent organic groups having polymerizable groups. 1 The preferred embodiments of alkyl groups with 1-10 carbon atoms, aralkyl groups with 7-10 carbon atoms, aryl groups with 6-10 carbon atoms, and monovalent organic groups having polymerizable groups are the same. Furthermore, in equation (1), when x is 0, based on the viewpoints of surface smoothness, durability, hydrophobicity, and stain resistance, the constituent unit (d) must have at least the structure represented by the following equation (S).

[0059] [Chemical Formula 7]

[0060] n represents a number greater than or equal to 3.

[0061] Furthermore, in the polysiloxane represented by formula (1), when x is 0, from the viewpoints of surface smoothness, durability, hydrophobicity, and antifouling properties, it contains the structure represented by formula (S). The structure represented by formula (S) is a so-called silicon chain structure, which is a silicon chain structure formed by connecting 3 or more constituent units (d) to each other. There is no particular limitation on n, as long as it is 3 or more. In addition, from the viewpoint of availability and the transparency of the cured film obtained by curing the obtained polysiloxane or curable composition, n is preferably 300 or less, more preferably 200 or less, and even more preferably 100 or less. In the structure represented by formula (S), n can be a single value or a mixture of multiple values. When n is present in a mixture, the average value N of n is preferably 3 or more, and from the viewpoint of the durability, hardness, and surface smoothness of the cured product, it is preferably 4 or more, more preferably 5-50, and particularly preferably 6-30. Furthermore, N can be calculated, for example, based on the average molecular weight of silicon used as a raw material when manufacturing the silsesquioxane derivative represented by formula (1) described later, and can include structures with n of 3 or more in the structure represented by formula (S), as well as structures with n of 1 or 2.

[0062] The proportion of the constituent unit (d) in the polysiloxane represented by formula (1) is not particularly limited. For example, when x > 0, from the viewpoints of durability, hydrophobicity, antifouling, hardness and surface smoothness, the molar ratio (y / (v + w + x + y + z)) of the constituent unit (d) of all constituent units is preferably 0-0.80, more preferably 0-0.70, further preferably 0-0.55, and particularly preferably 0-0.50.

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

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

[0065] From the viewpoints of durability, hydrophobicity, antifouling, hardness, and surface smoothness, the total molar ratio of constituent unit (c) and constituent unit (d) of all constituent units ((x + y) / (v + w + x + y + z)) is preferably 0.10-0.80, more preferably 0.15-0.70, and particularly preferably 0.20-0.50.

[0066] From the viewpoints of durability, hydrophobicity, antifouling, hardness and surface smoothness, the total mass ratio of the constituent unit (c) and constituent unit (d) to the total mass of the polysiloxane represented by formula (1) is preferably 5%-80% by mass, more preferably 10%-70% by mass, and particularly preferably 15%-65% by mass.

[0067] From the viewpoints of durability, hydrophobicity, antifouling, hardness, and surface smoothness, the total molar ratio ((w + x + y) / (v + w + x + y + z)) of all constituent units (b), (c), and (d)) is preferably 0.3-1, more preferably 0.5-1, further preferably 0.7-1, and particularly preferably 0.9-1.

[0068] From the viewpoints of durability, hydrophobicity, antifouling, hardness and surface smoothness, the total mass ratio of constituent unit (b), constituent unit (c) and constituent unit (d) of all constituent units relative to the total mass of polysiloxane represented by formula (1) is preferably 30%-100% by mass, more preferably 50%-100% by mass, further preferably 70%-100% by mass, and particularly preferably 90%-100% by mass.

[0069] (Constructing unit (e)) The constituent unit (e) has one O atom relative to one silicon atom (0.5 O atoms as oxygen atoms). 1 / 2 1 R 6 And 2 Rs 5 The M-unit is bonded to a silicon atom. Furthermore, the M-unit refers to a unit with one oxygen atom relative to one silicon atom. 1 / 2 The unit.

[0070] In the constituent unit (e), R 4 and R 5 Each of the following groups independently represents at least one group selected from the group consisting of alkyl groups having 1-10 carbon atoms, aralkyl groups having 7-10 carbon atoms, aryl groups having 6-10 carbon atoms, and monovalent organic groups having polymerizable groups, R 4 and R 5 The alkyl, aralkyl, aryl, and monovalent organic groups having polymerizable groups may be substituted by structures selected from the group consisting of halogen atoms, hydroxyl groups, alkoxy groups, aryloxy groups, arylalkoxy groups, and oxy groups. R 4 Preferably, it is at least one group selected independently from the group consisting of alkyl with 1-10 carbon atoms, aralkyl with 7-10 carbon atoms and aryl with 6-10 carbon atoms, more preferably alkyl or phenyl with 1-10 carbon atoms, further preferably methyl or phenyl, and particularly preferably methyl. R 5 More preferably, it is an organic group having 2 to 12 carbon atoms, which is an alkyl, phenyl, or vinyl unsaturated group having 1 to 10 carbon atoms, and even more preferably methyl, phenyl, or vinyl, particularly preferably methyl or vinyl. Furthermore, based on the viewpoints of reactivity and hardness, R 5 The polymerizable group is preferably at least one selected from the group consisting of vinyl, acryloyl, methacryloyl, epoxy and oxetyl, more preferably at least one selected from the group consisting of vinyl, acryloyl, methacryloyl and oxetyl, and particularly preferably vinyl. R 4 and R 5 In addition to the above, preferred embodiments of alkyl groups with 1-10 carbon atoms, aralkyl groups with 7-10 carbon atoms, aryl groups with 6-10 carbon atoms, and monovalent organic groups having polymerizable groups, are those related to R. 1 The preferred embodiments of alkyl groups with 1-10 carbon atoms, aralkyl groups with 7-10 carbon atoms, aryl groups with 6-10 carbon atoms, and monovalent organic groups having polymerizable groups are the same.

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

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

[0073] (Other constituent units (f)) The polysiloxane represented by formula (1) can also be used as a constituent unit that does not contain Si, and also contains (R 9 O 1 / 2 (Hereinafter also referred to as constituent unit (f)). Here, R 9 It is a hydrogen atom or an alkyl group having 1-6 carbon atoms. The alkyl group having 1-6 carbon atoms can be either an aliphatic group or an alicyclic group, and can also be either straight-chain or branched. Specific examples of alkyl groups having 1-6 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, and hexyl.

[0074] The constituent unit (f) can be an alkoxy group contained in the silicon compound as a hydrolyzable group or an alkoxy group generated by replacing the ethanol contained in the reaction solvent with a hydrolyzable group of the silicon compound, or it can be a group that does not hydrolyze or condense and remains in the molecule, or it can be a hydroxyl group that does not condense and remains in the molecule after hydrolysis.

[0075] The proportion of the constituent unit (f) in the polysiloxane represented by formula (1) is not particularly limited. For example, from the viewpoint of viscosity and hardness when formed into a cured product, the molar ratio of the constituent unit (f) to all constituent units is preferably 0.15 or less, more preferably 0.1 or less, even more preferably 0.05 or less, and may also be 0. Alternatively, it may be 0.01 or more.

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

[0077] (The weight-average molecular weight of polysiloxane represented by formula (1)) The weight-average molecular weight (hereinafter also referred to as "Mw") of the polysiloxane represented by formula (1) is not particularly limited, but is preferably 300-30000, more preferably 500-20000, further preferably 800-15000, and particularly preferably 1000-10000, from the viewpoints of durability, hydrophobicity, antifouling properties, hardness and surface smoothness. The number-average molecular weight (hereinafter also referred to as "Mn") of the polysiloxane represented by formula (1) is not particularly limited, but is preferably 300-30000, more preferably 400-20000, even more preferably 500-15000, and particularly preferably 800-10000, from the viewpoints of durability, hydrophobicity, antifouling properties, hardness and surface smoothness. Furthermore, in this disclosure, Mw and Mn refer to values ​​obtained by converting the molecular weight determined by GPC (gel permeation chromatography) using polystyrene as a standard substance. For example, the determination conditions described in the examples below can be used as the conditions for determining Mw.

[0078] (The content of polysiloxane represented by formula (1)) The curable composition disclosed herein comprises a polysiloxane represented by the formula (1), wherein the content of the polysiloxane is 0.1% by mass or more and less than 10% by mass relative to the total solids content of the curable composition. From the viewpoints of durability, hydrophobicity, antifouling properties, hardness, and surface smoothness, the content of polysiloxane represented by formula (1) is preferably 0.1%-8% by mass, more preferably 0.2%-6% by mass, and particularly preferably 0.5%-5% by mass, relative to the total solids content of the curable composition.

[0079] (The manufacturing method of polysiloxane represented by formula (1)) The polysiloxane represented by formula (1) can be manufactured by known methods. Methods for manufacturing polysiloxanes are disclosed in detail in International Patent Application Publication No. 2013 / 031798, Japanese Patent Application Publication No. 2000-044689, etc.

[0080] The method for manufacturing the polysiloxane represented by formula (1) preferably includes the following steps (hereinafter also referred to as the "hydrolysis step"): Regarding R m SiX k (m represents an integer from 0 to 3, k represents an integer from 1 to 4, m + k = 4, R represents a group in the polysiloxane represented by formula (1) that is bonded to silicon atoms via carbon atoms, and X represents a hydrolyzable group.) At least one organosilicon compound represented by the formula (1) is hydrolyzed using an organic solvent by adding water in an amount of 0.2 molar equivalents to 30 molar equivalents relative to the total amount of hydrolyzable groups present in the organosilicon compound. As R, suitable examples include groups (R1) that are bonded to silicon atoms via carbon atoms in polysiloxanes represented by formula (1). 1 -R 5 wait). Regarding X, alkoxy, siloxy, or halogen atom, more appropriately, alkoxy or siloxy.

[0081] In the hydrolysis process, it is preferable to not only hydrolyze the organosilicon compound, but also to perform hydrolysis and polycondensation reactions of the organosilicon compound and other silicon compounds as needed. Alternatively, in the hydrolysis process, after obtaining the intermediate product polysiloxane by hydrolysis and polycondensation of the organosilicon compound and other silicon compounds as needed, a further hydrolysis and polycondensation reaction with the obtained intermediate product, and then the organosilicon compound, may be carried out.

[0082] In cases where an intermediate product is obtained as described above, further hydrolysis and condensation reactions with a compound in which m is 3 and k is 1 can be carried out after hydrolysis and condensation reactions of the organosilicon compound and, if necessary, other silicon compounds. Thus, polysiloxanes with terminal portions capped by constituent units (e) derived from compounds in which m is 3 and k is 1 in the organosilicon compound can be suitably synthesized, resulting in suppressed viscosity increases and improved storage stability.

[0083] The manufacturing method of polysiloxane represented by formula (1) preferably includes a distillation removal step, in which the reaction solvent, byproducts, residual monomers and water in the reaction solution are removed by distillation after the silicon compound is hydrolyzed and polycondensed in the presence of a reaction solvent.

[0084] Examples of Q monomers, where m = 0 and k = 4, in the organosilicon compound that provides the constituent unit (a) through hydrolysis and condensation, include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, etc.

[0085] In the organosilicon compounds that provide constituent units (b) and (c) through hydrolysis and condensation, examples of T monomers providing constituent units (b) and (c) with m=1 and k=3 include (3-acryloyloxypropyl)trimethoxysilane, (3-acryloyloxypropyl)triethoxysilane, (8-acryloyloxyoctyl)trimethoxysilane, (3-acryloyloxypropyl)trichlorosilane, (3-methacryloyloxypropyl)trimethoxysilane, (3-methacryloyloxypropyl)triethoxysilane, and (8-methacryloyloxyoctyl)trimethoxysilane. Silane, (3-methacryloyloxypropyl)trichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, octyltrimethoxysilane, trimethoxy(trifluoromethyl)silane, triethoxy(trifluoromethyl)silane, trimethoxy(3,3,3-trifluoropropyl)silane, trimethoxy(4,4,4-trifluorobutyl)silane, triethoxy-1H,1H,2H,2H-heptadecylfluorodecylsilane, triethoxy-1H,1H,2H,2H-tetrafluoro-n-octylsilane, trimethoxy(1H,1H,2H,2H-nonafluoro)silane Hexyl)silane, phenyltrimethoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane, cyclohexyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, p-styryltrimethoxysilane, ethynyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane Hydrochloride salts of silanes, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-ureopropyltrimethoxysilane, 3-ureopropyltriethoxysilane, 3-isocyanate-propyltriethoxysilane, tris(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropyltrimethoxysilane, 3-ethyl-3-[{3-(trimethoxysilyl)propoxy}methyl]oxetane, 3-ethyl-3-[{3-(triethoxysilyl)propoxy}methyl]oxetane, (3-ethyl-3oxetane-butylmethoxy)propyltrimethoxysilane, etc.

[0086] Examples of D monomers, where m is 2 and k is 2, in the organosilicon compounds that provide the constituent unit (d) through hydrolysis and polycondensation, include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, diperfluoromethyldimethoxysilane, diperfluoroethyldiethoxysilane, propylmethyldimethoxysilane, octylmethyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, benzylmethyldimethoxysilane, cyclohexylmethyldimethoxysilane, vinylmethyldimethoxysilane, allylmethyldimethoxysilane, p-styrylmethyldimethoxysilane, and ethynylmethyldimethoxysilane. Hydrochloride salts of 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropylmethyldimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropylmethyldimethoxysilane, 3-ureidopropylmethyldialkoxysilane, 3-isocyanate-propylmethyldiethoxysilane, (3-acryloyloxypropyl)methyldimethoxysilane, and (3-methacryloyloxypropyl)methyldiethoxysilane, etc.

[0087] As a compound in which m is 3 and k is 1 in the organosilicon compound that provides the constituent unit (e) through hydrolysis and condensation, examples of monomers as M include trimethylmethoxysilane, trimethylethoxysilane, tris(perfluoromethyl)methoxysilane, tris(perfluoroethyl)methoxysilane, trimethylchlorosilane, dimethylphenylmethoxysilane, methoxydimethylvinylsilane, ethoxydimethylvinylsilane, dichlorodimethylvinylsilane, dimethylvinylsilanol, (3-acryloyloxypropyl)dimethylmethoxysilane, (3-methacryloyloxypropyl)dimethylmethoxysilane, p-styryldimethylmethoxysilane, and ethynyldimethylmethoxysilane. In addition, examples of M dimers that provide two constituent units (e) through hydrolysis and polycondensation include hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-bis(p-styryl)tetramethyldisiloxane, 1,3-bis(3-acryloyloxypropyl)tetramethyldisiloxane, 1,3-bis(3-methacryloyloxypropyl)tetramethyldisiloxane, and hexa(perfluoromethyl)disiloxane.

[0088] Furthermore, as a raw material for providing the constituent unit (d), a reactive silicon compound having a siloxane bond-forming group represented by formula (3) or formula (4) can be cited. When such a reactive silicon compound is used, the silicon chain structure represented by formula (S) can be efficiently introduced into the sesquioxane derivative represented by formula (1).

[0089] [Chemical Formula 8]

[0090] Y in equations (3) and (4) 1 The siloxane bond-forming group is a group of atoms or atomic groups capable of forming siloxane bonds with silicon atoms in a silane compound. Specific examples include alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, and tert-butoxy; cycloalkoxy groups such as cyclohexyloxy; aryloxy groups such as phenoxy; hydroxyl groups; and hydrogen atoms. In particular, reactive silicon compounds with a hydroxyl group as the siloxane bond-forming group are readily available and their reactions with silane compounds are easily controlled, making them preferred.

[0091] The reactive silicon compound represented by formula (3) has two siloxane-forming groups in one molecule, but these groups can be the same or different groups. The reactive silicon compound represented by formula (4) has one siloxane-forming group in one molecule. In this disclosure, either formula (3) or formula (4) can be used, but the reactive silicon compound having two siloxane-forming groups in one molecule represented by formula (3) is particularly preferred.

[0092] R in equations (3) and (4) 11 and R 14 Each of the following groups independently represents an alkoxy, aryloxy, alkyl, cycloalkyl, or aryl group, and two of these groups exist in one molecule. 11 and R 14 They can be the same group or different groups. R 11 and R 14 Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, cyclohexyloxy, phenoxy, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclohexyl, phenyl, etc.

[0093] R in equations (3) and (4) 12 R 13 and R 15 Each R can independently represent an alkyl, cycloalkyl, or aryl group, and multiple Rs can exist in a single molecule. 2 and R 3 They can be the same group or different groups. R 12 R 13 and R 15Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclohexyl, and phenyl. As reactive silicon compounds, multiple R groups can be produced from inexpensive raw materials, with each group existing in a single molecule. 12 and R 13 The cured product obtained by using a reactive silicon compound that is methyl or ethyl and is obtained by using a curable resin obtained by using a polysiloxane represented by formula (1) of this disclosure is particularly preferred from the viewpoints of durability, hydrophobicity, antifouling, hardness and surface smoothness. In particular, the reactive silicon compound that is entirely methyl is particularly effective and is therefore preferred.

[0094] The number of repeating units j in equations (3) and (4) represents a positive number. As a reactive silicon compound, j is preferably 1-300, more preferably 2-100, further preferably 3-100, and particularly preferably 4-50, based on the viewpoints of the transparency of the obtained polysiloxane, its compatibility with other components of the curable composition, the transparency, durability, hydrophobicity, antifouling properties, hardness, and surface smoothness of the cured composition. Furthermore, as reactive silicon compounds, j in formulas (3) and (4) can be a single value or a mixture of compounds with multiple values, but according to the same viewpoint as above, its average value J is a number of 1 or more, preferably 2 or more, more preferably 3-50, further preferably 4-30, and particularly preferably 6-20. In addition, the average value J can be calculated, for example, based on the average molecular weight of reactive silicon.

[0095] R in reactive silicon compounds 11 and R 14 Reactive silicon compounds with alkoxy or aryloxy groups can be obtained, for example, through the dealcoholization reaction of polysiloxane-α,ω-diol with trialkoxysilane or triaryloxysilane, or the de-alcoholization reaction of phenols. This reaction is preferably carried out without a catalyst, under conditions of excess trialkoxysilane or triaryloxysilane, but it can also be carried out using transesterification catalysts such as p-toluenesulfonic acid or trifluorinated acetic acid.

[0096] Examples of commercially available reactive silicon compounds that are constituent units (d) include dimethylpolysiloxanes (manufactured by Shin-Etsu Chemical Industry Co., Ltd., such as X-21-5841, KF-9701, and XF-3905).

[0097] In the hydrolysis process, there are no particular limitations on the reaction solvent, but ethanol is preferred as the organic solvent. Ethanol, in the narrow sense, is represented by the general formula R-OH, and is a compound that does not have functional groups other than the hydroxyl group. Ethanol is not particularly limited, 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. In the hydrolysis process, one or more of these ethanols can be used in combination.

[0098] The organic solvent used in the hydrolysis process can be ethanol alone, or it can be further prepared as a mixture with at least one type of auxiliary solvent. The auxiliary solvent can be either a polar solvent or a non-polar solvent, or a combination of both. Examples of organic solvents other than ethanol include xylene, toluene, methyl ethyl ketone, methyl isobutyl ketone, and propylene glycol monomethyl ether.

[0099] The hydrolysis and condensation reactions in the hydrolysis process are carried out in the presence of water. In the hydrolysis process, it is preferable to add water in an amount of 0.2 to 30 molar equivalents relative to the total amount of hydrolyzable groups in the organosilicon compound for hydrolysis, and then condensation. Furthermore, in the hydrolysis process, based on the viewpoints of the curing shrinkage rate, hardness, storage stability, and curl inhibition during curing of the obtained polysiloxane, the amount of water added relative to the total amount of hydrolyzable groups in the organosilicon compound is preferably 0.2 molar equivalents to 10 molar equivalents, more preferably 0.3 molar equivalents to 7 molar equivalents, even more preferably 0.4 molar equivalents to 7 molar equivalents, particularly preferably 0.5 molar equivalents to 7 molar equivalents, and most preferably 0.6 molar equivalents to 6 molar equivalents.

[0100] Furthermore, the hydrolysis and polycondensation reactions of silicon compounds can be carried out either without a catalyst or with a catalyst. When using a catalyst, it is preferable to use 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, or alkaline catalysts such as ammonia, tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate, and more preferably acid catalysts. The amount of catalyst used is preferably equivalent to 0.01 mol% to 20 mol% relative to the total amount (moles) of silicon atoms contained in the silicon compound, and more preferably equivalent to 0.1 mol% to 10 mol%.

[0101] The completion of hydrolysis and polycondensation reactions in the hydrolysis process can be appropriately detected by methods described in various publications. Furthermore, in the hydrolysis process of the method for manufacturing polysiloxane represented by formula (1), an additive can be added to the reaction system.

[0102] Following the hydrolysis step in the manufacture of the polysiloxane represented by formula (1), the aforementioned distillation removal step is performed, thereby improving the stability of the silsesquioxane derivative of this disclosure. The distillation removal can be performed under normal or reduced pressure, at room temperature or under heating, or under cooling.

[0103] The method for manufacturing polysiloxane represented by formula (1) includes a neutralization step for neutralizing the catalyst before the distillation removal step. Additionally, it includes a step for removing the salts generated during neutralization by means of water washing.

[0104] Furthermore, the polysiloxane represented by formula (1) may contain ring-opening groups derived from the side chain functional groups of the silicon compound used as a raw material, which are formed by the addition of acids or the like with oxetyl or epoxy groups. It may also contain hydroxyalkyl groups generated by the decomposition of organic groups having (meth)acryloyl groups, or groups formed by the addition of acids or the like with unsaturated hydrocarbon groups. As a specific example, a polysiloxane containing, for instance, the structure represented by formula (A) and / or the structure represented by formula (B) in a portion of formula (1) can be cited. As for its content ratio, as long as the amount equivalent to the organic groups having the original oxetyl or epoxy groups, the original (meth)acryloyl groups, or the original unsaturated hydrocarbon groups derived from the silicon compound used as a raw material is 50 mol% or less, it will not affect the implementation of this disclosure; preferably, it is 30 mol% or less, more preferably 10 mol% or less. In both formulas (A) and (B), T units are shown, but the same D units, M units, etc., may also be used.

[0105] [Chemical Formula 9]

[0106] [Chemical Formula 10]

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

[0108] [Chemical Formula 11]

[0109] In equation (2), R 6 R 7 and R 8 Each of the following groups independently represents at least one group selected from the group consisting of alkyl groups having 1-10 carbon atoms, aralkyl groups having 7-10 carbon atoms, aryl groups having 6-10 carbon atoms, and monovalent organic groups having polymerizable groups, R 6 R 7 and R 8 At least one of them is a monovalent organic group with a polymerizable group, R 6 R 7 and R 8 The alkyl, aralkyl, aryl, and monovalent organic groups having polymerizable groups can be substituted by structures selected from the group consisting of halogen atoms, hydroxyl groups, alkoxy groups, aryloxy groups, arylalkoxy groups, and oxy groups, where q represents a positive number, and p, r, and s independently represent 0 or a positive number, respectively.

[0110] R 6 R 7 and R 8 In addition to the above, preferred embodiments of alkyl groups with 1-10 carbon atoms, aralkyl groups with 7-10 carbon atoms, aryl groups with 6-10 carbon atoms, and monovalent organic groups having polymerizable groups, are those related to R. 1 The preferred embodiments of alkyl groups with 1-10 carbon atoms, aralkyl groups with 7-10 carbon atoms, aryl groups with 6-10 carbon atoms, and monovalent organic groups having polymerizable groups are the same.

[0111] Each constituent unit in the polysiloxane represented by equation (2) is referred to as constituent unit (g)-(j) as follows.

[0112] [Chemical Formula 12]

[0113] In the polysiloxane represented by equation (2), q represents a positive number, and p, r and s are independently 0 or positive numbers. That is to say, the polysiloxane represented by equation (2) may also include the constituent unit (h) in the constituent units (g)-(j) above, and may include at least one of the constituent units (g), (i) and (j) as needed. In addition, since the polysiloxane represented by formula (2) contains at least the constituent unit (h), there are cases where it is not called polysiloxane but sesquisiloxane.

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

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

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

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

[0118] (The weight-average molecular weight of polysiloxane represented by formula (2)) The Mw of the polysiloxane represented by formula (2) is not particularly limited. For example, it can be 300-30000, 500-15000, 700-10000, or 1000-5000.

[0119] (The viscosity of polysiloxane as expressed by equation (2)) The viscosity of the polysiloxane represented by formula (2) at 25°C is not particularly limited, and it can also be a solid. From a disposal point of view, the polysiloxane represented by formula (2) is preferably a liquid, and in this case, the viscosity is not particularly limited, but preferably 10 mPa·s-100000 mPa·s, more preferably 100 mPa·s-80000 mPa·s, even more preferably 300 mPa·s-60000 mPa·s, and particularly preferably 500 mPa·s-50000 mPa·s. Furthermore, in this disclosure, the viscosity at 25°C refers to the value measured using an E-type viscometer (cone-plate type viscometer; for example, the TVE22H type viscometer manufactured by Toki Kogyo Co., Ltd.).

[0120] (The content of polysiloxane as represented by formula (2)) From the viewpoints of durability, hardness and storage stability, the content of polysiloxane represented by formula (2) relative to the total solids content of the curable composition is preferably 50%-99.9% by mass, more preferably 65%-99.5% by mass, and particularly preferably 80%-99.5% by mass.

[0121] There are no particular limitations on the manufacturing method of the polysiloxane represented by formula (2), and it can be manufactured by known methods, which are disclosed in detail in International Publication No. 2013 / 031798, etc. Alternatively, the manufacturing method of the polysiloxane represented by the aforementioned formula (1) can also be referred to.

[0122] <Polymerization initiator> From the viewpoint of curability, the curable compositions of this disclosure preferably contain a polymerization initiator. The initiator is not particularly limited; examples include photopolymerization initiators and thermal polymerization initiators. Examples of photopolymerization initiators include photoradical polymerization initiators and photocationic polymerization initiators. Examples of thermal polymerization initiators include, for instance, thermal free radical polymerization initiators. Known compounds can be used as photopolymerization initiators and thermal polymerization initiators.

[0123] Examples of photoradical polymerization initiators include 2,2-dimethoxy-1,2-diphenylethyl-1-one, 1-hydroxycyclohexylphenyl one, 2-hydroxy-2-methyl-1-phenylprop-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-prop-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholino)propane-1-one. Acetophenone compounds such as phenyl-2-but-1-one, diethoxyacetophenone, oligomeric [2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone], and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)benzyl]phenyl}-2-methyl-prop-1-one; benzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone, and 4-benzoyl-4'-methyldiphenyl sulfide, etc. Benzophenone compounds; α-keto esters such as methyl benzoate, 2-[2-oxo-2-phenylacetoxyethoxy]ethyl oxyphenylacetate, and 2-[2-hydroxyethoxy]ethyl oxyphenylacetate; and phosphine oxides such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide. ; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; titanium octene compounds; acetophenone / benzophenone hybrid photoinitiators such as 1-(4-(4-benzoylbenzenesulfonyl)phenyl)-2-methyl-2-(4-methylphenylsulfinyl)prop-1-one; oxime ester photopolymerization initiators such as 1-(4-phenylthienyl)-2-(O-benzoyloxime)-1,2-octanedione; and camphorquinone, etc. Only one of these compounds can be used, or two or more can be used in combination.

[0124] Examples of photocationic polymerization initiators include iodonium salts, sulfonium salts, diazonium salts, selenium salts, pyridinium salts, ferrocene salts, and phosphonium salts. Among these, iodonium salts or sulfonium salts are preferred. When the photocationic polymerization initiator is an iodonium salt or a sulfonium salt, the anions that can be used as counterions include, for example, tetrafluoroborate anion, hexafluoroarsenate anion, hexafluoroantimonate anion, hexafluorophosphonate anion, etc.

[0125] Examples of iodonium salts include (triisopropyl)iodonium tetra(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetra(pentafluorophenyl)borate, bis(dodecylphenyl)iodonium hexafluorophosphate, bis(dodecylphenyl)iodonium hexafluoroantimonate, bis(dodecylphenyl)iodonium tetrafluoroborate, and bis(dodecylphenyl)iodonium tetrafluoroborate. Alkylphenyl)iodonium tetra(pentafluorophenyl)borate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluorophosphate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluoroantimonate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrafluoroborate, and 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetra(pentafluorophenyl)borate, etc. In addition, commercially available products can also be used for the above-mentioned iodonium salts. Specifically, examples include "UV9380C" (trade name) manufactured by Momentive Performance Materials Japan, "BLUESIL PI 2074" (trade name) manufactured by Elkem Silicones, and "WPI-116" (trade name) and "WPI-113" (trade name) manufactured by Fujifilm and Koko Pure Chemical Industries Co., Ltd., etc.

[0126] Examples of sulfonium salts include bis[4-(diphenylsulfonyl)phenyl]sulfide·bishexafluorophosphate, bis[4-(diphenylsulfonyl)phenyl]sulfide·bishexafluoroantimonate, bis[4-(diphenylsulfonyl)phenyl]sulfide·bistetrafluoroborate, bis[4-(diphenylsulfonyl)phenyl]sulfide·tetra(pentafluorophenyl)borate, diphenyl-4-(phenylthio)phenylsulfonium·hexafluorophosphate, diphenyl-4-(phenylthio)phenylsulfonium·hexafluoroantimonate, diphenyl-4-(phenylthio)phenylsulfonium·tetrafluoroborate, diphenyl-4-(phenylthio)phenylsulfonium·tetra(pentafluorophenyl)borate, and triphenylsulfonium... Phenylacetium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetra(pentafluorophenyl)borate, bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonyl)phenyl]sulfide bis(hexafluorophosphate), bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonyl)phenyl]sulfide bis(hexafluoroantimonate), bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonyl)phenyl]sulfide bis(tetrafluoroborate), and bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonyl)phenyl]sulfide bis(pentafluorophenyl)borate, etc. In addition, commercially available products can also be used for sulfonium salts. Specifically, examples include "Cyracure UVI-6990", "Cyracure UVI-6992" and "Cyracure UVI-6974" manufactured by Dow Chemical Company of Japan; "Adekaoptomer SP-150", "Adekaoptomer SP-152", "Adekaoptomer SP-170" and "Adekaoptomer SP-172" manufactured by ADEKA Co., Ltd.; and "WPAG-370" and "WPAG-638" manufactured by Fujifilm and Kouichi Chemical Co., Ltd.

[0127] Examples of such diazonium salts include benzenediazohexafluoroantimonate, benzenediazohexafluorophosphate, and benzenediazohexafluoroborate.

[0128] There are no particular limitations on thermal free radical polymerization initiators; examples include peroxides and azo initiators.

[0129] Examples of peroxides include hydrogen peroxide; inorganic peroxides such as sodium persulfate, ammonium persulfate, and potassium persulfate; and 1,1-bis(tert-butylperoxy)-2-methylcyclohexane, 1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-hexylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2, 2-Bis(4,4-di-butylperoxycyclohexyl)propane, 1,1-bis(tert-butylperoxy)cyclododecane, tert-hexylperoxyisopropyl monocarbonate, tert-butylperoxymaleic acid, tert-butylperoxy-3,5,5-trimethylhexanoate, tert-butylperoxylaurate, 2,5-dimethyl-2,5-di(m-toluylperoxy)hexane, tert-butylperoxyisopropyl monocarbonate, tert-butylperoxy-2-ethylhexyl monocarbonate, tert-hexyl benzoate peroxide, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, tert-butylperoxyacetate, 2,2-bis(tert-butylperoxy)butane, tert-butyl peroxide, n-butyl-4,4-bis(tert-butylperoxy)valerate, di-tert-butyl peroxide, α,α'-bis(tert-butylperoxy)diisopropylbenzene, diisopropylbenzene peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, ... Organic peroxides include butylperoxyhexane, tert-butylisopropylbenzene peroxide, di-tert-butyl peroxide, hydroperoxide-p-menthane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, diisopropylbenzene hydroperoxide, tert-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, tert-hexyl hydroperoxide, dilauroyl peroxide, and tert-butyl hydroperoxide. They can use only one type, or they can use two or more types together.

[0130] Examples of azo initiators include 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carboxylonitrile), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylpentanonitrile, azobis-tert-octane, and azobis-tert-butane. One or more of these compounds can be used. In addition, redox reactions can also be carried out by combining peroxides with reducing agents such as ascorbic acid, sodium ascorbate, sodium isoascorbate, tartaric acid, citric acid, metal salts of formaldehyde hyposulfite, sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium metabisulfite, and ferrous chloride.

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

[0132] <Other Ingredients> Other components are not particularly limited, and examples include solvents, polysiloxanes represented by formula (1) and polymeric compounds other than polysiloxanes represented by formula (2), resins, silicon, monomers, fillers, surfactants, antistatic agents (e.g., conductive polymers), leveling agents, photosensitizers, ultraviolet absorbers, antioxidants, heat resistance promoters, stabilizers, lubricants, pigments, dyes, plasticizers, suspending agents, adhesion promoters, nanoparticles, nanofibers, nanosheets, etc. As fillers, examples include silica particles (manufactured by Nichibukai Chemical Co., Ltd.: V-8804), silicon-modified silica (manufactured by BYK Corporation: NANOBYK-3650), and silicon-acrylic acid modified silica (manufactured by BYK Corporation: BYK-UV3518). The curable compositions disclosed herein may contain silane reactive diluents such as tetraalkoxysilanes, trialkoxysilanes, dialkoxysilanes, monoalkoxysilanes, and disiloxanes.

[0133] The curable compositions disclosed herein may or may not contain solvents. Examples of solvents include various organic solvents such as aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, chlorinated hydrocarbon solvents, ethanol solvents, ether solvents, amide solvents, ketone solvents, ester solvents, and cellulose solvents.

[0134] The curable compositions disclosed herein may contain either a polysiloxane represented by formula (1) and a polymeric compound other than a polysiloxane represented by formula (2) (hereinafter also referred to as "other polymeric compounds"). Other polymerizable compounds are not particularly limited as long as they are polysiloxanes represented by formula (1), polysiloxanes represented by formula (2) as needed, and compounds that can undergo polymerization reactions in the presence of a polymerization initiator. Examples of other polymerizable compounds include polysiloxanes other than those represented by formula (1) and polysiloxanes represented by formula (2), (meth)acrylate compounds, compounds having vinyl unsaturated groups, epoxy resin compounds (compounds having epoxy groups), compounds having oxetane groups (compounds containing oxetanes), and compounds having vinyl ether groups (vinyl ether compounds).

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

[0136] As (meth)acrylate compounds, there are no particular limitations, and examples include compounds having one (meth)acryloyl group (hereinafter also referred to as "monofunctional (meth)acrylates") and compounds having two or more (meth)acryloyl groups (hereinafter also referred to as "polyfunctional (meth)acrylates").

[0137] 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 with alicyclic groups, such as cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and tricyclodecane hydroxymethyl (meth)acrylate. Monofunctional (meth)acrylates having aromatic groups, including benzyl (meth)acrylates and phenyl (meth)acrylates; (Meth)acrylates of phenol ethylene oxide adducts, (meth)acrylates of phenol propylene oxide adducts, (meth)acrylates of modified nonylphenol ethylene oxide adducts, (meth)acrylates of nonylphenol propylene oxide adducts, (meth)acrylates of p-isopropylphenol alkylene oxide adducts, (meth)acrylates of o-phenylphenol (meth)acrylates, and (meth)acrylates of o-phenylphenol alkylene oxide adducts, etc., are alkylene oxide adducts of phenol derivatives. Monofunctional (meth) acrylates with alkoxyalkyl groups, such as 2-ethylhexyl carbitol (meth) acrylate; Tetrahydrofurfuryl (meth)acrylate and monofunctional (meth)acrylates such as N-(2-(meth)acryloyloxyethyl)hexahydrophthalimide have heterocyclic rings. Hydroxyalkyl methacrylates such as ethyl hydroxy(meth)acrylate, hydroxypropyl (meth)acrylate, butyl hydroxy(meth)acrylate, and hydroxyhexyl (meth)acrylate; Monofunctional (meth)acrylates having hydroxyl and aromatic groups, such as 2-hydroxy-3-phenoxypropyl (meth)acrylate; Diethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, tripropylene glycol mono(meth)acrylate, and other alkylene glycol mono(meth)acrylates; and ω-carboxylated polycaprolactone mono(meth)acrylate and phthalic acid monohydroxy(meth)acrylate ethyl ester, etc., are monofunctional (meth)acrylates with carboxyl groups.

[0138] Examples of polyfunctional (meth)acrylates include: Diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and other polyethylene glycol di(meth)acrylates; Polypropylene glycol di(meth)acrylates such as dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and tetrapropylene glycol di(meth)acrylate; 1,4-Butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide-modified neopentyl glycol di(meth)acrylate, ethylene oxide-modified bisphenol A di(meth)acrylate, propylene oxide-modified bisphenol A di(meth)acrylate, ethylene oxide-modified hydrogenated bisphenol A di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane allyl ether di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexaacrylate, etc.

[0139] As a multifunctional (meth)acrylate, urethane (meth)acrylates can also be used. Examples of urethane (meth)acrylates include compounds obtained by adding an organic polyisocyanate group to a hydroxyl-containing (meth)acrylate, and compounds obtained by adding an organic polyisocyanate group, a polyol, and a hydroxyl-containing (meth)acrylate. Monofunctional (meth)acrylates, polyfunctional (meth)acrylates, etc., can be used with only one type, or with two or more types, or with different types.

[0140] 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, cyclohexanediol, and 3-methyl-1,5-pentanediol. Examples of polyether polyols include polypropylene glycol and polytetramethylene glycol. Examples of polyester polyols include these low molecular weight polyols and / or polyether polyols reacting with dicarboxylic acids or their anhydrides, such as adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid, and terephthalic acid. They can use only one type, or use two or more types together, or use different types together.

[0141] Examples of organic polyisocyanate groups include toluene diisocyanate, xylene diisocyanate, tetramethylxylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Examples of hydroxyl-containing (meth)acrylates include hydroxyalkyl (meth)acrylates such as ethyl 2-hydroxy(meth)acrylate, propyl 2-hydroxy(meth)acrylate, and butyl 4-hydroxy(meth)acrylate; polyfunctional (meth)acrylates containing hydroxyl groups such as pentaerythritol tri(meth)acrylate, di(meth)acrylate of the alkylene oxide 3-molar adduct of isocyanuric acid, and pentaerythritol penta(meth)acrylate. They can use only one type, or use two or more types together, or use different types together.

[0142] In the curable compositions disclosed herein, the proportion of (meth)acrylate compounds used in combination is not particularly limited. For example, the proportion of (meth)acrylate compounds relative to the total solids content of the curable composition is preferably 0%-50% by mass, more preferably 0%-25% by mass, and even more preferably 0%-10% by mass. From the viewpoint of adhesion to the inorganic material layer, the proportion of (meth)acrylate compounds is preferably low, preferably absent, or more preferably absent at a content of 10% or less relative to the total solids content of the composition, or even more preferably absent at a content of 5% or less relative to the total solids content of the composition, or particularly preferably absent at a content of 1% or less relative to the total solids content of the composition.

[0143] Alternatively, a molecule other than the (meth)acrylate compound may contain one vinyl unsaturated group. Compounds are added to curable compositions. As the vinyl unsaturated group, (meth)acryloyl, maleimide, (meth)acrylamide, or vinyl are preferred. Specific examples of compounds having vinyl unsaturated groups include (meth)acrylic acid, Michael addition dimers of acrylic acid, N-(2-hydroxyethyl)citrimethyleneimide, N,N-dimethylacrylamide, acrylmorpholine, N-vinylpyrrolidone, and N-vinylcaprolactam. They can use only one type, or they can use two or more types together.

[0144] Examples of epoxy resin compounds include monofunctional epoxy resin compounds and polyfunctional epoxy resin compounds. Examples of compounds containing oxoheterobutyl groups include monofunctional oxoheterobutylane compounds and polyfunctional oxoheterobutylane compounds. Examples of vinyl ether compounds include monofunctional vinyl ether compounds and polyfunctional vinyl ether compounds. For example, the compounds described in Japanese Patent Application Publication No. 2011-42755 can be used as these compounds. There are no particular limitations on the silicon used; known materials can be used, such as polydimethylsilicon, polydiphenylsilicon, and polymethylphenylsilicon, preferably having functional groups at their ends and / or side chains. There are no particular limitations on the functional groups used; for example, (meth)acryloyl, epoxy, oxetyl, vinyl, hydroxyl, carboxyl, amino, and thiol groups can be included.

[0145] When the curable composition disclosed herein contains other polymeric compounds, the content of the other polymeric compounds relative to the total solids content of the curable composition is preferably 0.01%-50% by mass, more preferably 0.1%-25% by mass, and even more preferably 1%-15% by mass.

[0146] (Elastic modulus of the cured material) From the viewpoints of curing shrinkage rate, hardness, storage stability and curl suppression during curing, the elastic modulus of the cured product obtained by curing the curable composition of this disclosure at 23°C is preferably greater than 2.0 GPa, more preferably greater than 4.0 GPa, even more preferably greater than 4.0 GPa and less than 20.0 GPa, and particularly preferably greater than 4.2 GPa and less than 15.0 GPa.

[0147] The method for determining the elastic modulus of the cured material at 23°C in this disclosure is performed by the indentation elastic modulus determination method described in the examples. Furthermore, in this disclosure, a curable composition capable of producing a cured material with excellent hardness refers to a cured material formed by curing the curable composition that has an excellent elastic modulus.

[0148] [Cured material] The cured product of this disclosure is obtained by curing the curable composition of this disclosure. For example, the cured product of this disclosure can be obtained by irradiating the curable composition of this disclosure with activation energy rays or by heating the curable composition of this disclosure.

[0149] In the case of curing the curable composition disclosed herein, the curable composition may also be applied to the substrate after curing. The curable compositions disclosed herein may or may not contain a solvent. When a solvent is included, curing is preferably performed after the solvent is removed.

[0150] When applying the curable composition of this disclosure to a substrate, the method of application of the curable composition is not particularly limited. Examples of common application methods include casting, spin coating, rod coating, dip coating, spraying, roller coating, flow coating, and gravure coating. The coating thickness of the curable composition disclosed herein is not particularly limited and can be appropriately set according to the purpose. There are no particular limitations on the substrate for applying the cured composition disclosed herein, 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 alumina, 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; mortars; concrete; and glass. Specific examples of plastics include acrylic resins such as polymethyl methacrylate, polyester resins such as polyethylene terephthalate, polyvinyl chloride resins, polycarbonate resins, epoxy resins, polyamide resins such as nylon and aramid, polyimide resins, polyamide-imide resins, fluoropolymers such as tetrafluoroethylene resins, polyolefin resins such as cross-linked polyethylene resins, vinylidene chloride resins, acrylonitrile-butadiene-styrene (ABS) resins, polystyrene resins, polyacrylonitrile resins, cyclic olefin polymers (COP), cyclic olefin copolymers (COC), acetate resins, polyarylates, cellophane, norbornene resins, triacetyl cellulose (TAC) and other acetylcellulose resins, polychloroprene, polyphenylene sulfide, polysulfone, polyethersulfone, polyetheretherketone, polyurethane resins, and composite resins such as glass epoxy 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. Fabrics can be woven or non-woven, and can be made using the aforementioned fibers. These materials can be used individually, or in combination, mixture, or composite. There are no particular restrictions on the shape of the substrate, such as plate, sheet, film, rod, sphere, fiber, powder, lens, and other regular or irregular shapes.

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

[0152] (1) Activated energy X-ray curing method When this composition is an activation energy ray curable composition, its curing method can be achieved by irradiation with activation energy rays using a known activation energy ray irradiation device or the like. Examples of activation energy rays include electron beams, ultraviolet light, visible light, and X-rays, with light being preferred, and ultraviolet light being more preferred from the viewpoint of being able to use inexpensive devices. 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 lamps, microwave-excited mercury lamps, and light-emitting diodes (LEDs). The light irradiation intensity on the coating of this composition can be selected according to the purpose and application. The preferred light irradiation intensity is 0.1 mW / cm² within the effective activation wavelength range of the activating energy radiation polymerization initiator (referred to as a photopolymerization initiator in the case of photocurability). (This varies depending on the type of photopolymerization initiator, but light with wavelengths of 220 nm to 460 nm is preferred.) 2 -1000 mW / cm 2 . Furthermore, the irradiation energy should be appropriately set according to the type and composition of the activation energy rays. The irradiation time of the coating can also be selected according to the purpose and application, preferably such that the cumulative light intensity, expressed as the product of the light intensity and irradiation time in the wavelength region, is 10 mJ / cm². 2 -7000 mJ / cm 2 The light irradiation time is set in a specific manner. The cumulative light intensity is more preferably 200 mJ / cm². 2 -5000 mJ / cm 2 Further optimization of 500 mJ / cm 2 -4000 mJ / cm 2 As long as the cumulative light intensity is within the specified range, the composition can be cured smoothly, and a uniform cured product can be easily obtained.

[0153] In addition, heat curing can be appropriately combined before and / or after light curing. For example, a two-stage curing process is also possible: after the composition has penetrated into a substrate with shaded areas when exposed to light, the composition is first cured in the light-exposed areas, and then heat is applied to cure the composition in the areas not exposed to light. There are no particular limitations on the substrate; examples include substrates with complex shapes such as fabric, fiber, powder, porous, and textured surfaces, or substrates combining two or more of these shapes.

[0154] (2) Thermosetting method When this composition is a thermosetting composition, its curing method and curing conditions are not particularly limited. The curing temperature is preferably 80°C-200°C, more preferably 100°C-180°C, and even more preferably 110°C-150°C. Regarding the curing temperature, it can be kept constant or increased. A combination of increasing and decreasing the temperature is also possible. The curing time can be appropriately selected according to the type of thermal polymerization initiator and the content ratio of other components, 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 preferred conditions, a uniform cured film without bulging, cracks, etc., can be formed.

[0155] (Uses of curable compositions, etc.) The cured product of this disclosure exhibits excellent hardness, thus it can be applied to hard coatings, optical components, and the like. Furthermore, by curing a hard coating agent containing the curable composition of this disclosure, a hard coating with excellent hardness can be obtained. The hard coating agent of this disclosure can also be applied to a substrate; for example, by curing a hard coating agent applied to a substrate, a substrate with a hard coating can be obtained. The hard coating agent of this disclosure can also contain various components as needed. The cured or hard coating of this disclosure exhibits excellent weather resistance. This is presumably due to the excellent durability, hydrophobicity, and antifouling properties of the cured composition of this disclosure, which inhibits the deterioration of the cured product even under harsh conditions. The curable compositions disclosed herein can be applied, for example, to adhesive applications, printing applications such as inkjet and 3D printing, coating applications, and nanoprinting applications. The curable compositions disclosed herein may also be used in combination with fillers, other polymeric compounds, etc.

[0156] The elastic modulus of the cured product or the hard coating of this disclosure at 23°C is preferably greater than 2.0 GPa, more preferably greater than 4.0 GPa, even more preferably greater than 4.0 GPa and less than 20.0 GPa, and particularly preferably greater than 4.2 GPa and less than 15.0 GPa. Example

[0157] The present disclosure will now be described in detail based on embodiments and comparative examples. The present disclosure is not limited to the following embodiments.

[0158] <Synthesis of polysiloxanes represented by formula (1)> (Synthesis Example 1: Synthesis of Polysiloxane 1) In a 500 mL four-necked flask equipped with a stirrer, dropping funnel, and Demrod condenser, 19.7 g of 3-acryloyloxypropyltrimethoxysilane (0.08 mol, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), 73.5 g of triethoxytridecylfluoro-n-octylsilane (0.14 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), and 157 g of 2-propanol were weighed and added dropwise. 12.4 g of a 2% (w / w) aqueous solution of hydrochloric acid was added dropwise. After stirring for 1 hour, 1.12 g of dimethyldivinyldisiloxane (6 mmol, manufactured by Silicon Materials Development Co., Ltd.) was added dropwise, and the mixture was stirred overnight at room temperature. The solvent was removed from the resulting solution under vacuum to obtain 73 g of polysiloxane 1. 1 H-NMR analysis confirmed that each component was quantitatively introduced according to the feed ratio of the raw materials.

[0159] (Synthesis Example 2: Synthesis of Polysiloxane 2) Except for changing 3-acryloyloxypropyltrimethoxysilane to 30.9 g (0.13 mol) and triethoxytridecylfluoro-n-octylsilane to 49 g (0.07 mol), the same method as in Synthesis Example 1 was used to obtain 62 g of polysiloxane 2.

[0160] (Synthesis Example 3: Synthesis of Polysiloxane 3) Except for changing 3-acryloyloxypropyltrimethoxysilane to 36.5 g (0.16 mol) and triethoxytridecylfluoro-n-octylsilane to 36.7 g (0.1 mol), the same method as in Synthesis Example 1 was used to obtain 56 g of polysiloxane 3.

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

[0162] (Synthesis Example 5: Synthesis of Polysiloxane 5) Except for replacing 3-acryloyloxypropyltrimethoxysilane with 57.7 g of 3-methacryloyloxypropyltrimethoxysilane (0.23 mol, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), all other parts were synthesized in the same manner as in Synthesis Example 4, yielding 50 g of polysiloxane 5.

[0163] (Synthesis Example 6: Synthesis of Polysiloxane 6) Except for replacing 3-acryloyloxypropyltrimethoxysilane with (3-ethyl-3-oxecyclobutylmethoxy)propyltrimethoxysilane 61 g (0.22 mol, the compound below), all were synthesized in the same manner as in Synthesis Example 4, yielding 50 g of polysiloxane 6.

[0164] (Synthesis Example 7: Synthesis of Polysiloxane 7) In a 500 mL four-necked flask equipped with a stirrer, dropping funnel, and Demrod condenser, 46.86 g of 3-acryloyloxypropyltrimethoxysilane (0.20 mol, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), 3.68 g of polydimethylsiloxane (Shin-Etsu Chemical Industry Co., Ltd. X-21-5841), and 60 g of 2-propanol were weighed and added. Then, 1.5 g of a 10% (w / w) aqueous solution of tetramethylammonium hydroxide and 9.45 g of deionized water were added dropwise, and the mixture was stirred at room temperature for 8 hours. The resulting solution was concentrated under reduced pressure, dissolved in toluene, and washed with water using a separatory funnel. The solvent was removed from the organic layer by reduced pressure distillation to obtain polysiloxane 7.

[0165] (Synthesis Example 8: Synthesis of Polysiloxane 8) In a 2 L four-necked flask equipped with a stirrer, dropping funnel, and Demrod condenser, 210.8 g of 3-acryloyloxypropyltrimethoxysilane (0.90 mol, manufactured by Shin-Etsu Chemical Co., Ltd.), 148.7 g of polydimethylsiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.), and 582.4 g of 2-propanol were weighed and added dropwise. Then, 0.9 g of a 25% (w / w) aqueous solution of tetramethylammonium hydroxide and 12.3 g of deionized water were added dropwise, and the mixture was stirred at room temperature for 4 hours. The resulting solution was concentrated under reduced pressure, dissolved in toluene, and washed with water using a separatory funnel. The solvent was removed from the organic layer by reduced pressure distillation to obtain 297.4 g of polysiloxane 8.

[0166] <Synthesis of polysiloxanes represented by equation (2)> (Synthesis Example 9: Synthesis of Polysiloxane 9) In a 1 L four-necked round-bottom flask equipped with a thermometer, dropping funnel, and stirring blade, (3-acryloyloxy)propyltrimethoxysilane (140.6 g, 0.6 mol), 3-methacryloyloxypropyltrimethoxysilane (99.3 g, 0.4 mol), 2-propanol (64.6 g), and hydroquinone (0.085 g) were weighed and added. The mixture was stirred in a water bath at approximately 30°C. Separately, an aqueous solution was prepared by mixing 1.0 g of 35% hydrochloric acid (as hydrogen chloride, 9.6 mmol) and 150.7 g of deionized water. The reaction mixture was stirred while being added dropwise through the dropping funnel for approximately 1 hour, and then allowed to stand overnight at room temperature. The amount of water added was set to 2.8 moles relative to the total stoichiometry of the hydrolyzable groups of the starting organosilicon compounds. Then, while heating the reaction solution to 60°C, the solvent and other substances in the reaction solution were removed by vacuum distillation to obtain 170 g of colorless and transparent liquid polysiloxane 9. (The process was repeated in the original text.) 1 ¹H-NMR analysis confirmed that each constituent unit was quantitatively introduced according to the feed ratio of the raw materials. The synthesized polysiloxane 9 had a viscosity of 6,270 mPa·s at 25°C and a weight-average molecular weight (Mw) of 2,010.

[0167] (Synthesis Example 10: Synthesis of Polysiloxane 10) According to the method of Example 1 in Japanese Patent Application Publication No. 11-029640, a polysiloxane 10 having an oxetine group as a polymerizable group was synthesized as follows. In a reactor equipped with a stirrer, thermometer, and cooler, 12.37 g (38.6 mmol) of 3-(3-ethyl-3-oxetane-butylmethoxy)propyltriethoxysilane, 1.05 g (H₂O; 52.5 mmol, Me₄NOH; 1.2 mmol) of a 10% aqueous solution of tetramethylammonium hydroxide (hereinafter also referred to as "Me₄NOH"), 1.14 g (63.3 mmol) of water, and 300 mL of 1,4-dioxane as solvent were added, and the mixture was heated under reflux for 16 hours with stirring. At this point, the pH of the reaction system was 12.1. After reflux, 200 mL of solvent was distilled off, the reaction system was concentrated, and the reaction was continued for another 6 hours. After the reaction was completed, the solvent was distilled off under reduced pressure, and 200 mL of toluene was used to replace the solvent. The mixture was washed several times with water using a separatory funnel, dehydrated with anhydrous sodium sulfate, and then the toluene was distilled off under reduced pressure to obtain the target polysiloxane 10.

[0168] (Determination of molecular weight) The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of polysiloxanes were determined by gel permeation chromatography (using a Tosoh HLC-8320GPC, hereinafter referred to as "GPC") in tetrahydrofuran solvent at 40°C, using a GPC column "TSK gel SuperMultiporeHZ-M" (manufactured by Tosoh). The molecular weight converted to that of standard polystyrene was calculated based on the retention time.

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

[0170] The results are summarized in Table 1.

[0171] [Table 1]

[0172] In Table 1, the values ​​of af represent the molar ratio. In addition, as comparative examples 3-5, the following commercially available leveling agents were used. RS75A: DIC Corporation, a leveling agent containing a (meth)acryloyl group with a non-silsesquioxane structure and a perfluoropolyether group. RS57: DIC Corporation, a leveling agent containing a (meth)acryloyl group with a non-silsesquioxane structure and a dimethylsilyl group. F-44: A leveling agent from DIC Corporation that contains no polymerizable groups and is fluorinated.

[0173] <Examples 1-10 and Comparative Examples 1-8> (Preparation of curable compositions and fabrication of cured films) As the compound represented by formula (2), relative to 3 g of polysiloxane 9 or 10, 0.15 g of 2-hydroxy-2-methyl-1-phenylpropanone, 3 g of propylene glycol monobutyl ether, polysiloxane 1-8 as the compound represented by formula (1) or a commercially available leveling agent, and silica particles (manufactured by Nichibukai Chemical Co., Ltd.: V-8804) as other fillers were weighed, mixed and dissolved using a rotary mixer to prepare a curable composition (photocurable composition). The amount of silica particles weighed in Example 10 and Comparative Example 7 was 50% by mass relative to the total weight of the polysiloxane represented by formula (1) and the polysiloxane represented by formula (2). The photocurable composition was applied to either polyethylene terephthalate (PET) film (Toyosho Co., Ltd., A4360, 50 μm thick) or SPCC-SD steel sheet (matte cold-rolled steel sheet), and coated using a No. 8 bar coater. After drying in a ventilated oven at 60°C for 5 minutes, the film was irradiated with ultraviolet light under the following conditions to produce a cured film (photocurable film). The film thickness was approximately 5 μm. -Ultraviolet radiation conditions- Lamp: High-pressure mercury lamp Lamp height: 10 cm Conveyor belt speed: 5.75 m / min Cumulative light intensity per pass: 360 mJ / cm 2 (UV-A) Atmosphere: In the atmosphere Number of passes: 10

[0174] (Contact angle measurement) For the photocurable film prepared on SPCC-SD steel plate as described above, OCA20 was manufactured using Eiko Seiki Co., Ltd., and the deionized water contact angle at 23°C was evaluated.

[0175] (Determination of indentation elastic modulus) For the photocurable film fabricated on PET film as described above, indentation hardness was measured using a nanoindenter (Agilent Technologies G200, using a Burkevich indenter) at 23°C and a deformation rate of 0.05 / s. The elastic modulus was calculated by averaging the Modulus values ​​for indentation depths of 100 nm to 500 nm. In addition, in Examples 1-4, Examples 6-10, Comparative Examples 2-4, and Comparative Examples 6-8, the elastic modulus of the cured product without leveling agent compared to Comparative Example 1 was calculated, and the degree to which the elastic modulus of the cured product with leveling agent decreased was set as follows: Decrease rate (%) = {(elastic modulus of cured product without leveling agent - elastic modulus of cured product with leveling agent) / elastic modulus of cured product without leveling agent} × 100. Furthermore, in Example 5, the rate of decrease in elastic modulus relative to the cured product of Comparative Example 5 without the addition of leveling agent was calculated.

[0176] (Determination of kinetic friction coefficient) For the photocurable film fabricated on the SPCC-SD steel plate as described above, the coefficient of kinetic friction at 23°C was evaluated using a Tribo-Gear TYPE: 14FW manufactured by Shin-Tung Science & Technology Co., Ltd., following ISO 8295:1995(E). A spherical indenter was used, and the load was set to 200 g. The average value obtained from three measurements taken at a distance of 3 cm was taken as the coefficient of kinetic friction.

[0177] (Pencil hardness test) For the photocurable film produced on SPCC-SD steel plate as described above, tests were conducted in accordance with JIS K5600-5-4. Three scratch tests were performed using pencils of various hardnesses, and the highest value of the pencil type that produced no defects in the photocurable film was defined as the pencil hardness.

[0178] (Durability evaluation) For the photocurable film prepared on the SPCC-SD steel plate as described above, acetone-impregnated cotton, hexane-impregnated cotton, and steel wool #0000 were abraded 50 times with loads of 1 cm × 1 cm and 1 kg, respectively. The deionized water contact angle after abrasion was measured. S was defined as no decrease compared to before the test, A as a decrease of less than 5%, B as a decrease of less than 10%, and C as a decrease of more than 10%.

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

[0180] [Table 2]

[0181] As shown in Table 2, the cured films of Examples 1-10 exhibit superior durability, particularly against abrasion using steel wool, compared to the cured films of Comparative Examples 1-8. This means that the cured films of Examples 1-10 of the present invention are less prone to detachment and loss of function of the leveling agent due to exudation. In addition, as shown in Table 2, the cured films of Examples 1-10 also exhibited superior suppression of the decrease in indentation elastic modulus compared to the cured films of Comparative Examples 1-8.

[0182] The contact angle of Comparative Example 8 was 96°-107°, which showed a deviation. The specific reason is unknown, but it is speculated to be related to the whiteness of the cured film.

[0183] The publication of Japanese Patent Application No. 2023-177806, filed on October 13, 2023, is incorporated herein by reference in its entirety. All documents, patent applications and technical standards described in this specification are incorporated herein by reference to the same extent as those specifically described therein.

Claims

1. A curable composition comprising a polysiloxane represented by formula (1), wherein the polysiloxane content is 0.1% by mass or more and less than 10% by mass relative to the total solids content of the curable composition, and x / (v + w + x + y + z) is less than 0.

6. [Chemical Formula 1] ， In equation (1), R 1 Each of the following groups independently represents at least one group selected from the group consisting of alkyl groups having 1-10 carbon atoms, aralkyl groups having 7-10 carbon atoms, aryl groups having 6-10 carbon atoms, and monovalent organic groups having polymerizable groups, 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 can be substituted by structures selected from the group consisting of halogen atoms, hydroxyl groups, alkoxy groups, aryloxy groups, arylalkoxy groups, and oxygen groups, R 2 R represents, independently, a hydrocarbon group consisting of 1-20 carbon atoms substituted by a fluorine atom. 3 R 4 and R 5 Each of the following groups independently represents at least one group selected from the group consisting of alkyl groups having 1-10 carbon atoms, aralkyl groups having 7-10 carbon atoms, aryl groups having 6-10 carbon atoms, and monovalent organic groups having polymerizable groups, R 3 R 4 and R 5 The alkyl, aralkyl, aryl, and monovalent organic groups having polymerizable groups can be substituted by structures selected from the group consisting of halogen atoms, hydroxyl groups, alkoxy groups, aryloxy groups, arylalkoxy groups, and oxygen groups. w represents a positive number, and v, x, y, and z independently represent 0 or positive numbers, with at least one of x and y representing a positive number. When x is 0, the structure contains the structure represented by formula (S). [Chemical Formula 2] ， n represents a number greater than or equal to 3.

2. The curable composition according to claim 1, wherein, In addition to the polysiloxane represented by formula (1), it also contains the polysiloxane represented by formula (2). [Chemical Formula 3] ， In equation (2), R 6 R 7 and R 8 Each of the following groups independently represents at least one group selected from the group consisting of alkyl groups having 1-10 carbon atoms, aralkyl groups having 7-10 carbon atoms, aryl groups having 6-10 carbon atoms, and monovalent organic groups having polymerizable groups, R 6 R 7 and R 8 At least one of them is a monovalent organic group having a polymerizable group, R 6 R 7 and R 8 The alkyl, aralkyl, aryl, and monovalent organic groups having polymerizable groups can be substituted by structures selected from the group consisting of halogen atoms, hydroxyl groups, alkoxy groups, aryloxy groups, arylalkoxy groups, and oxy groups, where q represents a positive number, and p, r, and s independently represent 0 or a positive number, respectively.

3. The curable composition according to claim 1 or 2, wherein, R in equation (1) 1 The polymerizable group is selected from at least one of the group consisting of acryloyl, methacryloyl, epoxy, oxetyl, vinyl, and allyl.

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

80.

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

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

7. A hard coating comprising the curable composition of claim 1 or 2.

8. A hard coating formed by curing the hard coating agent of claim 7.

9. An article having the hard coating of claim 8.

10. A laminate having the hard coating and substrate as described in claim 9.

11. The cured product according to claim 6, wherein, The pencil hardness of the cured material obtained on the steel plate is above 5H, and the coefficient of dynamic friction is below 0.

35.

12. The cured product according to claim 6, wherein, The decrease rate of water contact angle before and after the wear test using acetone-impregnated degreased cotton, the wear test using hexane-impregnated degreased cotton, and the wear test using steel wool was all less than 10%.

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