TW202405057A - Silsesquioxane derivative and method of producing the same, curable composition, hard coating agent, cured product, hard coating, and base material - Google Patents

Abstract

A sesquisiloxane derivative and a manufacturing method thereof, the sesquisiloxane derivative is represented by formula (1); a curable composition comprising the aforementioned sesquisiloxane derivative and a polymerization initiator ; A hard coating agent, which contains the aforementioned hardening composition; a hardened material, which is formed by hardening the aforementioned hardening composition; a hard coating layer, which is formed by hardening the aforementioned hard coating agent; a base material, It has the aforementioned hard coating layer. In formula (1), v is a positive number.

Description

Sesesquioxane derivatives and manufacturing methods thereof, curable compositions, hard coating agents, cured products, hard coat layers, and base materials

This case is about a sesquisiloxane derivative and its manufacturing method, curable composition, hard coating agent, cured product, hard coating layer, and base material.

Hard coating agents are used in various locations such as displays and frames that require hardness. Various curable compositions are known as compositions used in hard coating agents, and for example, polyfunctional acrylates are known.

Organic-inorganic composite compositions made by mixing inorganic fillers and organic resins, and organic-inorganic hybrid materials in which organic units and inorganic units coexist or are chemically bonded at the nanometer level are also attracting attention. For example, sesquioxane derivatives are known as such organic-inorganic hybrid materials.

The formation method of the hard coat layer is known. For example, the curable composition is coated on the base material using various conventional coating methods, and then the coated curable composition is cured by irradiating active energy rays such as ultraviolet rays. . If the base material is in the form of a film, a coating and curing method by a roll-to-roll method can be used. It is known that the formation of hard coatings can also be achieved using nanoimprinting methods.

For example, Japanese Patent Application Laid-Open No. 10-030068 discloses a coating composition that uses an organopolysiloxane resin as the main component. The organopolysiloxane resin is produced by adding an organosilicon compound with a hydrolyzable group. It is obtained by adding 50 to 5,000 parts by weight of water to 100 parts by weight of the organosilicon compound without using an organic solvent and hydrolyzing the compound, and has a number average molecular weight of 500 or more, and contains 5 to 100 parts by weight in all silicon. mol% of silicon atoms containing (meth)acrylic acid functional substituents, and containing 30 to 100 mol% of R ¹ SiX ₃ (X is a group selected from a hydroxyl group, a hydrolyzable group and a siloxane residue, At least one of X is a unit represented by a siloxane residue), and 30 ^to 80 mol% of _{the aforementioned} R ¹ Si Silanol-based units.

[Problem to be solved by the invention] A hard coating agent and sesquioxane derivative with low hardening shrinkage are being sought.

Japanese Patent Application Publication No. 10-030068 discloses that after coating a coating agent with an organic polysiloxane resin as the main component on the surface of a clean plastic molded body, wood-based products, ceramics, glass, and metal, it is irradiated with high energy The wire is used to polymerize and harden the (meth)acrylyl group, and then the silanol group is condensed and hardened by heating, thereby obtaining an article covered with a cured film having excellent weather resistance and other properties. In addition, the coating composition disclosed in Japanese Patent Application Publication No. 10-030068 shows that it has scratch resistance, adhesion, weather resistance, flame retardancy, storage stability, and flexibility, and can be made to have flexibility. The film is formed on the surface of plastic moldings, wood products, ceramics, glass, and metal. However, hardening shrinkage is neither stated nor suggested.

In addition, conventional radical polymerization-based hard coating agents have a problem in that the film is insufficiently hardened due to polymerization inhibition by oxygen, making it difficult to form a thin film coating.

This case was developed in view of the above, and its purpose is to provide: a sesquisiloxane derivative and a manufacturing method thereof. The sesquisiloxane derivative has a low curing shrinkage; and a curable composition containing the sesquisiloxane. an oxane derivative; a hardened product formed by hardening the curable composition; and a hard coating agent containing the sesquioxane derivative; a hard coating formed by hardening the hard coating agent Hardened; and a base material provided with the aforementioned hard coating layer. [Technical means to solve problems]

Technical means to solve the aforementioned problems include the following aspects. <1> A sesquisiloxane derivative represented by the following formula (1) and having a curing shrinkage rate of less than 3.0%;

In the formula (1), R ^CE is each independently a group having a cyclic ether structure, and R ¹ is each independently an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, or An aryl group with 6 to 10 atoms, or an aralkyl group with 7 to 12 carbon atoms, R ² and R ³ are each independently a hydrogen atom, a saturated or unsaturated alkyl group with 1 to 20 carbon atoms, A saturated or unsaturated cycloalkyl group with 3 to 8 carbon atoms, an aryl group with 6 to 20 carbon atoms, or an aralkyl group with 7 to 20 carbon atoms. R ⁴ is each independently a cyclic ether structure. An organic group with 2 to 12 carbon atoms, R ⁵ and R ⁶ are each independently an alkyl group with 1 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, or an aralkyl group with 7 to 10 carbon atoms. , a plurality of R ³ may be the same or different from each other, a plurality of R ⁵ may be the same or different from each other, a plurality of R ⁶ may be the same or different from each other, and R ¹ to R ⁶ may be configured independently. A part of is substituted by a substituent or a halogen atom, v is a positive number, and u, w, x, y and z are independently 0 or a positive number.

<2> The sesquioxane derivative according to <1>, wherein u, y, and z are 0 and satisfy 0≦x/(v+w)≦0.5. <3> The sesquioxane derivative according to <1>, wherein the R ^CE is a group having an oxetane structure and/or an epoxy structure. <4> The sesquioxane derivative according to <1>, wherein the R ^CE is a group having an oxetane structure. <5> The sesquioxane derivative according to any one of <1> to <4>, wherein the elastic modulus at 23° C. of the cured product obtained after curing exceeds 2.3 GPa. <6> A curable composition containing: the sesquioxane derivative according to any one of <1> to <5>; and a polymerization initiator. <7> A hard coating agent containing the curable composition according to <6>. <8> A hardened product obtained by hardening the curable composition described in <6>. <9> A hard coat layer obtained by hardening the hard coat agent described in <7>. <10> A base material provided with the hard coat layer according to <9>. <11> A method for producing a sesquisiloxane derivative according to any one of <1> to <5>, which includes: at least one of the following A step of hydrolyzing an organosilicon compound using an organic solvent and adding a total amount of water of 2 mol equivalents to 30 mol equivalents relative to the hydrolyzable groups of the organosilicon compound, n represents an integer of 0 to 3, p represents an integer of 1 to 4, and n+p=4, R represents a group bonded to a silicon atom via a carbon atom in the sesquioxane derivative, and X represents a hydrolyzable group. . [effect]

According to this case, it is possible to provide: a sesquisiloxane derivative and a manufacturing method thereof, the sesquisiloxane derivative has a low curing shrinkage; a curable composition containing the sesquisiloxane derivative; A hardened material, which is formed by hardening the curable composition; and a hard coating agent, which contains the sesquioxane derivative; a hard coating, which is formed by hardening the hard coating agent; and A base material provided with the aforementioned hard coating layer.

The embodiment of this case will be described in detail below. However, this case is not limited by the following implementation forms. In the following embodiments, the constituent elements (including element steps, etc.) are not essential unless otherwise specified. The numerical values and their ranges are also the same and are not intended to limit this case. In this specification, the numerical range expressed using "～" includes the numerical values written before and after "～" as the minimum value and the maximum value respectively. Among the numerical ranges described in stages in this specification, the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of the other numerical range described in stages. In addition, in the numerical range described in this specification, the upper limit value or the lower limit value of this numerical range can be replaced with the value disclosed in an Example. In addition, in this specification, a combination of two or more preferred aspects is a more preferred aspect.

In this specification, R ^CE and R ¹ to R ⁶ in formula (1) each independently may have a part of the structure substituted by a substituent or a halogen atom. For example, R ^CE and R ¹ to R ⁶ may each independently have a part of the structure substituted by the following groups or halogen atoms: alkyl, aryl, aralkyl, vinyl, epoxy, oxetanyl, Hydroxyl group, amine group, alkylamino group, arylamine group, aralkylamine group, ammonium group, thiol group, isocyanuric acid group, urea group, isocyanato group, carboxyl group, acid anhydride group. R ¹ to R ⁶ in formula (1) may be independently unsubstituted. For example, R ^CE , R ¹ or R ⁴ to R ⁶ (preferably R ¹ and R ⁴ to R ⁶ ) may be unsubstituted.

[Sesesquioxane derivatives] The sesquisiloxane derivative in this case is represented by the following formula (1), and the curing shrinkage rate is less than 3.0%.

In the formula (1), R ^CE is each independently a group having a cyclic ether structure, and R ¹ is each independently an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, or An aryl group with 6 to 10 atoms, or an aralkyl group with 7 to 12 carbon atoms, R ² and R ³ are each independently a hydrogen atom, a saturated or unsaturated alkyl group with 1 to 20 carbon atoms, A saturated or unsaturated cycloalkyl group with 3 to 8 carbon atoms, an aryl group with 6 to 20 carbon atoms, or an aralkyl group with 7 to 20 carbon atoms. R ⁴ is each independently a cyclic ether structure. An organic group with 2 to 12 carbon atoms, R ⁵ and R ⁶ are each independently an alkyl group with 1 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, or an aralkyl group with 7 to 10 carbon atoms. , a plurality of R ³ may be the same or different from each other, a plurality of R ⁵ may be the same or different from each other, a plurality of R ⁶ may be the same or different from each other, and R ¹ to R ⁶ may be configured independently. A part of is substituted by a substituent or a halogen atom, v is a positive number, and u, w, x, y and z are independently 0 or a positive number.

As described above, it is known that the curing shrinkage of sesquioxane derivatives is insufficient. As a result of intensive research, the present inventors discovered that by adopting the above-mentioned constitution, a sesquioxane derivative having a low curing shrinkage can be provided. We speculate that in the above formula (1), v is a positive number, and the total amount of water relative to the hydrolyzable groups of the organosilicon compound is added to be 2 mol equivalents to 30 mol equivalents to hydrolyze it, and after hardening, it can A moderate cross-linked structure is obtained, thus low hardening shrinkage.

In addition, the sesquisiloxane derivative of the present invention is also excellent in the hardness of the obtained cured product and the indentation elastic modulus of the obtained cured product.

(hardening shrinkage) From the viewpoint of hardness and indentation elastic modulus, the curing shrinkage of the sesquisiloxane derivative in this case is preferably less than 3.0%, more preferably less than 2.8%, more preferably less than 2.6%, and can be 2.0% or less. In addition, the lower limit value of the hardening shrinkage is 0%.

The method for measuring the curing shrinkage of the sesquioxane derivative in this case is as follows.

＜Measurement of Density＞ The density of the sesquioxane derivative to be measured is measured in accordance with JIS K0061-7 (2001).

＜Preparation of photocurable composition＞ When measuring a sesquisiloxane derivative whose cyclic ether structure is an epoxy structure, add 4 (pentafluorophenyl) borate (tolyl cumene) to 1 part by mass of the sesquisiloxane derivative to be measured. 0.02 parts by mass of (tolylcumyl)iodonium tetrakis (pentafluorophenyl)borate) was added, and the mixture was stirred using a rotational and revolution mixer to prepare a photocurable composition. In addition, when measuring a sesquisiloxane derivative with a cyclic ether structure other than an epoxy structure, add 0.1 parts by mass of Celloxide 2021P and 4 (pentafluorofluoride) to 0.9 parts by mass of the sesquioxane derivative to be measured. Phenyl)boric acid (tolylcumyl)iodide 0.02 parts by mass, and the mixture was stirred using a rotational and revolution mixer to prepare a photocurable composition.

<Preparation of Photocured Material> The photocurable composition is poured into a silicone mold on a release polyethylene terephthalate (PET) film, and after the release PET film is overlapped, it is placed on a glass plate. After clamping and fixing these, ultraviolet rays were irradiated and hardened under the following conditions, and a photocured material was produced. - Ultraviolet irradiation conditions - Lamp: High-pressure mercury lamp (ECS-4011GX manufactured by EYE GRAPHICS Co., Ltd.) Lamp height: 10 cm Conveyor speed: 5.75 m/min Cumulative light amount per operation: 360 mJ/cm ² (UV- A, measured value of UV POWER PUCK II manufactured by EIT) Environment: In the atmosphere Number of operations: 20 times

<Measurement of density of photocured material> The density of the photocured material was measured in accordance with JIS K0061-8 (2001).

＜Calculation of hardening shrinkage＞ It is calculated according to (density of hardened material - density before hardening)/density before hardening × 100.

(Elastic modulus of hardened material) From the viewpoint of curing shrinkage, hardness, and indentation elastic modulus, the elastic modulus at 23°C of the cured product obtained after curing the sesquioxane derivative of the present invention is preferably more than 2.3 GPa, and more preferably Preferably it exceeds 2.3 GPa and is 10.0 GPa or less, more preferably it is 2.4 GPa or more and 9.5 GPa or less, and particularly preferably it is 2.4 GPa or more and 9.0 GPa or less.

The method for measuring the elastic modulus at 23° C. of the cured product of the sesquioxane derivative in this case is as follows.

<Preparation of photocurable coating agent> When measuring a sesquisiloxane derivative whose cyclic ether structure is an epoxy structure, add 4 (pentafluorophenyl) borate (tolyl cumene) to 1 part by mass of the sesquisiloxane derivative to be measured. 0.02 parts by mass of base) iodide and 1 part by mass of propylene glycol monobutyl ether, and the mixture was stirred using a rotation and revolution mixer to prepare a photocurable coating agent. In addition, when measuring a sesquisiloxane derivative with a cyclic ether structure other than an epoxy structure, add 0.1 parts by mass of Celloxide 2021P and 4 (pentafluorofluoride) to 0.9 parts by mass of the sesquioxane derivative to be measured. A photocurable coating agent was prepared by mixing the mixture with 0.02 parts by mass of phenyl)boric acid (tolylcumenyl)iodide and 1 part by mass of propylene glycol monobutyl ether using a rotation and revolution mixer.

<Preparation of photocurable film> After applying the photocurable coating agent to the TAC (cellulose triacetate) film using a No. 20 rod coater, the applied photocurable coating was applied at 60°C. After the agent was dried for 10 minutes, ultraviolet rays were irradiated and cured under the following conditions to produce a photocured film. Under the aforementioned coating conditions, the film thickness is approximately 10 μm. - Ultraviolet irradiation conditions - Lamp: High-pressure mercury lamp (ECS-4011GX manufactured by EYE GRAPHICS Co., Ltd.) Lamp height: 10 cm Conveyor speed: 5.75 m/min Cumulative light amount per operation: 360 mJ/cm ² (UV- A, measured value of UV POWER PUCK II manufactured by EIT) Environment: In the atmosphere Number of operations: 10 times

＜Measurement of elastic modulus＞ Using the obtained photocured film, an indentation hardness measurement was performed at 23° C. using a nano indenter (Nano Indenter G200 manufactured by Agilent Technologies, using a Berkovich indenter) at a strain rate of 0.05/s. The elastic modulus is calculated by averaging the modulus values at an indentation depth of 500 nm to 800 nm.

Each structural unit that the sesquioxane derivative of the present invention can contain is called structural units (a) to (f) as follows.

In the sesquioxane derivative of this case, in formula (1), v is a positive number, and u, w, x, y and z are each independently 0 or a positive number. In other words, the sesquisiloxane derivative of the present invention contains the structural unit (b) among the above-mentioned structural units (a) to (f), and may include the structural unit (a), the structural unit (c), and the structural unit (c) as necessary. At least one kind among the structural unit (d), the structural unit (e) and the structural unit (f).

In the formula (1), u, v, w, x, y and z represent the molar ratio of the constituent units (a) to (f). In addition, in the formula (1), u, v, w, x, y and z represent the relative mol of the structural units (a) to (f) that the sesquioxane derivative represented by the formula (1) can contain. Compare. The molar ratio can be determined, for example, from the NMR (nuclear magnetic resonance) analysis value of the sesquioxane derivative in this case. In addition, when the reaction rate of each raw material of the sesquisiloxane derivative is clear, or when the yield is 100%, it can be determined from the feed amount of the raw material. For example, for the molar ratio of each structural unit of a sesquisiloxane derivative, ¹ H-NMR analysis can be performed on a sample dissolved in deuterated chloroform, and ²⁹ Si can be further analyzed if necessary. -NMR analysis to calculate. The structure of the original sesquioxane derivative can be decomposed into constituent units by a base or the like, and then the structure of the original sesquioxane derivative can be estimated from the ratio of the constituent units. The molar ratio of each structural unit of the sesquioxane derivative can be determined by combining conventional methods such as mass analysis and IR (infrared absorption spectrometry) analysis as needed.

Each of the structural units (b) to (f) in the formula (1) may be of only one type, or may be of two or more types. In addition, the arrangement order in formula (1) indicates the composition of the structural units and does not mean the arrangement order of the sesquioxane derivatives. Therefore, the condensed form of the structural units in the sesquioxane derivative of the present invention may not necessarily be as shown in the arrangement order of formula (1). Details of the structural units (a) to (f) will be described below.

(Structural unit (a)) The structural unit (a) is a Q unit having four O _1/2 (two oxygen atoms) per silicon atom. In addition, the Q unit means a unit having four O _1/2 units per silicon atom.

The proportion of the structural unit (a) in the sesquioxane derivative of the present invention is not particularly limited. For example: From the viewpoint of the viscosity of the sesquioxane derivative and the hardness of the cured product, the molar ratio (u/(u＋v＋w＋x＋y＋z)) of the structural unit (a) in all the structural units is 0.1 or less. is better, 0.05 or less is better, and 0 is better. Here, the molar ratio of 0 means that no corresponding structural unit is included, and the same meaning is used below.

(Structural unit (b)) The structural unit (b) is a group having 3 O _1/2 (1.5 as an oxygen atom) per silicon atom and having a cyclic ether structure connected to the silicon atom via R ¹ T units bonded together. In addition, the T unit means a unit having 3 O _1/2 per silicon atom.

In the structural unit (b), R ^CE is each independently a group having an oxetane structure and/or a group having an epoxy structure from the viewpoint of curing shrinkage, hardness, and indentation elastic modulus, More preferably, it is a group having an oxetane structure. In addition, from the viewpoint of curing shrinkage, hardness, press-fit elastic modulus, and ease of synthesis, R ^CE is preferably a group bonded to R ¹ with an oxygen atom. R ^CE may have only one cyclic ether structure or may have two or more cyclic ether structures, but from the viewpoint of curing shrinkage, hardness, and press-fit elastic modulus, it is preferable to have only one cyclic ether structure. Specific examples of R ^CE include: 3-ethyl-3-oxetanylmethoxy, glycidoxy, 3-methyl-3-oxetanylmethoxy, and 3 -oxetanylmethoxy, etc.

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

The alkylene group having 1 to 10 carbon atoms is preferably an alkylene group having 1 to 6 carbon atoms, an alkylene group having 2 to 4 carbon atoms is more preferred, and a propylene group is more preferred. The alkylene group having 1 to 10 carbon atoms may be a straight chain or may have branches. The cycloalkyl group having 3 to 10 carbon atoms is preferably a cycloalkyl group having 3 to 6 carbon atoms, and a cycloalkyl group having 4 to 6 carbon atoms is more preferred. The cycloalkylene group having 3 to 10 carbon atoms may have branches.

The ratio of the structural unit (b) in the sesquioxane derivative of the present invention is not particularly limited. For example: from the viewpoint of curing shrinkage, hardness, indentation elastic modulus, and ultraviolet (hereinafter also referred to as UV) curability, the mol ratio of the structural unit (b) in all the structural units (v/( u+v+w+x+y+z)) is preferably 0.3~1, more preferably 0.5~1, more preferably 0.7~1, and particularly preferably 0.9~1.

(Structural unit (c)) The structural unit (c) is a T unit having 3 O _1/2 (1.5 in terms of oxygen atom) per silicon atom, and R ² is bonded to the silicon atom.

In the structural unit (c), R ² is a hydrogen atom, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a saturated or unsaturated cycloalkyl group having 3 to 8 carbon atoms, or a saturated or unsaturated cycloalkyl group having 6 to 20 carbon atoms. an aryl group, or an aralkyl group having 7 to 20 carbon atoms.

The saturated or unsaturated alkyl group having 1 to 20 carbon atoms may be linear or branched. The saturated or unsaturated alkyl group having 1 to 20 carbon atoms is preferably a saturated or unsaturated alkyl group having 1 to 10 carbon atoms, and a saturated alkyl group having 1 to 10 carbon atoms is preferred.

Examples of the saturated alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. From the viewpoint of heat resistance and hardness of the cured product, a methyl group or an ethyl group is preferable, and a methyl group is more preferable.

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

The saturated or unsaturated cycloalkyl group having 3 to 8 carbon atoms may have branches. The saturated or unsaturated cycloalkyl group having 3 to 8 carbon atoms is preferably a saturated or unsaturated cycloalkyl group having 4 to 6 carbon atoms.

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

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

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

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

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

The proportion of the structural unit (c) in the sesquioxane derivative of the present invention is not particularly limited. For example, from the viewpoint of the hardness of a hardened material, the molar ratio (w/(u+v+w+x+y+z)) of the structural unit (c) in all structural units is preferably 0.1 or less, more preferably 0.05 or less, and 0 is better.

(Structural unit (d)) The structural unit (d) is a D unit having two O _1/2 (one oxygen atom) per silicon atom and two R ³ bonded to the silicon atom. . In addition, the D unit means a unit having two O _1/2 units per one silicon atom.

In the structural unit (d), R ³ is a hydrogen atom, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a saturated or unsaturated cycloalkyl group having 3 to 8 carbon atoms, or a saturated or unsaturated cycloalkyl group having 6 to 20 carbon atoms. an aryl group, or an aralkyl group having 7 to 20 carbon atoms. In the structural unit (d), a plurality of R ³ may be the same or different from each other. A preferred aspect of R ³ is the same as R ² in the constituent unit (c).

The proportion of the structural unit (d) in the sesquioxane derivative of the present invention is not particularly limited. For example, from the viewpoint of the hardness of a hardened product, the molar ratio (x/(u+v+w+x+y+z)) of the structural unit (d) in all the structural units is preferably 0.1 or less, more preferably 0.05 or less, and Below 0 is better. On the other hand, from the viewpoint of hardening shrinkage and bending resistance, x is preferably a positive number.

(Structural unit (e)) The structural unit (e) has 1 O _1/2 (0.5 in terms of oxygen atom) per 1 silicon atom, and 1 R ⁴ and 2 R ⁵ are bonded to the silicon atom. M unit together. In addition, the M unit means a unit having one O _1/2 per one silicon atom.

In the structural unit (e), R ⁴ is each independently an organic group having 2 to 12 carbon atoms having a cyclic ether structure. R ⁴ is preferably R ^CE -R ¹ - in the structural unit (b). In addition, the preferred aspects are also the same as the preferred aspects of R ^CE and R ¹ in the structural unit (b).

In the structural unit (e), R ⁵ is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. In the structural unit (e), a plurality of R ⁵ 's may be the same or different from each other.

Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. From the viewpoint of heat resistance and hardness of the cured product, a methyl group or an ethyl group is preferable, and a methyl group is more preferable.

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

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

The ratio of the structural unit (e) in the sesquioxane derivative of the present invention is not particularly limited. For example, from the viewpoint of curing shrinkage, hardness, storage stability, and UV curability, the mol ratio (y/(u+v+w+x+y+z)) of the structural unit (e) among all structural units is preferably 0.5 or less. It is preferably 0.3 or less, and more preferably 0.1 or less. The mol ratio (y/(u+v+w+x+y+z)) of the structural unit (e) in all the structural units may be 0 or 0.01 or more.

(Structural unit (f)) The structural unit (f) is an M unit having 1 O _1/2 (0.5 in terms of oxygen atom) per silicon atom and 3 R ⁶ bonded to the silicon atom. .

In the structural unit (f), R ⁶ is an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. In the structural unit (f), a plurality of R ^6s may be the same or different from each other. A preferred aspect of R ⁶ is the same as R ⁵ in constituent unit (e).

The proportion of the structural unit (f) in the sesquioxane derivative of the present invention is not particularly limited. For example, from the viewpoint of the hardness of a hardened material, the mol ratio (z/(u+v+w+x+y+z)) of the structural unit (f) in all the structural units is preferably 0.1 or less, more preferably 0.05 or less, and 0 is better.

(Other structural unit (g)) The sesquisiloxane derivative of the present invention may further contain (R ⁷ O _1/2 ) as a Si-free structural unit (hereinafter also referred to as structural unit (g)). Here, R ⁷ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms may be either an aliphatic group or an alicyclic group, and may be either linear or branched. Specific examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, and hexyl.

The structural unit (g) is an alkoxy group that is a hydrolyzable group contained in the silicon compound described below, or an alkoxy group generated by substituting an alcohol contained in the reaction solvent with a hydrolyzable group of the silicon compound, and may be an alkoxy group. It may be a group that remains in the molecule without hydrolysis or polycondensation, or it may be a hydroxyl group that remains in the molecule after hydrolysis without polycondensation.

In formula (1), from the viewpoint of hardening shrinkage, hardness, and indentation elastic modulus, it is preferable that u, y, and z are 0 and w and x are each independently 0 or a positive number, and it is more preferable that u , w, x, y and z are 0. In addition, in the formula (1), from the viewpoint of hardening shrinkage, hardness, and press-in elasticity modulus, it is preferable that 0≦x/(v+w)≦0.5 is satisfied, and 0≦x/(v+w) is more preferably satisfied. )≦0.3, and even better is to satisfy 0≦x/(v+w)≦0.1.

(weight average molecular weight of sesquioxane derivative) The weight average molecular weight (hereinafter also referred to as "Mw") of the sesquisiloxane derivative in this case is not particularly limited. For example, it can be 300 to 30,000, or it can be 500 to 15,000, or it can be 700 to 10,000, or it can be It is 1,000~5,000. In addition, in this case, Mw means a value obtained by converting the molecular weight measured by GPC (gel permeation chromatography) using polystyrene as a standard material. As the measurement conditions for Mw, for example, the measurement conditions in [Examples] described below can be used.

(Viscosity of sesquioxane derivatives) Among the sesquioxane derivatives in this case, the viscosity at 25°C is preferably 10 mPa·s to 50,000 mPa·s, 100 mPa·s to 40,000 mPa·s is more preferred, and 1,000 mPa·s to 30,000 mPa is preferred.・s is better, especially 2,000 mPa・s～25,000 mPa・s. Furthermore, in this case, the viscosity at 25°C refers to the value measured using an E-type viscometer (cone and plate viscometer; for example, TVE22H type viscometer manufactured by Toki Industrial Co., Ltd.).

(Production method of sesquioxane derivatives) The sesquisiloxane derivative in this case can be produced by a conventional method. The method for producing a sesquioxane derivative is disclosed in detail in International Publication No. 2013/031798 and the like as a method for producing polysiloxane.

Among them, the method for producing the sesquioxane derivative of the present invention preferably includes: using an organic solvent to at least one organosilicon compound represented below, and adding a total amount of hydrolyzable groups relative to the organosilicon compound. The step of hydrolyzing 2 mol equivalents to 30 mol equivalents of water (hereinafter also referred to as the "hydrolysis step"), n represents an integer from 0 to 3, p represents an integer from 1 to 4, and n+p=4, R represents a group bonded to a silicon atom via a carbon atom in the sesquioxane derivative, and X represents a hydrolyzable group. . Suitable examples of R include groups bonded to silicon atoms via carbon atoms in the aforementioned sesquioxane derivatives (R ^CE -R ¹ - and R ² to R ⁶ , etc.). X is preferably, for example, an alkoxy group, a silyloxy group, or a halogen atom, and more suitably is, for example, an alkoxy group, or a silyloxy group.

In the hydrolysis step, it is preferable to perform not only the hydrolysis of the aforementioned organosilicon compound, but also the hydrolysis and polycondensation reaction of the aforementioned organosilicon compound and other silicon compounds as needed. In addition, in the hydrolysis step, after the hydrolysis and polycondensation reaction of the aforementioned organic silicon compound and other silicon compounds as needed is performed to obtain an intermediate product, that is, a sesquioxane derivative, the obtained intermediate product can be further combined with the aforementioned organic silicon compound. Hydrolysis and polycondensation reactions of silicon compounds, etc.

When the intermediate product is obtained as described above, the hydrolysis and polycondensation reaction of the aforementioned organosilicon compound and other silicon compounds as required can be carried out, and then the obtained intermediate product can be further reacted with the aforementioned organosilicon compound. In the aforementioned organosilicon compound, n is 3 and p is Hydrolysis and polycondensation reactions of compounds 1. Thereby, a sesquisiloxane derivative can be more suitably synthesized, the terminal portion of which is sealed with the structural unit (e) derived from the compound in which n is 3 and p is 1 among the aforementioned organosilicon compounds, and Suppresses the viscosity increase of sesquioxane derivatives and improves storage stability.

The preferred method for producing a sesquisiloxane derivative in this case includes: performing a hydrolysis and polycondensation reaction on a silicon compound in the presence of a reaction solvent, and then distilling the reaction solvent, by-products, residual monomers and water in the reaction solution. distillation step.

Examples of the organosilicon compound having an oxetanyl group include: (3-ethyl-3-oxetanylmethoxypropyl)trimethoxysilane, (3-ethyl- 3-oxetanylmethoxypropyl)triethoxysilane, and (3-methyl-3-oxetanylmethoxypropyl)trimethoxysilane, (3-oxetanylmethoxypropyl)trimethoxysilane Heterocyclobutanylmethoxypropyl)trichlorosilane.

Examples of the epoxy group-containing organosilicon compound include: (glycidoxypropyl)trimethoxysilane, (glycidoxypropyl)triethoxysilane, and 2-(3,4 -Epoxycyclohexyl)ethyltrimethoxysilane.

Examples of organosilicon compounds that can obtain two structural units (e) by hydrolysis include: 1,3-bis(3-ethyl-3-oxetanylmethoxypropyl)tetramethyl In addition to disiloxane and 1,3-bis(glycidoxypropyl)tetramethyldisiloxane, there are also methoxydimethylvinylsilane, ethoxydimethylvinylsilane, Chlorodimethylvinylsilane, dimethylvinylsilanol, (3-acrylyloxypropyl)dimethylmethoxysilane, (3-methacrylyloxypropyl)dimethylmethoxysilane Oxysilane, p-styryldimethylmethoxysilane, and ethynyldimethylmethoxysilane, etc.

Examples of silicon compounds that can obtain the structural unit (a) by hydrolysis include tetramethoxysilane, tetraethoxysilane, and the like.

Examples of the aforementioned organosilicon compounds in which n is 3 and p is 1 include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, and octyltrimethoxysilane. Trimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane, cyclohexyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, p-styryltrimethoxysilane, ethynyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, N -2-(Aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl Butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane Silane hydrochloride, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, trimethoxysilane Propyl)isocyanurate, 3-mercaptopropyltrimethoxysilane, 3-ethyl-3-[{3-(trimethoxysilyl)propoxy}methyl]oxetane, And 3-ethyl-3-[{3-(triethoxysilyl)propoxy}methyl]oxetane, etc.

Examples of the aforementioned organosilicon compounds in which n is 2 and p is 2 include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, and propylmethyl silane. Dimethoxysilane, octylmethyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, benzylmethyldimethoxysilane, cyclohexylmethyl Dimethoxysilane, vinylmethyldimethoxysilane, allylmethyldimethoxysilane, p-styrylmethyldimethoxysilane, ethynylmethyldimethoxysilane, 2 -(3,4-Epoxycyclohexyl)ethylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, N-2-(aminoethyl)-3 -Aminopropylmethyldimethoxysilane, 3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropylmethyldimethoxysilane, N-(ethylene (benzyl)-2-aminoethyl-3-aminopropylmethyldimethoxysilane hydrochloride, 3-ureidopropylmethyldialkoxysilane, 3-isocyanic acid Propylmethyldiethoxysilane, (3-propyloxypropyl)methyldimethoxysilane, and (3-methacryloxypropyl)methyldiethoxysilane, etc. .

Among the aforementioned organosilicon compounds, compounds in which n is 1 and p is 3 include, for example: hexamethyldisiloxane, trimethylmethoxysilane, triethylethoxysilane, trimethylsilyl chloride, and Dimethylphenylmethoxysilane, etc.

In the hydrolysis step, the reaction solvent is not particularly limited, but alcohols as organic solvents are preferably used. Alcohols are alcohols in a narrow sense represented by the general formula R—OH, and are compounds having no functional groups other than alcoholic hydroxyl groups. The alcohol is not particularly limited, and examples thereof include methanol, ethanol, 1-propanol, 2-propanol, 2-butanol, 2-pentanol, 3-pentanol, 2-methyl-2-butanol, 3 -Methyl-2-butanol, cyclopentanol, 2-hexanol, 3-hexanol, 2-methyl-2-pentanol, 3-methyl-2-pentanol, 2-methyl-3- Pentanol, 3-methyl-3-pentanol, 2-ethyl-2-butanol, 2,3-dimethyl-2-butanol, and cyclohexanol, etc. Among them, 2-propanol, 2-butanol, 2-pentanol, 3-pentanol, 3-methyl-2-butanol, cyclopentanol, 2-hexanol, 3-hexanol, 3 Secondary alcohols such as methyl-2-butanol and cyclohexanol are preferred. In the hydrolysis step, one type of these alcohols may be used, or two or more types of these alcohols may be used in combination.

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

The hydrolysis and polycondensation reactions in the hydrolysis step are carried out in the presence of water. In the hydrolysis step, it is preferable to add water in a total amount of 2 mol equivalents to 30 mol equivalents based on the total amount of hydrolyzable groups of the organosilicon compound to cause hydrolysis and further condensation. In addition, in the hydrolysis step, from the viewpoint of curing shrinkage, hardness, storage stability, and curl-inhibiting properties during curing of the obtained sesquioxane derivative, the hydrolyzable group possessed by the organosilicon compound is The total amount of water added is preferably 2 mol equivalent to 8 mol equivalent, preferably 2.2 mol equivalent to 7 mol equivalent, and particularly preferably 2.4 mol equivalent to 6 mol equivalent.

In addition, the hydrolysis and polycondensation reaction of the silicon compound may be performed without using a catalyst, or may be performed using 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; ammonia, tetramethylammonium hydroxide, Alkaline catalysts such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, etc. It is better to use an alkaline catalyst. Relative to the total amount of silicon atoms (mol) contained in the silicon compound, the amount of the catalyst used is preferably equivalent to 0.01 mol% to 20 mol%, and is preferably equivalent to 0.1 mol% to 10 mol%. good.

The completion of the hydrolysis and polycondensation reactions in the hydrolysis step can be appropriately detected by methods described in various publications and the like. Furthermore, in the hydrolysis step of the method for producing a sesquioxane derivative of the present invention, an auxiliary agent can be added to the reaction system.

By providing the aforementioned distillation step after the hydrolysis step in the production of the sesesquioxane derivative of the present invention, the stability of the produced sesquisiloxane derivative of the present invention can be improved. Distillation can be performed under normal pressure or reduced pressure, at normal temperature or under heating, or under cooling.

The method for producing a sesquioxane derivative can include a neutralization step of neutralizing the catalyst before the distillation step. In addition, a step of removing salt generated by neutralization by washing with water or the like may be provided.

In addition, the sesquisiloxane derivative represented by the formula (1) may include a cyclic ether structure added to a side chain functional group derived from a silicon compound used as a raw material during production by adding an acid or the like to open the ring. It may also include a hydroxyalkyl group generated by the decomposition of an organic group having a cyclic ether structure, or a group in which an acid or the like is added to an unsaturated hydrocarbon group or the like. Specific examples thereof include those in which a part of the formula (1) contains a structure represented by the following formula (A) and/or a structure represented by the formula (B). The content ratio only needs to be relative to an organic group having an original oxetane structure or an epoxy structure, an organic group having an original (meth)acrylyl group, or an organic group having an original (meth)acrylyl group derived from the silicon compound that is the raw material. If the amount of the unsaturated hydrocarbon organic group is 50 mol% or less, it will not hinder the implementation of the present invention. It is preferably 30 mol% or less, and more preferably 10 mol% or less. In formula (A) and formula (B), T unit is exemplified, but the same D unit, M unit, etc. may also be used.

[Hardening composition] The curable composition in this case includes: the sesquioxane derivative in this case; and a polymerization initiator. The curable composition of this invention can be suitably used as a hard coating agent. The curable composition in this case may contain various components (hereinafter also referred to as "other components") as needed.

(polymerization initiator) The polymerization initiator is not particularly limited, and examples thereof include photopolymerization initiators and thermal polymerization initiators. Examples of the photopolymerization initiator include photocationic polymerization initiators. Examples of the thermal polymerization initiator include thermal cationic polymerization initiators. As the photopolymerization initiator and the thermal polymerization initiator, conventional compounds can be used.

Examples of the photocationic polymerization initiator include onium salts such as iodonium salts, sulfonium salts, diazonium salts, selenium salts, pyridinium salts, ferrocenium salts, and phosphonium salts. Among these, iodine salt or strontium salt is preferred. When the photocationic polymerization initiator is a iodonium salt or a sulfonium salt, the relative anion may be, for example: BF ₄ ^- , ASF ₆ ^- , SbF ₆ ^- , PF ₆ ^- , B(C ₆ F ₅ ) ₄ ^- , etc.

Examples of the aforementioned iodonium salts include: tetrafluorophenyl (tricumenyl)iodonium borate, diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoroantimonate, diphenyl iodonium tetrafluoroborate, iodine ( Diphenyl pentafluorophenyl)borate, bis(dodecylphenyl)iodide hexafluorophosphate, bis(dodecylphenyl)iodino hexafluoroantimonate, bis(dodecylbenzene tetrafluoroborate) 4-(pentafluorophenyl)boronate, 4-methylphenyl-4-(1-methylethyl)phenylphosphine hexafluorophosphate, antimony hexafluoride 4-Methylphenyl-4-(1-methylethyl)phenylphosphonium acid, 4-methylphenyl-4-(1-methylethyl)phenylphosphonium tetrafluoroborate, tetrafluoroborate Phenyl)boronic acid 4-methylphenyl-4-(1-methylethyl)phenyl iodide, etc. In addition, commercially available products can also be used as the above-mentioned ion salt. Specific examples include: "UV9380C" (trade name) manufactured by Mentive Performance Materials Japan; "PHOTOINITIATOR2074" (trade name) manufactured by Solvay Japan; FUJIFILM Wako Pure Chemical Co., Ltd. Co., Ltd. "WPI-116" (trade name) and "WPI-113" (trade name), etc.

Examples of the aforementioned sulfonium salt include: bis(hexafluorophosphoric acid)bis[4-(diphenylsoniumyl)phenyl]sulfide, bis(hexafluoroantimonate)bis[4-(diphenylsoniumyl)phenyl ] sulfide, bis(tetrafluoroborate)bis[4-(diphenylsulfonyl)phenyl]sulfide, tetrafluoroborate bis[4-(diphenylsulfonyl)phenyl]sulfide Ether, diphenyl-4-(phenylthio)phenylsulfonium hexafluorophosphate, diphenyl-4-(phenylthio)phenylsulfonate hexafluoroantimonate, diphenyl-4-(phenyltetrafluoroborate) Thio)phenylsulfonium, diphenyl-4-(phenylthio)phenylsulfonium tetra(pentafluorophenyl)borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, tetrafluoroboric acid Triphenylsulfonium, tetra(pentafluorophenyl)triphenylsulfonate, bis(hexafluorophosphoric acid)bis[4-(bis(4-(2-hydroxyethoxy))phenylsulfonyl)phenyl] Sulfide, bis(hexafluoroantimonate)bis[4-(bis(4-(2-hydroxyethoxy))phenylsulfonyl)phenyl]sulfide, bis(tetrafluoroborate)bis[4-( Bis(4-(2-hydroxyethoxy)phenylsulfonyl)phenyl]sulfide, and bis(pentafluorophenyl)borate bis[4-(bis(4-(2-hydroxyethoxy)) )phenyl sulfonyl) phenyl] sulfide, etc. In addition, commercially available strontium salts can also be used. Specific examples include "CYRACURE UVI-6990" (trade name), "CYRACURE UVI-6992" (trade name) and "CYRACURE UVI-6974" manufactured by Dow Chemical Co., Ltd. of Japan. "(trade name); "Adeka Optomer SP-150" (trade name), "Adeka Optomer SP-152" (trade name), "Adeka Optomer SP-170" (trade name), "Adeka Optomer" made by ADEKA Co., Ltd. SP-172" (trade name); "WPAG-370" (trade name) and "WPAG-638" (trade name) manufactured by FUJIFILM Wako Pure Chemical Co., Ltd., etc.

Examples of the aforementioned diazonium salt include benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, and benzenediazonium hexafluoroborate.

The thermal cationic polymerization initiator is not particularly limited, and examples thereof include sulfonium salts, phosphonium salts, quaternary ammonium salts, and the like. Among these, sodium salt is the best. Examples of the relative anion in the thermal cationic polymerization initiator include AsF ₆ ^- , SbF ₆ ^- , PF ₆ ^- , B(C ₆ F ₅ ) ₄ ^- , etc.

Examples of the aforementioned sulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsenate, tris(4-methoxyphenyl)sulfonium hexafluoroarsenate, and Diphenyl(4-phenylthiophenyl)hexafluoroarsenate, etc. In addition, commercially available products can also be used as the above-mentioned strontium salt. Specific examples include "Adeka Optomer CP-66" (trade name) and "Adeka Optomer CP-77" (trade name) manufactured by ADEKA Co., Ltd.; Sanshin "SAN-AID SI-60L" (trade name), "SAN-AID SI-80L" (trade name), "SAN-AID SI-100L" (trade name), etc. manufactured by Chemical Industry Co., Ltd.

Examples of the phosphonium salt include ethyltriphenylphosphonium hexafluoroantimonate, tetrabutylphosphonium hexafluoroantimonate, and the like. Examples of the aforementioned quaternary ammonium salt include: N,N-dimethyl-N-benzylanilinium hexafluoroantimonate, N,N-diethyl-N-benzylanilinium tetrafluoroborate, hexafluoroantimonate N,N-dimethyl-N-phenylpyridinium antimonate, N,N-diethyl-N-phenylpyridinium trifluoromethanesulfonate, N,N-dimethylhexafluoroantimonate Methyl-N-(4-methoxybenzyl)pyridinium salt, N,N-diethyl-N-(4-methoxybenzyl)pyridinium hexafluoroantimonate, hexafluoroantimonyate N,N-diethyl-N-(4-methoxybenzyl)toluidine acid, and N,N-dimethyl-N-(4-methoxybenzyl)toluene hexafluoroantimonate Ammonium etc.

A polymerization initiator can be used individually by 1 type, or in combination of 2 or more types. In the curable composition of the present invention, the content of the polymerization initiator is preferably 0.01 to 20 parts by mass, and preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the sesquioxane derivative represented by formula (1). 10 parts by mass is preferred, and 1 to 5 parts by mass is more preferred.

(other ingredients) Other components are not particularly limited, and examples thereof include solvents, polymerizable compounds other than the sesquisiloxane derivative represented by formula (1), resins, silica, monomers, fillers, surfactants, and antistatic agents (for example, Conductive polymer), leveling agent, photosensitizer, ultraviolet absorber, antioxidant, heat resistance improver, stabilizer, lubricant, pigment, dye, plasticizer, suspending agent, adhesion imparting agent agents, nanoparticles, nanofibers, nanoflakes, etc. The curable composition in this case may include: silane-based reactive diluents such as tetraalkoxysilanes, trialkoxysilanes, dialkoxysilanes, monoalkoxysilanes, and disiloxanes, etc. .

The curable composition in this case may or may not contain a solvent. Examples of the solvent include aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, chlorinated hydrocarbon solvents, alcohol solvents, ether solvents, amide solvents, ketone solvents, ester solvents, and cellulose solvents. organic solvents.

The curable composition of the present invention may or may not contain polymerizable compounds other than the sesquioxane derivative represented by formula (1) (hereinafter also referred to as "other polymerizable compounds"). The other polymerizable compound is not particularly limited as long as it can undergo a polymerization reaction in the presence of the sesquioxane derivative represented by formula (1) and a polymerization initiator. Examples of other polymerizable compounds include sesquisiloxane derivatives other than the sesquisiloxane derivative represented by formula (1), epoxy compounds (compounds having an epoxy group), compounds having an oxetanyl group compounds (oxetanyl group-containing compounds), compounds having vinyl ether groups (vinyl ether compounds), (meth)acrylate compounds, compounds having ethylenically unsaturated groups, etc. Among them, when R ^CE in formula (1) is a group having an oxetane structure, from the viewpoint of curing shrinkage, hardness, and indentation elastic modulus, it is preferable to contain an epoxy compound. and a compound having an oxetanyl group, preferably at least one compound selected from the group consisting of an epoxy compound, and particularly preferably a polyfunctional epoxy compound.

Examples of sesquisiloxane derivatives other than the sesquisiloxane derivative represented by formula (1) include sesquisiloxane derivatives consisting only of T units, and sesquisiloxane derivatives containing T units and D units. Siloxane derivatives, etc.

Examples of the epoxy compound include monofunctional epoxy compounds, polyfunctional epoxy compounds, and the like. Examples of the oxetanyl group-containing compound include monofunctional oxetane compounds, polyfunctional oxetane compounds, and the like. Examples of vinyl ether compounds include monofunctional vinyl ether compounds, polyfunctional vinyl ether compounds, and the like. As such compounds, for example, compounds described in Japanese Patent Application Laid-Open No. 2011-42755 can be used.

Examples of polyfunctional epoxy compounds include: dicyclopentadiene dioxide, limonene dioxide, 4-vinylcyclohexene dioxide, 3,4-epoxycyclohexylcarboxylic acid (3,4-cyclohexylcarboxylic acid) Oxycyclohexyl)methyl ester (such as "CELLOXIDE 2021P" (trade name) manufactured by DAICEL Co., Ltd.), di(3,4-epoxycyclohexyl adipate), bisphenol A type epoxy resin, halogenated Bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol S diglycidyl ether, bisphenol F epoxy resin, 1,6-hexanediol diglycidyl ether, polytetraethylene Methyl glycol diglycidyl ether, a compound in which both ends of polybutadiene are etherified with glycidyl groups, o-cresol novolak type epoxy resin, m-cresol novolak type epoxy resin, para-cresol novolak type epoxy resin, Phenol novolak type epoxy resin, phenol novolak type epoxy resin, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, polybutadiene internal epoxide, manufactured by DAICEL Co., Ltd. Compounds such as "EPOFRIEND" (trade name) in styrene-butadiene copolymers in which part of the double bonds are epoxidized, "L-207" (trade name) manufactured by KRATON, etc., which have an ethylene-butene copolymer part and Compounds in which a part of the isoprene polymer part in the block copolymer of the isoprene polymer part is epoxidized, such as "EHPE3150" (trade name) manufactured by DAICEL Co., Ltd., has a 4-vinyl ring Compounds with a structure in which a vinyl group is epoxidized in a ring-opened polymer of hexene oxide, and cage-like sesquioxanes having a glycidyl group such as "Q-4" in the "Q8 series" manufactured by Mayaerials. , "Q-5" in the "Q8 Series" manufactured by Mayaerials Corporation, alicyclic cage-type sesquioxanes with epoxy groups, epoxy group-containing sesquioxane compounds, epoxidized vegetable oils, etc. Examples of monofunctional epoxy compounds include α-olefin epoxides such as 1,2-epoxyhexadecane, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, and dodecyl ether. Glycidyl ether, glycidyl methacrylate, etc. Examples of polyfunctional oxetane compounds include: 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene (XDO), bis[2- (3-oxetanyl)butyl]ether (DOX), 1,4-bis[(3-ethyloxetan-3-yl)methoxy]benzene (HQOX), 1, 3-bis[(3-ethyloxetan-3-yl)methoxy]benzene (RSOX), 1,2-bis[(3-ethyloxetan-3-yl)methyl Oxy]benzene (CTOX), 4,4'-bis[(3-ethyloxetan-3-yl)methoxy]biphenyl (4,4'-BPOX), 2,2'- Bis[(3-ethyl-3-oxetanyl)methoxy]biphenyl (2,2'-BPOX), 3,3',5,5'-tetramethyl[4,4' -Bis(3-ethyloxetan-3-yl)methoxy]biphenyl (TM-BPOX), 2,7-bis[(3-ethyloxetan-3-yl) Methoxy]naphthalene (2,7-NpDOX), 1,6-bis[(3-ethyloxetan-3-yl)methoxy]-2,2,3,3,4,4 ,5,5-octafluorohexane (OFH-DOX), 3(4),8(9)-bis[(1-ethyl-3-oxetanyl)methoxymethyl]-tris Cycl[5.2.1.0 ^2.6 ]decane, 1,2-bis[2-[(1-ethyl-3-oxetanyl)methoxy]ethylthio]ethane, 4,4'- Bis[(1-ethyl-3-oxetanyl)methyl]thiodiphenyl sulfide, 2,3-bis[(3-ethyloxetan-3-yl)methoxy methyl]norbornane (NDMOX), 2-ethyl-2-[(3-ethyloxetan-3-yl)methoxymethyl]-1,3-0-bis[( 1-ethyl-3-oxetanyl)methyl]propane-1,3-diol (TMPTOX), 2,2-dimethyl-1,3-0-bis[(3-ethyl) Oxetan-3-yl)methyl]propan-1,3-diol (NPGOX), 2-butyl-2-ethyl-1,3-0-bis[(3-ethyloxa) cyclobutan-3-yl)methyl]propan-1,3-diol, 1,4-0-bis[(3-ethyloxetan-3-yl)methyl]butan-1, 4-diol, 2,4,6-0-shen[(3-ethyloxetan-3-yl)methyl]isocyanuric acid, bisphenol A and 3-ethyl-3-chloro Methyl oxetane (hereinafter referred to as "OXC") etherate (BisAOX), bisphenol F and OXC etherate (BisFOX), phenol novolac and OXC etherate (PNOX), cresol novolac And OXC etherate (CNOX), oxetanyl sesquioxane (OX-SQ), 3-ethyl-3-hydroxymethyloxetane silane oxide (OX-SC) wait.

Examples of polyfunctional vinyl ether compounds include cyclohexanedimethanol divinyl ether, triethylene glycol divinyl ether, novolak-type divinyl ether, and the like. Examples of the monofunctional vinyl ether compound include hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, dodecyl vinyl ether, allyl ether propylene carbonate, and cyclohexyl vinyl ether.

The silicone is not particularly limited, and conventional ones can be used. Examples include: polydimethylsiloxy, polydiphenylsiloxy, and polymethylphenylsiloxy. Preferably, the terminals and/or side chains thereof are Has functional groups. The functional group is not particularly limited, and examples thereof include: (meth)acrylyl group, epoxy group, oxetanyl group, vinyl group, hydroxyl group, carboxyl group, amino group, and thiol group.

The (meth)acrylate compound is not particularly limited, and examples thereof include compounds having one (meth)acrylyl group (hereinafter also referred to as “monofunctional (meth)acrylate”), and compounds having two or more (meth)acrylyl compound (hereinafter also referred to as "polyfunctional (meth)acrylate").

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; Cyclohexyl (meth)acrylate, tertiary butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and tricyclodecanemethanol (meth)acrylate have alicyclic groups. Monofunctional (meth)acrylate; Monofunctional (meth)acrylates with aromatic groups such as benzyl (meth)acrylate and phenyl (meth)acrylate; (Meth)acrylate of phenol ethylene oxide adduct, (meth)acrylate of phenol ethylene oxide adduct, (meth)acrylate of modified nonylphenol ethylene oxide adduct , and (meth)acrylate of nonylphenol propylene oxide adduct, (meth)acrylate of alkylene oxide adduct of p-cumenylphenol, o-phenylphenol (meth)acrylate, and (meth)acrylate esters of alkylene oxide adducts of phenolic derivatives such as o-phenylphenol and other alkylene oxide adducts; Monofunctional (meth)acrylates with alkoxyalkyl groups such as 2-ethylhexylcarbitol (meth)acrylate; Monofunctional (meth)acrylates with heterocyclic rings such as tetrahydrofurfuryl (meth)acrylate and N-(2-(meth)acryloxyethyl)hexahydrophthalimide; (Meth)hydroxyalkyl acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and hydroxyhexyl (meth)acrylate; Monofunctional (meth)acrylates with hydroxyl and aromatic groups such as 2-hydroxy-3-phenoxypropyl (meth)acrylate; Alkanediol mono(meth)acrylate, diethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, tripropylene glycol mono(meth)acrylate, etc. base) acrylate; and Monofunctional (meth)acrylates having carboxyl groups such as ω-carboxy polycaprolactone mono(meth)acrylate and mono(meth)acryloyloxyethyl phthalate.

Examples of polyfunctional (meth)acrylates include: Polyethylene glycol di(meth)acrylate such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate; Polypropylene glycol di(meth)acrylate 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, ethylene 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 triacrylate Methylolpropane tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dimethacrylate Pentaerythritol hexaacrylate, etc.

Polyfunctional (meth)acrylates can also use urethane (meth)acrylates. Examples of urethane (meth)acrylates include compounds obtained by addition reaction of organic polyisocyanates and hydroxyl-containing (meth)acrylates; polyisocyanates, polyols, and hydroxyl-containing (meth)acrylic acid; Compounds formed by the addition reaction of esters, etc. Only one type of monofunctional (meth)acrylate, polyfunctional (meth)acrylate, etc. may be used, two or more types may be used in combination, and different types may be used in combination.

Here, examples of polyols include low molecular weight polyols, polyether polyols, polyester polyols, polycarbonate polyols, and the like. Examples of low molecular weight polyols include ethylene glycol, propylene glycol, neopentyl glycol, cyclohexanedimethanol, and 3-methyl-1,5-pentanediol. Examples of the polyether polyol include polypropylene glycol, polytetramethylene glycol, and the like. Examples of polyester polyols include reactants of low molecular weight polyols and/or polyether polyols; and adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid, and terephthalic acid. Dibasic acids such as dicarboxylic acid or acid components such as their anhydrides. Only one type of these may be used, two or more types may be used in combination, and different types may be used in combination.

Examples of the organic polyisocyanate include toluene diisocyanate, xylene diisocyanate, tetramethylxylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and hexylene diisocyanate. Methyl diisocyanate, isophorone diisocyanate, etc. Examples of the hydroxyl-containing (meth)acrylate include: (meth)acrylic acid 2-hydroxyethyl ester, (meth)acrylic acid 2-hydroxypropyl ester, (meth)acrylic acid 4-hydroxybutyl ester, etc. (meth) Hydroxyalkyl acrylate; pentaerythritol tri(meth)acrylate, di(meth)acrylate of 3 mol alkylene oxide adduct of isocyanuric acid, and dipentaerythritol penta(meth)acrylate and other hydroxyl-containing Multifunctional (meth)acrylates, etc. Only one type of these may be used, two or more types may be used in combination, and different types may be used in combination.

In the curable composition of this case, when a (meth)acrylate compound is used together, the blending ratio is not particularly limited. For example, the (meth)acrylate compound is derived from the sesquioxane represented by the aforementioned formula (1). The blending ratio of 100 parts by mass of the material is preferably 0 to 100 parts by mass, more preferably 0 to 50 parts by mass, and even more preferably 0 to 20 parts by mass. From the viewpoint of adhesion to the inorganic material layer, the proportion of the (meth)acrylate compound is preferably low, and preferably does not contain it or is 10% by mass or less based on the total amount of the composition. Content, more preferably does not contain or has a content of 5% by mass or less relative to the total amount of the composition, still more preferably does not contain or has a content of 1% by mass or less relative to the total amount of the composition, particularly preferably does not contain .

A compound having one ethylenically unsaturated group per molecule other than the aforementioned (meth)acrylate compound may be added to the curable composition. The aforementioned ethylenically unsaturated group is preferably a (meth)acrylyl group, a maleimide group, a (meth)acrylamide group, or a vinyl group. Specific examples of the compound having an ethylenically unsaturated group include: (meth)acrylic acid, a Michael addition type dimer of acrylic acid, N-(2-hydroxyethyl)citraconidine, N,N-dimethylacrylamide, acryloylmorpholine, N-vinylpyrrolidone, and N-acetylcaprolactamide, etc. Only one type of these may be used, or two or more types may be used in combination.

When the curable composition of the present invention contains other polymerizable compounds, the content of the other polymerizable compounds is preferably 0.01 to 100 parts by mass relative to 100 parts by mass of the sesquioxane derivative represented by formula (1). The amount is preferably from 0.1 parts by mass to 50 parts by mass, and more preferably from 1 to 25 parts by mass.

[hardened material] The cured product in this case is obtained by hardening the curable composition in this case. For example, the cured product of the present invention can be obtained by irradiating the curable composition of the present invention with active energy rays or heating the curable composition of the present invention.

When the curable composition of the present invention is cured, the curable composition may be applied to the base material. The curable composition in this case may or may not contain a solvent. When a solvent is included, it is preferred to remove the solvent before hardening.

When the curable composition of the present invention is applied to a base material, the method of applying the curable composition is not particularly limited. Examples of the coating method include general coating methods such as casting method, spin coating method, rod coating method, dip coating method, spray coating method, roll coating method, flow coating method, and gravure coating method. method. The thickness of the curable composition applied in this case is not particularly limited and can be appropriately set depending on the purpose. The base material to be coated with the curable composition in this case is not particularly limited, and examples include wood, metal, inorganic materials, plastic, paper, fiber, and cloth. Examples of metals include copper, silver, iron, aluminum, silicon, silicon steel, and stainless steel. Examples of inorganic materials include: metal oxides such as aluminum oxide, silicon oxide, magnesium oxide, zirconium oxide, zinc oxide, indium tin oxide, and gallium oxide; metal nitrides such as aluminum nitride, gallium nitride, and silicon nitride; silicon carbide , and boron nitride and other ceramics; mortar, concrete, and glass, etc. Specific examples of plastics include acrylic resins such as polymethyl methacrylate, polyester resins such as polyethylene terephthalate, polyvinyl chloride resin, polycarbonate resin, epoxy resin, and nylon. , polyamide resins such as arylamide resins, polyimide resins, polyamide imine resins, fluororesins such as tetrafluoroethylene resins, polyolefin resins such as cross-linked polyethylene resins, vinylidene chloride resins, acrylonitrile -Butadiene-styrene (ABS) resin, polystyrene resin, polyacrylonitrile resin, cycloolefin polymer (COP), cycloolefin copolymer (COC), acetate resin, polyacrylate, celluloid Triacetate, norbornene-based resin, cellulose acetate resin such as triacetylcellulose (TAC), polychloroprene, polyphenylene sulfide, polyether, polyetheretherketone, polyurethane (polyurethane) resin, And composite resins such as glass epoxy resin; various fiber reinforced resins, etc. Examples of fibers include natural fibers, regenerated fibers, semi-synthetic fibers, metal fibers, glass fibers, carbon fibers, ceramic fibers, and conventional chemical fibers. The fabric may be a woven fabric or a non-woven fabric, and may be produced using, for example, the aforementioned fibers. These materials can be used alone, or two or more types can be used in combination, mixture, or compounding. The shape of the substrate is not particularly limited, and examples thereof include plate, flake, film, rod, ball, fiber, powder, lens, and other regular or irregular shapes.

(hardening method) In this case, the hardening method and hardening conditions are selected depending on whether the hardenable composition is active energy ray hardenable and/or thermal hardenable. In addition, the curing conditions (for example, the type of light source and the amount of irradiation in the case of active energy ray curability, and the heating temperature and heating time in the case of thermosetting property) are determined according to the polymerization agent contained in the present composition. The type and amount of the initiating agent and the type of other polymerizable compounds should be appropriately selected.

(1) Active energy ray curing method When the present composition is an active energy ray curable composition, the curing method may be irradiation with active energy rays using a conventional active energy ray irradiation device or the like. Examples of active energy rays include electron beams, light such as ultraviolet rays, visible rays, and X-rays. Light is preferred, and ultraviolet rays are preferred because a low-cost device can be used. Examples of ultraviolet irradiation devices include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, ultraviolet (UV) electrodeless lamps, chemical lamps, black light lamps, microwave-excited mercury lamps, and luminescent lamps. Diode (LED), etc. The irradiation intensity of the film coated with this composition can be selected according to the purpose, use, etc., and the activation of the active energy ray polymerization initiator (when it is photocurable, it is called a photopolymerization initiator) The effective light wavelength range (although it varies depending on the type of photopolymerization initiator, it is preferable to use light with a wavelength of 220 nm to 460 nm) is 0.1 mW/cm ² to 1000 mW/cm ² good. In addition, the irradiation energy should be appropriately set according to the type, deployment composition, etc. of the active energy rays. The irradiation time of the film can be selected according to the purpose, use, etc., but it is preferable that the cumulative light amount expressed as the product of the irradiation intensity and the irradiation time in the above-mentioned light wavelength range is 10 mJ/cm ² to 7,000 mJ/ Set the illumination time in cm ² . The cumulative light amount is preferably 200 mJ/cm ² to 5,000 mJ/cm ² , and further preferably 500 mJ/cm ² to 4,000 mJ/cm ² . If the integrated light amount is within the above range, the composition will be cured smoothly, and a uniform cured product can be easily obtained.

In addition, heat hardening can also be appropriately combined before and/or after light hardening. For example, it is also possible to perform two-stage curing in which the present composition is immersed in a base material or the like having a portion that will become a dark place when illuminated, and then the composition is irradiated, and the portion that is exposed to light is first exposed to the present composition. The object is hardened, and then heated to harden the composition in the parts that cannot be exposed to light. Such a base material is not particularly limited, and examples thereof include fabric-like, fibrous, powdery, porous, concavo-convex, and other complex-shaped base materials. It may also be a combination of two or more of these shapes. shape.

(2) Thermal hardening method When the present composition is a thermosetting composition, its hardening method and hardening conditions are not particularly limited. The hardening temperature is preferably 80°C to 200°C, more preferably 100°C to 180°C, and more preferably 110°C to 150°C. The hardening temperature can be set to a constant temperature or can be raised. It is also possible to combine heating and cooling. The hardening time is appropriately selected depending on the type of thermal polymerization initiator and the content ratio of other components. It is preferably 10 minutes to 360 minutes, more preferably 30 minutes to 300 minutes, and more preferably 60 minutes to 240 minutes. By curing the composition under the above-mentioned preferred conditions, a uniform cured film without swelling, cracks, etc. can be formed.

(Applications of sesquioxane derivatives, etc.) Since the hardened material in this case has excellent hardness, it can be used in hard coatings, optical components, etc. Furthermore, by hardening the hard coating agent containing the curable composition of the present invention, a hard coating layer having excellent hardness can be obtained. The hard coating agent in this case can be disposed on the base material. For example, by hardening the hard coating agent coated on the base material, a base material with a hard coating layer can be obtained. The hard coating agent in this case can contain various ingredients according to needs. The sesquisiloxane derivative in this case has low viscosity and can produce a cured product with excellent hardness. Due to its low viscosity, it has excellent coating properties without solvent, and even if a solvent is used, its usage amount can be reduced. Since the sesquisiloxane derivative in this case has low viscosity, it can be suitably used for applications requiring low viscosity. For example: adhesive applications, printing applications such as inkjet and 3D printing, coating agent applications, nanoprinting applications, etc. In addition, when applied to nanoprinting applications, the sesquioxane derivative in this case has excellent fine transferability due to its low viscosity. In addition, since the sesquisiloxane derivative of the present invention can be used without a solvent, it can be hardened directly after flowing into the mold. The sesquisiloxane derivative of this invention can be used together with a filler, other polymerizable compounds, etc. In addition, since the sesquisiloxane derivative in this case has low viscosity, it can also be mixed with a large amount of fillers.

The elastic modulus at 23°C of the hardened material of this application or the hard coating layer of this application is preferably more than 2.3 GPa, more preferably more than 2.3 GPa and not more than 10.0 GPa, still more preferably not less than 2.4 GPa and not more than 9.5 GPa, The best value is 2.4 GPa or more and 9.0 GPa or less. [Example]

This case will be specifically described below based on Examples and Comparative Examples. This case is not limited by the following examples.

(Measurement of weight average molecular weight) The weight average molecular weight (Mw) of the sesquioxane derivative in each Example and each Comparative Example was measured in the following manner. Specifically, a gel permeation chromatograph (manufactured by TOSOH Co., Ltd., HLC-8320GPC, hereinafter abbreviated as "GPC") was used, and a GPC column "TSK gel SuperMultiporeHZ-M" was used at 40°C in a tetrahydrofuran solvent. (manufactured by TOSOH Co., Ltd.), and the molecular weight in terms of standard polystyrene was calculated from the residence time.

(Measurement of viscosity) The viscosity at 25° C. of the sesquisiloxane derivative in each Example and each Comparative Example was measured using a TVE22H viscometer manufactured by Toki Sangyo Co., Ltd.

(Measurement of density) The density of the sesquioxane derivative in each Example and each Comparative Example was measured based on JIS K0061-7.

(Calculation of the molar ratio of each structural unit of the sesquioxane derivative) For the molar ratio of each structural unit of the sesquioxane derivative in each example and each comparative example, for the molar ratio of each structural unit dissolved in deuterated chloroform The sample is subjected to ¹ H-NMR analysis, and if necessary, further ²⁹ Si-NMR analysis is performed to calculate.

<Example 1> (Synthesis of sesquioxane derivatives) Measure (3-ethyl-3-oxetanylmethoxy)propyltrimethoxysilane (the following compound, 83.5 g, 0.3 mol) and 2-propanol (44.9 g) until a thermometer is installed , dropping funnel and stirring wing in a 300 mL 4-neck round-bottomed flask. Separately, tetramethylammonium hydroxide (2.74 g, 7.5 mmol) and pure water (43.4 g) were mixed to prepare an aqueous solution. The reaction solution was stirred while the aqueous solution prepared as a mixed solution was added dropwise from a dropping funnel over about 1 hour, and then stirred at 80° C. for 1 hour. The amount of water added was 2.8 mol times with respect to the total amount of hydrolyzable groups of the raw material organosilicon compound. The reaction solution was neutralized with a mixed aqueous solution of concentrated sulfuric acid (0.41 g, 4 mmol) and pure water (7.7 g), and then the solvent and the like were distilled off under reduced pressure. After adding diisopropyl ether, the solution was moved to a separatory funnel, washed with pure water, dehydrated, and the solvent was distilled off under reduced pressure to obtain sesquioxane, a colorless and transparent liquid. Derivative (OX-1) 60 g. The synthesized sesquisiloxane derivative (OX-1) has a viscosity of 10,000 mPa·s at 25°C and a weight average molecular weight (Mw) of 2,530.

<Examples 2 and 3> Except for changing the heating temperature as shown in Table 1 instead of Example 1, the same procedure as in Example 1 was carried out to obtain sesquioxane derivatives (OX-2, GL-1). Furthermore, in Example 3, glycidoxypropyltrimethoxysilane was used instead of (3-ethyl-3-oxetanylmethoxy)propyltrimethoxysilane. Regarding the synthesized sesquisiloxane derivatives (OX-2, GL-1), the amount of water added during synthesis, the molar ratio of each structural unit in the sesquisiloxane derivative, the viscosity at 25°C, and The weight average molecular weight (Mw) is shown in Table 1.

<Comparative Examples 1 to 3> Except for changing the amount of water added and the heating temperature as shown in Table 1 instead of Example 1, the same procedure as Example 1 was carried out to obtain sesquioxane derivatives (OX-C1, OX-C2, GL-C1). ). Furthermore, in Comparative Example 3, glycidoxypropyltrimethoxysilane was used instead of (3-ethyl-3-oxetanylmethoxy)propyltrimethoxysilane. Regarding the synthesized sesquisiloxane derivatives OX-C1, OX-C2, and GL-C1, the amount of water added during synthesis, the viscosity at 25°C, and the weight average molecular weight (Mw) are as shown in Table 1.

(Preparation of photocurable coating agent when R ^CE in formula (1) is a group having an oxetane structure) CELLOXIDE 2021P was added to 0.9 parts by mass of the synthesized sesquioxane derivative. (manufactured by DAICEL Co., Ltd.) 0.1 part by mass, BLUESIL PI2074 (fourth (pentafluorophenyl)boric acid (tolylcumenyl)quinodium, cationic polymerization initiator, manufactured by Elkem Silicones Co., Ltd.) 0.02 part by mass, propylene glycol monobutyl 1 mass part of ether was added, and the mixture was stirred using a rotation and revolution mixer to prepare photocurable coating agents respectively.

(Preparation of photocurable coating agent when R ^CE in formula (1) is a group having an epoxy structure) BLUESIL PI2074 (4( Pentafluorophenyl)borate (tolylcumenyl)quinone, cationic polymerization initiator, manufactured by Elkem Silicones Co., Ltd.) 0.02 parts by mass, propylene glycol monobutyl ether 1 part by mass, and the mixture was stirred using a rotational-revolution mixer, and Photocurable coating agents are prepared separately.

(Preparation of photocurable film) The photocurable coating agent prepared in the above manner was applied to an 80 μm thick TAC (cellulose triacetate) film. Specifically, after applying each photocurable coating agent using a No. 20 rod coater, each applied photocurable coating agent was dried at 60° C. for 10 minutes, and then irradiated under the following conditions. It is cured by ultraviolet rays to produce a photocurable film. The film thickness is approximately 10 μm. - Ultraviolet irradiation conditions - Lamp: High-pressure mercury lamp (ECS-4011GX manufactured by EYE GRAPHICS Co., Ltd.) Lamp height: 10 cm Conveyor speed: 5.75 m/min Cumulative light amount per operation: 360 mJ/cm ² (UV- A, measured value of UV POWER PUCK II manufactured by EIT) Environment: In the atmosphere Number of operations: 10 times

(Pencil hardness test) The photocured film obtained in the above manner was subjected to a pencil hardness test in accordance with JIS K5600-5-4 (1999) (ISO/DIS 15184: 1996). The experimental results are shown in Table 1.

(Measurement of indentation elastic modulus) The elastic modulus of the photocured film produced in the above manner is measured in the following manner. Specifically, the indentation hardness measurement was performed at 23° C. using a nano indenter (Nano Indenter G200 manufactured by Agilent Technologies, using a Berkovich indenter) at a strain rate of 0.05/s. The modulus values at an indentation depth of 500 nm to 800 nm are averaged to calculate the indentation elastic modulus. The experimental results are shown in Table 1. A larger value for the press-fit elastic modulus is preferred.

(Calculation of hardening shrinkage) It is calculated according to (density of hardened material - density before hardening)/density before hardening × 100. The results are shown in Table 1.

[Table 1]

As shown in Table 1, compared with Comparative Examples 1 to 3, the sesquioxane derivatives obtained in Examples 1 to 3 had a lower curing shrinkage rate. Furthermore, the sesquisiloxane derivatives obtained in Examples 1 to 3 were also excellent in the hardness of the cured product and the indentation elastic modulus of the cured product.

In addition, the entire disclosure of Japanese Patent Application No. 2022-094444 filed on June 10, 2022 is incorporated into this specification by reference. Furthermore, all documents, patent applications, and technical specifications described in this specification are expressly incorporated by reference into this specification to the same extent as if each document, patent application, and technical specification were individually described.

Domestic storage information (please note in order of storage institution, date and number) without Overseas storage information (please note in order of storage country, institution, date, and number) without

Claims (11)

A sesquisiloxane derivative, which is represented by the following formula (1) and has a hardening shrinkage rate of less than 3.0%; In the formula (1), R ^CE is each independently a group having a cyclic ether structure, and R ¹ is each independently an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, or An aryl group with 6 to 10 atoms, or an aralkyl group with 7 to 12 carbon atoms, R ² and R ³ are each independently a hydrogen atom, a saturated or unsaturated alkyl group with 1 to 20 carbon atoms, A saturated or unsaturated cycloalkyl group with 3 to 8 carbon atoms, an aryl group with 6 to 20 carbon atoms, or an aralkyl group with 7 to 20 carbon atoms. R ⁴ is each independently a cyclic ether structure. An organic group with 2 to 12 carbon atoms, R ⁵ and R ⁶ are each independently an alkyl group with 1 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, or an aralkyl group with 7 to 10 carbon atoms. , a plurality of R ³ may be the same or different from each other, a plurality of R ⁵ may be the same or different from each other, a plurality of R ⁶ may be the same or different from each other, and R ¹ to R ⁶ may be configured independently. A part of is substituted by a substituent or a halogen atom, v is a positive number, and u, w, x, y and z are independently 0 or a positive number. The sesquioxane derivative as claimed in claim 1, wherein u, y and z are 0, and satisfy 0≦x/(v+w)≦0.5. The sesquioxane derivative according to claim 1, wherein the R ^CE is a group having an oxetane structure and/or an epoxy structure. The sesquisiloxane derivative according to claim 1, wherein the R ^CE is a group having an oxetane structure. The sesquisiloxane derivative according to claim 1, wherein the elastic modulus of the cured product obtained after curing exceeds 2.3 GPa at 23°C. A hardening composition containing: The sesquioxane derivative described in any one of claims 1 to 5; and Polymerization initiator. A hard coating agent containing the curable composition according to claim 6. A hardened product obtained by hardening the curable composition according to claim 6. A hard coating layer obtained by hardening the hard coating agent according to claim 7. A base material provided with: the hard coat layer according to claim 9. A method for producing a sesquisiloxane derivative according to any one of claims 1 to 5, comprising: preparing at least one organosilicon compound represented below , a step of hydrolyzing the organosilicon compound by adding a total amount of water of 2 mol equivalents to 30 mol equivalents based on the total amount of hydrolyzable groups of the organosilicon compound using an organic solvent, n represents an integer of 0 to 3, p represents an integer of 1 to 4, and n+p=4, R represents a group bonded to a silicon atom via a carbon atom in the sesquioxane derivative, and X represents a hydrolyzable group. .