JP2018053073A - Silsesquioxane, curable composition, cured product, and hard coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel silsesquioxane and also provide silsesquioxane that can form a cured product having high surface hardness.SOLUTION: Silsesquioxane has a constitutional unit represented by formula (1) [RSiO] [where, Ris a group containing an epoxy group consisting of adjacent two carbon atoms and an oxygen atom on an alicycle having a bicyclo [2.2.1]heptane skeleton].SELECTED DRAWING: None

Description

  The present invention relates to a novel silsesquioxane, a curable composition containing the silsesquioxane, and a cured product thereof. The present invention also relates to a hard coat film having a hard coat layer formed from a hard coat liquid (hard coat agent) containing the silsesquioxane.

  Conventionally, a hard coat film having a hard coat layer on one side or both sides of a substrate has been distributed. As a material for forming a hard coat layer in such a hard coat film, a UV acrylic monomer is mainly used (for example, see Patent Document 1). There is also an example in which nanoparticles are added to the hard coat layer in order to further improve the pencil hardness of the hard coat layer surface.

JP 2009-279840 A

  In recent years, polyorganosilsesquioxane has been used from the viewpoint of increasing the hardness of the hard coat layer because it has a siloxane bond (Si—O—Si) inside and the cage structure has a skeleton close to glass. The used hard coat layer may be used. However, the pencil hardness of the hard coat layer surface using polyorganosilsesquioxane is often about 2B, and the hard coat film using polyorganosilsesquioxane still has sufficient surface hardness. I could not say.

  Accordingly, an object of the present invention is to provide a novel silsesquioxane. Another object of the present invention is to provide an organosilsesquioxane that can be cured to form a cured product having a high surface hardness.

  Furthermore, the applications where hard coat films are used have been increasing in recent years, and in addition to having a high surface hardness as described above, the hard coat layer of the hard coat film has particularly excellent heat resistance. It is also required to have

  As a result of intensive studies to solve the above problems, the present inventors have found that silsesquiskies containing a group containing an epoxy group composed of two adjacent carbon atoms and oxygen atoms on an alicyclic ring having a bicycloheptane skeleton. According to the silsesquioxane having an oxan structural unit (unit structure), it was found that a cured product having high surface hardness can be formed by curing a curable composition containing the silsesquioxane. The present invention has been completed based on these findings.

That is, the present invention provides the following formula (1):
[R ¹ SiO _3/2 ] (1)
[In the formula (1), R ¹ represents a group containing an epoxy group composed of two adjacent carbon atoms and an oxygen atom on an alicyclic ring having a bicyclo [2.2.1] heptane skeleton. ]
The silsesquioxane characterized by having the structural unit represented by these is provided.

  The silsesquioxane preferably has an epoxy equivalent of 100 to 1000 g / eq.

  The silsesquioxane preferably has a number average molecular weight in terms of standard polystyrene by gel permeation chromatography of 500 to 3000, and a molecular weight dispersity of 1.0 to 2.0.

［式（１ａ）中、Ｒ^1aは、単結合又は直鎖若しくは分岐鎖状のアルキレン基を示す。但し、脂環を構成する炭素原子の１以上には置換基が結合していてもよい。］
で表される基、及び／又は下記式（１ｂ）

［式（１ｂ）中、Ｒ^1bは、単結合又は直鎖若しくは分岐鎖状のアルキレン基を示す。但し、脂環を構成する炭素原子の１以上には置換基が結合していてもよい。］
で表される基であることが好ましい。 R ¹ in the structural unit represented by the formula (1) is represented by the following formula (1a)

[In Formula (1a), R ^1a represents a single bond or a linear or branched alkylene group. However, a substituent may be bonded to one or more carbon atoms constituting the alicyclic ring. ]
And / or the following formula (1b)

[In Formula (1b), R ^1b represents a single bond or a linear or branched alkylene group. However, a substituent may be bonded to one or more carbon atoms constituting the alicyclic ring. ]
It is preferable that it is group represented by these.

The silsesquioxane has the following formula (I)
[R ^a SiO _3/2 ] (I)
[In the formula (I), R ^a is a group containing a substituted or unsubstituted epoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, substituted or unsubstituted An unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom is shown. ]
And a structural unit represented by the following formula (II)
[R ^b SiO _2/2 (OR ^c )] (II)
[In the formula (II), R ^b represents a group containing a substituted or unsubstituted epoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, substituted or unsubstituted An unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom is shown. R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]
It is preferable that the ratio [the structural unit represented by Formula (I) / the structural unit represented by Formula (II)] is 1-8.

  Moreover, this invention provides the curable composition containing the said silsesquioxane.

  The curable composition preferably further contains a curing catalyst.

  The curable composition is preferably a curable composition for forming a hard coat layer.

  Moreover, this invention provides the hardened | cured material of the said curable composition.

  Further, the present invention is a hard coat film having a substrate and a hard coat layer formed on at least one surface of the substrate, wherein the hard coat layer is a cured product of the curable composition. Provided is a hard coat film characterized by being a layer.

  Since the silsesquioxane of this invention has the said structure, the hardened | cured material which has high surface hardness can be formed by hardening the curable composition which contains this silsesquioxane as an essential component.

2 is a diagram showing ¹ H-NMR measurement results of a monohydrosilylation product obtained in Synthesis Example 1. FIG. 6 is a diagram showing ¹ H-NMR measurement results of silsesquioxane obtained in Synthesis Example 2. FIG. 6 is a diagram showing ¹ H-NMR measurement results of silsesquioxane obtained in Synthesis Example 3. FIG. Is a diagram showing the ²⁹ Si-NMR measurement results of the silsesquioxane obtained in Synthesis Example 3. It is a figure which shows the < ¹ > H-NMR measurement result of the monohydrosilylation product obtained in the synthesis example 4. 6 is a diagram showing ¹ H-NMR measurement results of silsesquioxane obtained in Synthesis Example 5. FIG. It is a figure which shows the < ¹ > H-NMR measurement result of the silsesquioxane obtained by the synthesis example 6. FIG. Is a diagram showing the ²⁹ Si-NMR measurement results of the silsesquioxane obtained in Synthesis Example 6.

[Silsesquioxane]
The silsesquioxane (organosilsesquioxane) of this invention has a structural unit represented by following formula (1).
[R ¹ SiO _3/2 ] (1)

The structural unit represented by the above formula (1) is a silsesquioxane structural unit (so-called T unit) generally represented by [RSiO _3/2 ]. In the above formula, R represents a hydrogen atom or a monovalent organic group, and the same applies to the following. The structural unit represented by the above formula (1) is a hydrolysis and condensation reaction of a corresponding hydrolyzable trifunctional silane compound (specifically, for example, a compound represented by the following formula (a)), or These are formed by hydrolysis and condensation reactions of other hydrolyzable trifunctional silane compounds (specifically, for example, compounds represented by the following formula (b)) and subsequent epoxidation reactions.

R ¹ in the formula (1) is a group containing an epoxy group composed of two adjacent carbon atoms and an oxygen atom on the alicyclic ring having a bicyclo [2.2.1] heptane skeleton (monovalent Group). That is, the silsesquioxane of the present invention is composed of an alicyclic ring having a bicyclo [2.2.1] heptane skeleton, two adjacent carbon atoms and an oxygen atom on the alicyclic ring. And a cationically curable compound (cationic polymerizable compound) having at least a group containing an epoxy group.

R ¹ is an alicyclic ring having a bicyclo [2.2.1] heptane skeleton, an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and an oxygen atom on the alicyclic ring, Is a group containing The alicyclic ring having a bicyclo [2.2.1] heptane skeleton may be a bicyclo [2.2.1] heptane ring, or a bicyclo [2.2.1] heptane ring and one or more other alicyclic rings. A bridged ring in combination with an alicyclic ring (for example, a 3- to 8-membered alicyclic ring such as a cyclopentane ring, a cyclohexane ring, or a cycloheptane ring) may be used. In addition, a substituent such as an alkyl group may be bonded to one or more carbon atoms constituting the alicyclic ring. In the alicyclic ring, the alicyclic epoxy group may be on the bicyclo [2.2.1] heptane skeleton or on the other alicyclic ring.

Examples of the alicyclic ring include a bicyclo [2.2.1] heptane ring, a tricyclo [5.2.1.0 ^2,6 ] decane ring, and a tricyclo [6.2.1.0 ^2,7 ] undecane ring. , Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecane ring and the like.

As the R ^1, is not particularly limited, in terms of surface hardness of the cured product, a group represented by the following formula (1a), a group represented by the following formula (1b), is represented by the following formula (1c) A group represented by the following formula (1d), a group represented by the following formula (1e), a group represented by the following formula (1a), and a group represented by the following formula (1b) are more preferable. preferable. In addition, the group represented by the following formula (1a), the group represented by the following formula (1b), the group represented by the following formula (1c), the group represented by the following formula (1d), and the following formula ( In the group represented by 1e), a substituent such as an alkyl group may be bonded to one or more carbon atoms constituting the alicyclic ring.

In the above formula (1a), R ^1a represents a single bond or a linear or branched alkylene group. Examples of the linear or branched alkylene group include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and a decamethylene group. Examples thereof include a linear or branched alkylene group having 1 to 10 carbon atoms. Among these, R ^1a is preferably a linear alkylene group having 1 to 4 carbon atoms, more preferably a methylene group, an ethylene group, a trimethylene group, a propylene group, or the like from the viewpoint of the surface hardness or curability of the cured product. An ethylene group is preferred.

In the above formula (1b), R ^1b represents a single bond or a linear or branched alkylene group, and examples thereof include the same groups as R ^1a . Among these, R ^1b is preferably a single bond from the viewpoint of curability of the curable composition.

In the above formula (1c), R ^1c represents a single bond or a linear or branched alkylene group, and examples thereof include the same groups as R ^1a . Among these, R ^1c is preferably a single bond from the viewpoint of curability of the curable composition.

In the above formula (1d), R ^1d represents a single bond or a linear or branched alkylene group, and examples thereof include the same groups as R ^1a . Among these, R ^1d is preferably a single bond from the viewpoint of curability of the curable composition.

In the above formula (1e), R ^1e represents a single bond or a linear or branched alkylene group, and examples thereof include the same groups as R ^1a . Among these, R ^1e is preferably a linear alkylene group having 1 to 4 carbon atoms, more preferably a methylene group, an ethylene group, a trimethylene group, a propylene group, from the viewpoint of the surface hardness or curability of the cured product. An ethylene group is preferred.

Among them, the group represented by the above formula (1a) is preferably a 2- (3,4-epoxybicyclo [2.2.1] heptanyl) ethyl group. The group represented by the formula (1b) is preferably a 4,5-epoxytricyclo [5.2.1.0 ^2,6 ] decanyl group. In addition, examples of the group represented by the above formula (1c) include a 3,4-epoxytricyclo [6.2.1.0 ^2,7 ] undec-9-yl group and a 3,4-epoxytricyclo group. A [6.2.1.0 ^2,7 ] undec-10-yl group is preferred. The group represented by the above formula (1d) is preferably a 4,5-epoxytricyclo [6.2.1.0 ^2,7 ] undec-9-yl group. Further, the group represented by the formula (1e), among others, 2- (4,5-epoxy-tetracyclo [6.2.1.1 ^3,6 .0 ^2,7] dodeca-9-yl) An ethyl group is preferred.

  The silsesquioxane of the present invention may have only one type of structural unit represented by the above formula (1), or may have two or more types of structural units represented by the above formula (1). It may be.

The silsesquioxane of the present invention includes a structural unit represented by the following formula (2) in addition to the structural unit represented by the above formula (1) as the silsesquioxane structural unit [RSiO _3/2 ]. You may have.
[R ² SiO _3/2 ] (2)

The structural unit represented by the above formula (2) is a silsesquioxane structural unit (T unit) generally represented by [RSiO _3/2 ]. That is, the structural unit represented by the above formula (2) is a hydrolysis and condensation reaction of a corresponding hydrolyzable trifunctional silane compound (specifically, for example, a compound represented by the following formula (b)). Alternatively, it is formed by hydrolysis and condensation reaction of another hydrolyzable trifunctional silane compound (specifically, for example, a compound represented by the following formula (b)) and subsequent epoxidation reaction.

R ² in the above formula (2) is a group containing a substituted or unsubstituted epoxy group not corresponding to the above R ¹ (sometimes referred to as “substituted or unsubstituted other epoxy group-containing group”), substituted Or an unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group; Examples of the other epoxy group-containing groups include known or conventional groups having an oxirane ring (for example, a group containing a glycidyl group or a group containing an epoxycyclohexyl group). As said aryl group, a phenyl group, a tolyl group, a naphthyl group etc. are mentioned, for example. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the cycloalkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like. Examples of the alkyl group include linear or branched alkyl groups such as methyl group, ethyl group, propyl group, n-butyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, and isopentyl group. Groups. As said alkenyl group, linear or branched alkenyl groups, such as a vinyl group, an allyl group, and an isopropenyl group, are mentioned, for example.

  As the other substituted epoxy group-containing groups, substituted aryl groups, substituted aralkyl groups, substituted cycloalkyl groups, substituted alkyl groups, and substituted alkenyl groups, the other epoxy group-containing groups, aryl groups, aralkyl groups, A hydrogen atom or a part or all of the main chain skeleton in each of the cycloalkyl group, the alkyl group, and the alkenyl group is an alkyl group (particularly, a linear or branched alkyl group having 1 to 10 carbon atoms), an ether group, A group substituted with at least one selected from the group consisting of an ester group, a carbonyl group, a siloxane group, a halogen atom (such as a fluorine atom), an acrylic group, a methacryl group, a mercapto group, an amino group, and a hydroxy group (hydroxyl group) Is mentioned.

Among them, R ² is preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, and more preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group. More preferably a phenyl group, an allyl group, and particularly preferably an allyl group.

  The ratio of each of the above silsesquioxane structural units (the structural unit represented by the formula (1) and the structural unit represented by the formula (2)) in the silsesquioxane of the present invention forms these structural units. It is possible to adjust appropriately according to the composition of the raw material (hydrolyzable trifunctional silane) for

In addition to the structural unit represented by the above formula (1) and the structural unit represented by the formula (2), the silsesquioxane of the present invention further comprises the structural unit and the formula represented by the above formula (1). Silsesquioxane structural units other than the structural unit represented by (2) [RSiO _3/2 ], structural units represented by [R ₃ SiO _1/2 ] (so-called M units), [R ₂ SiO _{2 / 2} ] and at least one siloxane structural unit selected from the group consisting of a structural unit represented by [SiO ₂ ] (so-called Q unit). Good. In addition, as a silsesquioxane structural unit other than the structural unit represented by the said Formula (1) and the structural unit represented by Formula (2), the structural unit etc. which are represented by following formula (3) etc. are mentioned, for example. Can be mentioned.
[HSiO _3/2 ] (3)

The silsesquioxane of this invention contains the structural unit (T3 body) represented by the following formula (I) as an essential structural unit. Furthermore, the structural unit (T2 body) represented by the following formula (II) may be included.
[R ^a SiO _3/2 ] (I)
[R ^b SiO _2/2 (OR ^c )] (II)

When the structural unit represented by the above formula (I) is described in more detail, it is represented by the following formula (I ′). Further, when the structural unit represented by the above formula (II) is described in more detail, it is represented by the following formula (II ′). Each of the three oxygen atoms bonded to the silicon atom shown in the structure represented by the following formula (I ′) is bonded to another silicon atom (a silicon atom not shown in the formula (I ′)). . On the other hand, two oxygen atoms located above and below the silicon atom shown in the structure represented by the following formula (II ′) are respectively replaced with other silicon atoms (silicon atoms not shown in the formula (II ′)). Are connected. That is, the T3 body and the T2 body are structural units (T units) formed by hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compound.

R ^a in the above formula (I) (formula (I ') in the R ^a same) and formula (II) in the R ^b (wherein (II') in the R ^b versa), respectively, substituted or A group containing an unsubstituted epoxy group (for example, the above R ¹ , the above substituted or unsubstituted other epoxy group-containing group, etc.) a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted group A cycloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom. Specific examples of R ^a and R ^b are the same as R ¹ in the above formula (1) and R ² in the above formula (2). In addition, R ^a in formula (I) and R ^b in formula (II) are groups bonded to silicon atoms in the hydrolyzable trifunctional silane compound used as a raw material for the silsesquioxane of the present invention ( A group other than an alkoxy group and a halogen atom; for example, R ¹ , R ² in the formulas (a) to (c) described later, a hydrogen atom, etc.), or the silsesquioxane of the present invention It is a group obtained by epoxidizing a group bonded to a silicon atom (a group other than an alkoxy group and a halogen atom; for example, R ² in formula (b) described later) in the hydrolyzable trifunctional silane compound used as a raw material. .

R ^c in the formula (II) (Formula (II ') in the R ^c versa) is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include linear or branched alkyl groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. . The alkyl group in R ^c in the formula (II) is generally an alkoxy group in the hydrolyzable silane compound used as a raw material for the silsesquioxane of the present invention (for example, as X ^{1 to} X ³ described later). Derived from an alkyl group forming an alkoxy group or the like.

  The ratio [T3 body / T2 body] of the structural unit (T3 body) represented by the above formula (I) and the structural unit (T2 body) represented by the above formula (II) in the silsesquioxane of the present invention is Although not specifically limited, 0.5-10 are preferable, More preferably, it is 1-8, More preferably, it is 1.2-5. By setting the ratio [T3 body / T2 body] within the above range, the surface hardness of the cured product or the hard coat layer is remarkably improved.

The said ratio [T3 body / T2 body] in the silsesquioxane of this invention can be calculated | required by ²⁹ Si-NMR spectrum measurement, for example. ^{29 In the} Si-NMR spectrum, the silicon atom in the structural unit (T3 form) represented by the formula (I) is different from the silicon atom in the structural unit (T2 form) represented by the formula (II). In order to show a signal (peak) in (chemical shift), the ratio [T3 body / T2 body] can be obtained by calculating the integration ratio of these respective peaks. Specifically, for example, when silsesquioxane has a structural unit represented by the above formula (2) and R ² is a 2- (3,4-epoxycyclohexyl) ethyl group, the above formula ( The signal of the silicon atom in the structure (T3 form) represented by I) appears at −64 to −70 ppm, and the signal of the silicon atom in the structure (T2 form) represented by the formula (II) is −54 to −60 ppm. Appear in Therefore, in this case, the ratio [T3 body / T2 body] can be obtained by calculating the integral ratio of the signal (T3 body) of −64 to −70 ppm and the signal (T2 body) of −54 to −60 ppm. it can. Instead of the constitutional unit represented by the formula R ² is 2- (3,4-epoxycyclohexyl) ethyl (2), for example in the case of structural units represented by the above formula (1) However, the silicon atom signal in the T3 body and the silicon atom signal in the T2 body may fluctuate, respectively. However, the silicon atom signal in the T3 body and the silicon atom signal in the T2 body appear in different ranges. Similarly, the ratio [T3 / T2] can be determined.

The ²⁹ Si-NMR spectrum of the silsesquioxane of the present invention can be measured by, for example, the following apparatus and conditions.
Measuring apparatus: Trade name “JNM-ECA500NMR” (manufactured by JEOL Ltd.)
Solvent: Deuterated chloroform Accumulated times: 1800 times Measurement temperature: 25 ° C

As said T2 body, the structural unit represented by following formula (4), the structural unit represented by following formula (5), the structural unit represented by following formula (6), etc. are mentioned, for example. R ² in R ¹ and the following formula (5) in the following equation (4) is the same as R ² in R ¹ and the formula in the formula (1) (2). R ^c in the formula (4) to (6), like the R ^c in Formula (II), a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
[R ¹ SiO _2/2 (OR ^c )] (4)
[R ² SiO _2/2 (OR ^c )] (5)
[HSiO _2/2 (OR ^c )] (6)

As the T2 body, R ¹ is preferably contains a structural unit represented by the above radicals or the formula represented by (1a) is a group represented by (1b) above formula (4).

  The silsesquioxane of the present invention is not particularly limited, and a silsesquioxane having a ladder skeleton (ladder-type silsesquioxane) or a silsesquioxane having a cage structure (complete cage structure, incomplete cage structure) ( Any of a cage type (complete cage type, incomplete cage type) silsesquioxane) and a silsesquioxane having a random structure (random silsesquioxane) may be used. The silsesquioxane of the present invention may be a silsesquioxane in which two or more of the above structures are mixed. In the ladder-type silsesquioxane, the ratio of the siloxane constitutional units constituting the ladder structure in all the siloxane constitutional units (100 mol%) constituting the silsesquioxane is preferably 50 mol% or more. In the cage silsesquioxane, the ratio of the siloxane structural unit constituting the cage structure in all the siloxane structural units (100 mol%) constituting the silsesquioxane is preferably 50 mol% or more. In the random silsesquioxane, the ratio of the siloxane constituent units constituting the ladder structure and the cage structure in all the siloxane constituent units (100 mol%) constituting the silsesquioxane is less than 50 mol%. preferable.

The silsesquioxane has an incomplete cage silsesquioxane structure, respectively, in FT-IR spectrum in the vicinity of 1050 cm ^-1 and near 1150 cm ^-1 have no intrinsic absorption peaks, one around 1100 cm ^-1 It is confirmed by having an intrinsic absorption peak [Reference: R.R. H. Raney, M.M. Itoh, A.D. Sakakibara and T. Suzuki, Chem. Rev. 95, 1409 (1995)]. On the other hand, in general, when the FT-IR spectrum has intrinsic absorption peaks near 1050 cm ⁻¹ and 1150 cm ⁻¹ , it is identified as having a ladder-type silsesquioxane structure. Further, when the silsesquioxane has a complete cage silsesquioxane structure, since the silsesquioxane does not include the T3 form, [T3 form / T2 form] becomes 0. And when silsesquioxane does not correspond to any of a ladder type, a complete cage type, and an incomplete cage type, it can identify as a random type silsesquioxane. However, when it is difficult to identify the type from the intrinsic absorption peak in the FT-IR spectrum, in addition to the intrinsic absorption peak in the FT-IR spectrum, considering the molecular weight (number average molecular weight, etc.), [T3 body / T2 body] is a ladder. It can be identified by comprehensively judging whether it corresponds to a mold or a cage type. In addition, the FT-IR spectrum of the silsesquioxane of this invention can be measured with the following apparatus and conditions, for example.
Measuring device: Trade name “FT-720” (manufactured by Horiba, Ltd.)
Measurement method: Transmission method Resolution: 4 cm ^-1
Measurement wavenumber range: 400 to 4000 cm ⁻¹
Integration count: 16 times

  The total amount of siloxane structural units in the silsesquioxane of the present invention [all siloxane structural units; the total amount of M units, D units, T units, and Q units] (100 mol%) is represented by the above formula (1). The proportion (total amount) of the structural unit and the structural unit represented by the above formula (4) is not particularly limited, but is preferably 50 mol% or more (for example, 50 to 100 mol%), more preferably 60 mol% or more, More preferably, it is 80 mol% or more, Most preferably, it is 90 mol% or more. When the ratio is 50 mol% or more, the curability of the curable composition is improved, and the surface hardness of the cured product tends to be extremely high. In addition, the ratio of each siloxane structural unit in the silsesquioxane of this invention is computable by a raw material composition, NMR spectrum measurement, etc., for example.

The total amount of siloxane structural units in the silsesquioxane of the present invention [all siloxane structural units; the total amount of M units, D units, T units, and Q units] (100 mol%) is represented by the above formula (1). A structural unit, a structural unit represented by the above formula (2), wherein R ² is a substituted or unsubstituted other epoxy group-containing group, a structural unit represented by the above formula (4), and R ² is substituted or unsubstituted. The ratio (total amount) of the structural unit represented by the above formula (5) which is another epoxy group-containing group (that is, the ratio of the structural unit having a group containing a substituted or unsubstituted epoxy group) is particularly limited. Although it is not, 50 mol% or more (for example, 50-100 mol%) is preferable, More preferably, it is 55-100 mol%, More preferably, it is 60-100 mol%. When the ratio is 50 mol% or more, the curability of the curable composition is improved, and the surface hardness of the cured product tends to be extremely high.

  The total amount of siloxane structural units in the silsesquioxane of the present invention [all siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%) is represented by the above formula (2). The proportion (total amount) of the structural unit and the structural unit represented by the above formula (5) is not particularly limited, but is preferably 0 to 70 mol%, more preferably 0 to 60 mol%, and still more preferably 0 to 40 mol. %, Particularly preferably 1 to 15 mol%. Since the ratio of the structural unit represented by the formula (1) and the structural unit represented by the formula (4) can be relatively increased by setting the ratio to 70 mol% or less, the curable composition The curability of the cured product is improved, and the surface hardness and adhesiveness of the cured product tend to be higher. On the other hand, when the ratio is 1 mol% or more, the gas barrier property of the cured product tends to be improved.

  The total amount of siloxane structural units in the silsesquioxane of the present invention [all siloxane structural units; the total amount of M units, D units, T units, and Q units] (100 mol%) is represented by the above formula (1). The proportion (total amount) of the structural unit, the structural unit represented by the formula (2), the structural unit represented by the formula (4), and the structural unit represented by the formula (5) is not particularly limited. 60-100 mol% is preferable, More preferably, it is 70-100 mol%, More preferably, it is 80-100 mol%. When the ratio is 60 mol% or more, the surface hardness of the cured product tends to be higher.

  Although the epoxy equivalent (g / eq) of the silsesquioxane of this invention is not specifically limited, 2000 or less (for example, 50-2000) is preferable, More preferably, it is 100-1500, More preferably, it is 170-1000, Especially preferably Is 200-800. When the epoxy equivalent is within the above range, the amount of epoxy groups in the silsesquioxane becomes appropriate, and the surface hardness of the cured product tends to be higher. The epoxy equivalent is measured according to JIS K7236: 2001.

  The number average molecular weight (Mn) in terms of standard polystyrene by gel permeation chromatography of the silsesquioxane of the present invention is not particularly limited, but is preferably 300 to 5000, more preferably 500 to 3000, and more preferably 650 to 2500. It is. When the number average molecular weight is 300 or more, the surface hardness of the cured product is remarkably improved, and the heat resistance, scratch resistance, and adhesion of the cured product tend to be further improved. Further, when the curable composition containing the silsesquioxane of the present invention is applied to a substrate or the like, repelling is unlikely to occur, and dents and dents are unlikely to be generated on the surface of the coating film, which tends to improve film forming properties. . On the other hand, when the number average molecular weight is 5000 or less, the compatibility with other components in the curable composition is improved, and the surface hardness and heat resistance of the cured product tend to be further improved.

  The molecular weight dispersity (Mw / Mn) in terms of standard polystyrene by gel permeation chromatography of the silsesquioxane of the present invention is not particularly limited, but is preferably 1.0 to 3.0, more preferably 1.0 to 2.0, more preferably 1.0 to 1.5, and still more preferably 1.0 to 1.3. When the molecular weight dispersity is 3.0 or less, the surface hardness of the cured product tends to be higher.

In addition, the number average molecular weight and molecular weight dispersion degree of the silsesquioxane of this invention can be measured with the following apparatus and conditions.
Measuring device: Product name “LC-20AD” (manufactured by Shimadzu Corporation)
Columns: Shodex KF-801 × 2, KF-802, and KF-803 (manufactured by Showa Denko KK)
Measurement temperature: 40 ° C
Eluent: THF, sample concentration 0.1-0.2% by weight
Flow rate: 1 mL / min Detector: UV-VIS detector (trade name “SPD-20A”, manufactured by Shimadzu Corporation)
Molecular weight: Standard polystyrene conversion

  The silsesquioxane of the present invention can be produced by a known or conventional polysiloxane production method, and is not particularly limited. For example, one or two or more hydrolyzable silane compounds are hydrolyzed and condensed. It can be manufactured by using the method.

More specifically, for example, a compound represented by the following formula (b) which is a hydrolyzable silane compound for forming a silsesquioxane structural unit (T unit) in the silsesquioxane of the present invention, necessary Further, the silsesquioxane of the present invention is produced by a method of hydrolyzing and condensing a compound represented by the following formula (a) and a compound represented by the following formula (c) and then epoxidizing the compound. it can. However, as a compound represented by the following formula (b), R ² is a substituted or unsubstituted alkenyl group (specifically, a substituted or unsubstituted alicyclic ring having a bicyclo [2.2.1] heptane skeleton). And a group in which two adjacent carbon atoms on the alicyclic ring form a carbon-carbon double bond (sometimes referred to as “an alkenyl group-containing group corresponding to R ¹ ”). It is necessary to use the compound represented by b) as an essential hydrolyzable silane compound.
R ¹ Si (X ¹ ) ₃ (a)
R ² Si (X ² ) ₃ (b)
HSi (X ³ ) ₃ (c)

The compound represented by the above formula (a) is a compound that forms the structural unit represented by the formula (1) in the silsesquioxane of the present invention. R ¹ in the formula (a) it is composed of R ¹ in the formula (1) as well, and bicyclo [2.2.1] two adjacent carbon atoms and oxygen atoms on the alicyclic ring having heptane skeleton A group containing an epoxy group. That is, R ¹ in the formula (a) is preferably a group represented by the above formula (1a) or a group represented by the above formula (1b).

X ¹ in the above formula (a) represents an alkoxy group or a halogen atom. The alkoxy group in X ^1, for example, a methoxy group, an ethoxy group, a propoxy group, isopropyloxy group, a butoxy group, an alkoxy group having 1 to 4 carbon atoms such as isobutyl group and the like. As the halogen atom in X ^1, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, X ¹ is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. The three X ¹ may be the same or different.

The compound represented by the above formula (b) is a compound that forms the structural unit represented by the formula (2) in the silsesquioxane of the present invention. R ² in formula (b) is the same as R ² in formula (2) above, other substituted or unsubstituted epoxy group-containing groups, substituted or unsubstituted aryl groups, substituted or unsubstituted aralkyl groups, substituted Or an unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group; However, at least the compound represented by the above formula (b) in which R ² is a substituted or unsubstituted alkenyl group (specifically, an alkenyl group-containing group corresponding to the above R ¹ ) is used. It is preferably controlled in a range of 10 to 100 mol% with respect to the siloxane structural unit. The R ² in the formula other than the alkenyl group-containing group (b) corresponding to the R ^1, a substituted or unsubstituted alkenyl groups other than the alkenyl group-containing group corresponding to the R ^1, a substituted or unsubstituted aryl group A substituted or unsubstituted alkyl group is preferred, a substituted or unsubstituted aryl group is more preferred, and a phenyl group is more preferred.

X ² in the above formula (b) represents an alkoxy group or a halogen atom. Specific examples of X ² include those exemplified as X ¹ . Among them, X ² is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. The three X ² may be the same or different.

The compound represented by the above formula (c) is a compound that forms the structural unit represented by the formula (3) in the silsesquioxane of the present invention. X ³ in the above formula (c) represents an alkoxy group or a halogen atom. Specific examples of X ³ include those exemplified as X ¹ . Among them, X ³ is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. The three X ³ may be the same or different.

As the compounds represented by the above formulas (a) to (c), commercially available products may be used, or manufactured products may be used. The compound represented by the above formula (b) in which R ² is an alkenyl group-containing group corresponding to R ¹ includes, for example, an alicyclic ring having a bicyclo [2.2.1] heptane skeleton in the presence of a catalyst. A compound having two carbon atoms adjacent to each other on the alicyclic ring forming a carbon-carbon double bond, and further having a group having a carbon-carbon double bond; and trimethoxysilane; Can be made to react.

  As said hydrolysable silane compound, you may use together hydrolysable silane compounds other than the compound represented by said formula (a)-(c). For example, hydrolyzable trifunctional silane compounds other than the compounds represented by the above formulas (a) to (c), hydrolyzable monofunctional silane compounds that form M units, and hydrolyzable bifunctional silanes that form D units Examples thereof include hydrolyzable tetrafunctional silane compounds that form compounds and Q units.

  The amount and composition of the hydrolyzable silane compound can be appropriately adjusted according to the desired structure of the silsesquioxane of the present invention. For example, although the usage-amount of the compound represented by the said Formula (b) is not specifically limited, 10-100 mol% is preferable with respect to the whole quantity (100 mol%) of the hydrolysable silane compound to be used, More preferably Is 65 to 100 mol%, more preferably 80 to 99 mol%.

The amount of the compound represented by the above formula (b) in which R ² is a group other than the alkenyl group-containing group corresponding to R ¹ is not particularly limited, but the total amount of hydrolyzable silane compound to be used ( 100 mol%) is preferably 0 to 70 mol%, more preferably 0 to 60 mol%, still more preferably 0 to 40 mol%, and particularly preferably 1 to 15 mol%.

  Furthermore, the ratio of the compound represented by the formula (a) and the compound represented by the formula (b) (the ratio of the total amount) to the total amount (100 mol%) of the hydrolyzable silane compound to be used is not particularly limited. 60-100 mol% is preferable, More preferably, it is 70-100 mol%, More preferably, it is 80-100 mol%.

  Moreover, when using together 2 or more types as said hydrolysable silane compound, the hydrolysis and condensation reaction of these hydrolysable silane compounds can also be performed simultaneously, and can also be performed sequentially. When performing the said reaction sequentially, the order which performs reaction is not specifically limited.

  The hydrolysis and condensation reaction of the hydrolyzable silane compound can be performed in the presence of a solvent or in the absence. Among these, it is preferable to carry out in the presence of a solvent. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran (THF), and dioxane; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone (MIBK). ; Esters such as methyl acetate, ethyl acetate, isopropyl acetate and butyl acetate; Amides such as N, N-dimethylformamide and N, N-dimethylacetamide; Nitriles such as acetonitrile, propionitrile and benzonitrile; Methanol, ethanol and isopropyl Alcohols, such as alcohol and butanol, etc. are mentioned. Among them, ketone and ether are preferable. In addition, a solvent can also be used individually by 1 type and can also be used in combination of 2 or more type.

  The usage-amount of a solvent is not specifically limited, It can adjust suitably according to desired reaction time etc. within the range of 0-2000 weight part with respect to 100 weight part of whole quantity of a hydrolysable silane compound. .

  The hydrolysis and condensation reaction of the hydrolyzable silane compound is preferably allowed to proceed in the presence of a catalyst and water. The catalyst may be an acid catalyst or an alkali catalyst. Examples of the acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and boric acid; phosphoric acid esters; carboxylic acids such as acetic acid, formic acid and trifluoroacetic acid; methanesulfonic acid, trifluoromethanesulfonic acid, p -Sulfonic acids such as toluenesulfonic acid; solid acids such as activated clay; Lewis acids such as iron chloride. Examples of the alkali catalyst include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; alkaline earth metals such as magnesium hydroxide, calcium hydroxide, and barium hydroxide. Hydroxides; carbonates of alkali metals such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate; carbonates of alkaline earth metals such as magnesium carbonate; lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate Alkali metal bicarbonates such as lithium acetate, sodium acetate, potassium acetate, cesium acetate, etc. (for example, acetate); alkaline earth metal organic acid salts, such as magnesium acetate (for example, Acetate); lithium methoxide, sodium methoxide, sodium ethoxide Alkali metal alkoxides such as sodium phenoxide, sodium isopropoxide, potassium ethoxide, potassium t-butoxide; alkali metal phenoxides such as sodium phenoxide; triethylamine, N-methylpiperidine, 1,8-diazabicyclo [5.4.0] Amines such as undec-7-ene and 1,5-diazabicyclo [4.3.0] non-5-ene (tertiary amine and the like); pyridine, 2,2′-bipyridyl, 1,10-phenanthroline and the like And nitrogen-containing aromatic heterocyclic compounds. In addition, a catalyst can also be used individually by 1 type and can also be used in combination of 2 or more type. Further, the catalyst can be used in a state dissolved or dispersed in water, a solvent or the like.

  The usage-amount of the said catalyst is not specifically limited, It can adjust suitably in the range of 0.002-0.200 mol with respect to 1 mol of whole quantity of a hydrolysable silane compound.

  The amount of water used in the hydrolysis and condensation reaction is not particularly limited, and can be appropriately adjusted within a range of 0.5 to 20 mol with respect to 1 mol of the total amount of the hydrolyzable silane compound.

  The method for adding water is not particularly limited, and the total amount of water to be used (total amount used) may be added all at once or sequentially. When adding sequentially, you may add continuously and may add intermittently.

  Although the reaction temperature of the said hydrolysis and condensation reaction is not specifically limited, 0-100 degreeC is preferable, More preferably, it is 15-50 degreeC. By controlling the reaction temperature within the above range, the degree of polymerization tends to be improved. Moreover, the reaction time of the said hydrolysis and condensation reaction is although it does not specifically limit, 0.1 to 30 hours are preferable, More preferably, it is 1.5 to 20 hours. The hydrolysis and condensation reaction can be performed under normal pressure, or can be performed under pressure or under reduced pressure. In addition, the atmosphere at the time of performing the hydrolysis and condensation reaction is not particularly limited, and may be any of, for example, in an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere, or in the presence of oxygen such as in the air. However, an inert gas atmosphere is preferred.

  By the hydrolysis and condensation reaction of the hydrolyzable silane compound, silsesquioxane having an alkenyl group bonded to a silicon atom (sometimes referred to as “alkenyl group-containing silsesquioxane”) is obtained.

  Thereafter, the alkenyl group-containing silsesquioxane is converted into an epoxy group by epoxidizing the carbon-carbon double bond portion in the alkenyl group by a known or conventional epoxidation reaction, and the silsesquioxane of the present invention. Is obtained. Although the said epoxidation reaction is not specifically limited, For example, it can perform using oxidizing agents, such as a peracid.

  The oxidant may be a known or conventional oxidant such as hydrogen peroxide or organic peracid, and is not particularly limited. Examples of the organic peracid include performic acid, peracetic acid, peroxygen. Examples include benzoic acid, trifluoroperacetic acid, and metachloroperbenzoic acid (mCPBA). In addition, an oxidizing agent can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  The above-described epoxidation reaction can be carried out more specifically according to a well-known and commonly used method described in, for example, JP-A-60-161973.

  After completion of the epoxidation reaction, it is preferable to neutralize the catalyst in order to suppress ring opening of the epoxy group. Further, the silsesquioxane of the present invention can be separated from, for example, water washing, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination of these. It may be separated and purified by such as

The method of hydrolyzing and condensing the compound represented by the formula (b) in which R ² is an alkenyl group-containing group corresponding to R ¹ described above and then epoxidizing was described. The production method of Sun is not limited to this method, but may be produced by, for example, a method of hydrolysis and condensation using a compound represented by the above formula (a) as a hydrolyzable silane compound.

  Since the silsesquioxane of the present invention has the above-described configuration, a cured product having a high surface hardness can be formed by curing a curable composition containing the polyorganosilsesquioxane as an essential component.

[Curable composition]
The curable composition of the present invention is a curable composition (curable resin composition) containing the above-described silsesquioxane of the present invention as an essential component. As will be described later, the curable composition of the present invention may further contain other components such as a curing catalyst (particularly a photocationic polymerization initiator), a surface conditioner or a surface modifier.

  In the curable composition of this invention, the silsesquioxane of this invention can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  The content (blending amount) of the silsesquioxane of the present invention in the curable composition of the present invention is not particularly limited, but is 70% by weight with respect to the total amount (100% by weight) of the curable composition excluding the solvent. As mentioned above, less than 100 weight% is preferable, More preferably, it is 80-99.8 weight%, More preferably, it is 90-99.5 weight%. By setting the content of the silsesquioxane of the present invention to 70% by weight or more, the surface hardness of the cured product tends to be further improved. On the other hand, when the content of the silsesquioxane of the present invention is less than 100% by weight, a curing catalyst can be contained, and thereby the curing of the curable composition tends to proceed more efficiently. There is.

  Although the ratio of the silsesquioxane of this invention with respect to the whole quantity (100 weight%) of the cationic curable compound contained in the curable composition of this invention is not specifically limited, 70-100 weight% is preferable, More preferably, it is 75. It is -98 weight%, More preferably, it is 80-95 weight%. By setting the content of the silsesquioxane of the present invention to 70% by weight or more, the surface hardness of the cured product tends to be further improved.

  The curable composition of the present invention preferably further contains a curing catalyst. Among these, it is particularly preferable to include a photocationic polymerization initiator as a curing catalyst in that the curing time until tack-free can be shortened.

  The said curing catalyst is a compound which can start thru | or accelerate | stimulate the cationic polymerization reaction of cationic curable compounds, such as silsesquioxane of this invention. Although it does not specifically limit as said curing catalyst, For example, polymerization initiators, such as a photocationic polymerization initiator (photoacid generator) and a thermal cationic polymerization initiator (thermal acid generator), are mentioned.

  As the photocationic polymerization initiator, known or commonly used photocationic polymerization initiators can be used. For example, sulfonium salts (salts of sulfonium ions and anions), iodonium salts (salts of iodonium ions and anions). Selenium salt (selenium ion and anion salt), ammonium salt (ammonium ion and anion salt), phosphonium salt (phosphonium ion and anion salt), transition metal complex ion and anion salt, etc. . These can be used individually by 1 type or in combination of 2 or more types.

Examples of the anion constituting the salt in the photocationic polymerization initiator include SbF ₆ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , (CF ₃ CF ₂ ) ₃ PF ₃ ⁻ , and (CF ₃ CF ₂ CF ₂ ) ₃ PF _{3. ^{-, (C 6 F 5)}} 4 B -, (C 6 F 5) 4 Ga -, a sulfonate anion (trifluoromethanesulfonic acid anion, pentafluoroethanesulfonate anion, nonafluorobutanesulfonic acid anion, methanesulfonic acid anion , Benzenesulfonate anion, p-toluenesulfonate anion, etc.), (CF ₃ SO ₂ ) ₃ C ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , perhalogenate ion, halogenated sulfonate ion, sulfate ion, carbonate Ion, aluminate ion, hexafluorobismuth ion, carboxylate ion, arylborate ion, thiocyanate ion, nitrate ion, etc. Is mentioned.

  Examples of the sulfonium salt include triphenylsulfonium salt, tri-p-tolylsulfonium salt, tri-o-tolylsulfonium salt, tris (4-methoxyphenyl) sulfonium salt, 1-naphthyldiphenylsulfonium salt, and 2-naphthyldiphenyl. Sulfonium salt, tris (4-fluorophenyl) sulfonium salt, tri-1-naphthylsulfonium salt, tri-2-naphthylsulfonium salt, tris (4-hydroxyphenyl) sulfonium salt, diphenyl [4- (phenylthio) phenyl] sulfonium salt , Triarylsulfonium salts such as 4- (p-tolylthio) phenyldi- (p-phenyl) sulfonium salt; diphenylphenacylsulfonium salt, diphenyl-4-nitrophenacylsulfonium salt, diphenylbenzyl Diarylsulfonium salts such as ruphonium salt and diphenylmethylsulfonium salt; monoarylsulfonium salts such as phenylmethylbenzylsulfonium salt, 4-hydroxyphenylmethylbenzylsulfonium salt and 4-methoxyphenylmethylbenzylsulfonium salt; dimethylphenacylsulfonium salt, phena And trialkylsulfonium salts such as siltetrahydrothiophenium salt and dimethylbenzylsulfonium salt. Of these, triarylsulfonium salts are preferred.

  Examples of the diphenyl [4- (phenylthio) phenyl] sulfonium salt include a trade name “CPI-101A” (manufactured by San Apro Co., Ltd., diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate 50% propylene carbonate solution). ), Trade name “CPI-100P” (manufactured by San Apro Co., Ltd., diphenyl [4- (phenylthio) phenyl] sulfonium hexafluorophosphate 50% propylene carbonate solution) and the like can be used.

  Examples of the iodonium salt include a trade name “UV9380C” (manufactured by Momentive Performance Materials Japan GK, bis (4-dodecylphenyl) iodonium hexafluoroantimonate 45% alkyl glycidyl ether solution), a trade name “ RHODORSIL PHOTOINITIATOR 2074 "(Rhodia Japan KK, Tetrakis (pentafluorophenyl) borate / [(1-methylethyl) phenyl] (methylphenyl) iodonium), trade name" WPI-124 "(Wako Pure Chemical Industries, Ltd.) Co., Ltd.), diphenyliodonium salt, di-p-tolyliodonium salt, bis (4-dodecylphenyl) iodonium salt, bis (4-methoxyphenyl) iodonium salt, and the like.

  Examples of the selenium salt include triaryl selenium such as triphenyl selenium salt, tri-p-tolyl selenium salt, tri-o-tolyl selenium salt, tris (4-methoxyphenyl) selenium salt, and 1-naphthyldiphenyl selenium salt. Salts: Diaryl phenacyl selenium salts, diphenyl benzyl selenium salts, diaryl selenium salts such as diphenyl methyl selenium salts; monoaryl selenium salts such as phenyl methyl benzyl selenium salts; trialkyl selenium salts such as dimethyl phenacyl selenium salts, etc. .

  Examples of the ammonium salt include tetramethylammonium salt, ethyltrimethylammonium salt, diethyldimethylammonium salt, triethylmethylammonium salt, tetraethylammonium salt, trimethyl-n-propylammonium salt, and trimethyl-n-butylammonium salt. Pyrrolium salts such as alkyl ammonium salts; N, N-dimethylpyrrolidinium salts, N-ethyl-N-methylpyrrolidinium salts; N, N′-dimethylimidazolinium salts, N, N′-diethylimidazolinium salts, etc. Imidazolinium salts; tetrahydropyrimidinium salts such as N, N′-dimethyltetrahydropyrimidinium salt, N, N′-diethyltetrahydropyrimidinium salt; N, N-dimethylmorpholinium salt, N, N -Diethylmorpholini Morpholinium salts such as N salt, piperidinium salts such as N, N-dimethylpiperidinium salt and N, N-diethylpiperidinium salt; pyridinium salts such as N-methylpyridinium salt and N-ethylpyridinium salt; N, N '-Imidazolium salt such as dimethylimidazolium salt; Quinolium salt such as N-methylquinolium salt; Isoquinolium salt such as N-methylisoquinolium salt; Thiazonium salt such as benzylbenzothiazonium salt; And the like.

  Examples of the phosphonium salt include tetraarylphosphonium salts such as tetraphenylphosphonium salt, tetra-p-tolylphosphonium salt and tetrakis (2-methoxyphenyl) phosphonium salt; triarylphosphonium salts such as triphenylbenzylphosphonium salt; Examples thereof include tetraalkylphosphonium salts such as benzylphosphonium salt, tributylbenzylphosphonium salt, tetraethylphosphonium salt, tetrabutylphosphonium salt, and triethylphenacylphosphonium salt.

Examples of the salt of the transition metal complex ion include chromium such as (η ⁵ -cyclopentadienyl) (η ⁶ -toluene) Cr ⁺ and (η ⁵ -cyclopentadienyl) (η ⁶ -xylene) Cr ^+. Salts of complex cations; salts of iron complex cations such as (η ⁵ -cyclopentadienyl) (η ⁶ -toluene) Fe ⁺ and (η ⁵ -cyclopentadienyl) (η ⁶ -xylene) Fe ⁺ It is done.

  Examples of the thermal cationic polymerization initiator include arylsulfonium salts, aryliodonium salts, allene-ion complexes, quaternary ammonium salts, aluminum chelates, and boron trifluoride amine complexes.

  Examples of the anion constituting the salt in the thermal cationic polymerization initiator include the same examples as the anion constituting the salt in the above-mentioned photocationic polymerization initiator.

  In the curable composition of the present invention, one type of curing catalyst can be used alone, or two or more types can be used in combination.

  The content (blending amount) of the curing catalyst in the curable composition of the present invention is not particularly limited, but is preferably 0.01 to 3.0 parts by weight with respect to 100 parts by weight of the silsesquioxane of the present invention. More preferably, it is 0.05-3.0 weight part, More preferably, it is 0.1-1.0 weight part (for example, 0.3-1.0 weight part). By setting the content of the curing catalyst to 0.01 parts by weight or more, the curing reaction can be efficiently and sufficiently advanced, and the surface hardness of the cured product tends to be further improved. On the other hand, when the content of the curing catalyst is 3.0 parts by weight or less, the storability of the curable composition tends to be further improved, and coloring of the cured product tends to be suppressed.

  The curable composition of the present invention may further contain a cationic curable compound other than the silsesquioxane of the present invention (sometimes referred to as “other cationic curable compounds”). As other cationic curable compounds, known or commonly used cationic curable compounds can be used, and are not particularly limited. For example, epoxy compounds other than the silsesquioxane of the present invention ("other epoxy compounds" and Oxetane compounds, vinyl ether compounds, and the like. In addition, in the curable composition of this invention, another cationic curable compound can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  As said other epoxy compound, the well-known thru | or usual compound which has one or more epoxy groups (oxirane ring) in a molecule | numerator can be used, Although it does not specifically limit, For example, an alicyclic epoxy compound (alicyclic) Epoxy resin), aromatic epoxy compounds (aromatic epoxy resins), aliphatic epoxy compounds (aliphatic epoxy resins), and the like.

  Examples of the alicyclic epoxy compound include known or conventional compounds having one or more alicyclic rings and one or more epoxy groups in the molecule, and are not particularly limited. For example, (1) A compound having an epoxy group (referred to as “alicyclic epoxy group”) composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring; (2) the epoxy group is directly bonded to the alicyclic ring by a single bond. (3) compounds having an alicyclic ring and a glycidyl ether group in the molecule (glycidyl ether type epoxy compound) and the like.

As said (1) compound which has an alicyclic epoxy group in a molecule | numerator, the compound represented by following formula (i) is mentioned.

  In the above formula (i), Y represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include divalent hydrocarbon groups, alkenylene groups in which part or all of carbon-carbon double bonds are epoxidized, carbonyl groups, ether bonds, ester bonds, carbonate groups, amide groups, and the like. And a group in which a plurality of are connected. In addition, a substituent such as an alkyl group may be bonded to one or more carbon atoms constituting the cyclohexane ring (cyclohexene oxide group) in the formula (i).

  As said bivalent hydrocarbon group, a C1-C18 linear or branched alkylene group, a bivalent alicyclic hydrocarbon group, etc. are mentioned. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclopentylene group, And divalent cycloalkylene groups (including cycloalkylidene groups) such as cyclohexylene group, 1,4-cyclohexylene group, and cyclohexylidene group.

  Examples of the alkenylene group in the alkenylene group in which part or all of the carbon-carbon double bond is epoxidized (sometimes referred to as “epoxidized alkenylene group”) include, for example, a vinylene group, a propenylene group, and a 1-butenylene group. , A 2-butenylene group, a butadienylene group, a pentenylene group, a hexenylene group, a heptenylene group, an octenylene group, etc., and a linear or branched alkenylene group having 2 to 8 carbon atoms. In particular, the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds are epoxidized, more preferably 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized. Alkenylene group.

Representative examples of the alicyclic epoxy compound represented by the above formula (i) include 3,4,3 ′, 4′-diepoxybicyclohexane, and the following formulas (i-1) to (i-10): The compound etc. which are represented by these are mentioned. In the following formulas (i-5) and (i-7), l and m each represent an integer of 1 to 30. R ′ in the following formula (i-5) is an alkylene group having 1 to 8 carbon atoms, and among them, a linear or branched chain having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a propylene group, and an isopropylene group. -Like alkylene groups are preferred. N1-n6 in following formula (i-9) and (i-10) show the integer of 1-30, respectively. Other examples of the alicyclic epoxy compound represented by the above formula (i) include 2,2-bis (3,4-epoxycyclohexyl) propane and 1,2-bis (3,4-epoxycyclohexyl). ) Ethane, 2,3-bis (3,4-epoxycyclohexyl) oxirane, bis (3,4-epoxycyclohexylmethyl) ether and the like.

Examples of the compound (2) in which the epoxy group is directly bonded to the alicyclic ring with a single bond include compounds represented by the following formula (ii).

In formula (ii), R ″ is a group (p-valent organic group) obtained by removing p hydroxyl groups (—OH) from the structural formula of a p-valent alcohol, and p and n each represent a natural number. Examples of the valent alcohol [R ″ (OH) _p ] include polyhydric alcohols (such as alcohols having 1 to 15 carbon atoms) such as 2,2-bis (hydroxymethyl) -1-butanol. p is preferably 1 to 6, and n is preferably 1 to 30. When p is 2 or more, n in each group in () (inside the outer parenthesis) may be the same or different. Specific examples of the compound represented by the above formula (ii) include 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol [for example, , Trade name “EHPE3150” (manufactured by Daicel Corporation), etc.].

  Examples of the compound (3) having an alicyclic ring and a glycidyl ether group in the molecule include glycidyl ethers of alicyclic alcohols (particularly alicyclic polyhydric alcohols). More specifically, for example, 2,2-bis [4- (2,3-epoxypropoxy) cyclohexyl] propane, 2,2-bis [3,5-dimethyl-4- (2,3-epoxypropoxy) Compound obtained by hydrogenating bisphenol A type epoxy compound such as cyclohexyl] propane (hydrogenated bisphenol A type epoxy compound); bis [o, o- (2,3-epoxypropoxy) cyclohexyl] methane, bis [o , P- (2,3-epoxypropoxy) cyclohexyl] methane, bis [p, p- (2,3-epoxypropoxy) cyclohexyl] methane, bis [3,5-dimethyl-4- (2, 3-epoxypropoxy) cyclohexyl] a compound obtained by hydrogenating a bisphenol F-type epoxy compound such as methane (hydrogenated bisphenol F-type epoxy compound); Hydrogenated phenol novolac epoxy compound; Hydrogenated cresol novolac epoxy compound; Hydrogenated cresol novolac epoxy compound of bisphenol A; Hydrogenated naphthalene epoxy compound; Epoxy compound obtained from trisphenolmethane Hydrogenated epoxy compounds; hydrogenated epoxy compounds of the following aromatic epoxy compounds and the like.

  Examples of the aromatic epoxy compound include epibis type glycidyl ether type epoxy resins obtained by condensation reaction of bisphenols [for example, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol and the like] and epihalohydrin; High molecular weight epibis type glycidyl ether type epoxy resin obtained by addition reaction of bis type glycidyl ether type epoxy resin with the above bisphenols; phenols [eg, phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, bisphenol S, etc.] and aldehyde [eg, formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, salicy A novolak alkyl type glycidyl ether type epoxy resin obtained by further condensing a polyhydric alcohol obtained by a condensation reaction with an aldehyde etc. with an epihalohydrin; two phenol skeletons are bonded to the 9-position of the fluorene ring. In addition, an epoxy compound in which a glycidyl group is bonded to an oxygen atom obtained by removing a hydrogen atom from the hydroxy group of the phenol skeleton, either directly or via an alkyleneoxy group.

  Examples of the aliphatic epoxy compound include a glycidyl ether of an alcohol having no q-valent cyclic structure (q is a natural number); a monovalent or polyvalent carboxylic acid [for example, acetic acid, propionic acid, butyric acid, stearic acid, Adipic acid, sebacic acid, maleic acid, itaconic acid, etc.] glycidyl ester; epoxidized oils and fats having double bonds such as epoxidized linseed oil, epoxidized soybean oil, epoxidized castor oil; polyolefins such as epoxidized polybutadiene (poly Epoxidized product of alkadiene). Examples of the alcohol having no q-valent cyclic structure include monohydric alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, and 1-butanol; ethylene glycol, 1,2-propanediol, 1 , 3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and other dihydric alcohols; Examples include trihydric or higher polyhydric alcohols such as glycerin, diglycerin, erythritol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and sorbitol. That. The q-valent alcohol may be polyether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol, or the like.

  Examples of the oxetane compound include known or commonly used compounds having one or more oxetane rings in the molecule, and are not particularly limited. For example, 3,3-bis (vinyloxymethyl) oxetane, 3-ethyl-3- (Hydroxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-[(phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3- Ethyl-3- (chloromethyl) oxetane, 3,3-bis (chloromethyl) oxetane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, bis {[1-ethyl (3- Oxetanyl)] methyl} ether, 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] bisi Chlohexyl, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] cyclohexane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, 3-ethyl-3- {[(3-ethyloxetane-3-yl) methoxy] methyl)} oxetane, xylylene bisoxetane, 3-ethyl-3-{[3- (triethoxysilyl) propoxy] methyl} oxetane, oxetanylsilsesquioxane And phenol novolac oxetane.

  The vinyl ether compound may be a known or conventional compound having one or more vinyl ether groups in the molecule, and is not particularly limited. For example, 2-hydroxyethyl vinyl ether (ethylene glycol monovinyl ether), 3-hydroxy Propyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxyisobutyl vinyl ether, 2-hydroxyisobutyl vinyl ether, 1-methyl-3 -Hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl vinyl ether, 1-hydroxymethylpropyl vinyl ether 4-hydroxycyclohexyl vinyl ether, 1,6-hexanediol monovinyl ether, 1,6-hexanediol divinyl ether, 1,8-octanediol divinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, 1,4-cyclohexanedi Methanol divinyl ether, 1,3-cyclohexanedimethanol monovinyl ether, 1,3-cyclohexanedimethanol divinyl ether, 1,2-cyclohexanedimethanol monovinyl ether, 1,2-cyclohexanedimethanol divinyl ether, p-xylene glycol monovinyl ether P-xylene glycol divinyl ether, m-xylene glycol monovinyl ether, m-xylene glycol divinyl ether, o-xy Glycol monovinyl ether, o-xylene glycol divinyl ether, ethylene glycol divinyl ether, diethylene glycol monovinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, triethylene glycol divinyl ether, tetraethylene glycol monovinyl ether, tetraethylene glycol divinyl ether, penta Ethylene glycol monovinyl ether, pentaethylene glycol divinyl ether, oligoethylene glycol monovinyl ether, oligoethylene glycol divinyl ether, polyethylene glycol monovinyl ether, polyethylene glycol divinyl ether, dipropylene glycol monovinyl ether, dipropylene glycol Coal divinyl ether, tripropylene glycol monovinyl ether, tripropylene glycol divinyl ether, tetrapropylene glycol monovinyl ether, tetrapropylene glycol divinyl ether, pentapropylene glycol monovinyl ether, pentapropylene glycol divinyl ether, oligopropylene glycol monovinyl ether, oligopropylene glycol di Vinyl ether, polypropylene glycol monovinyl ether, polypropylene glycol divinyl ether, isosorbide divinyl ether, oxanorbornene divinyl ether, phenyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octyl vinyl ether, cyclohexyl vinyl ether, ha Droquinone divinyl ether, 1,4-butanediol divinyl ether, cyclohexane dimethanol divinyl ether, trimethylolpropane divinyl ether, trimethylolpropane trivinyl ether, bisphenol A divinyl ether, bisphenol F divinyl ether, hydroxyoxanorbornane methanol divinyl ether, 1, Examples include 4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, and dipentaerythritol hexavinyl ether.

  In the curable composition of the present invention, a vinyl ether compound is preferably used in combination with the silsesquioxane of the present invention as another cationic curable compound. This tends to increase the curing rate. In particular, when the curable composition of the present invention is cured by irradiation with active energy rays (particularly ultraviolet rays), a cured product having a very high surface hardness is excellent even when the irradiation amount of active energy rays is reduced. For example, there is an advantage that it can be obtained with high productivity (for example, it is not necessary to perform heat treatment for aging). For this reason, it becomes possible to make the manufacturing line speed of hardened | cured material and a hard coat film higher, and these productivity improves further.

  In addition, when a vinyl ether compound having one or more hydroxyl groups in the molecule is used as the other cationic curable compound, the curing rate is increased, and further, heat-resistant yellowing (yellowing due to heating hardly occurs). There is an advantage that a cured product having excellent properties can be obtained. For this reason, the hardened | cured material and hard coat film of higher quality and durability are obtained. The number of hydroxyl groups in the molecule of the vinyl ether compound having one or more hydroxyl groups in the molecule is not particularly limited, but is preferably 1 to 4, more preferably 1 or 2. Specifically, examples of the vinyl ether compound having one or more hydroxyl groups in the molecule include 2-hydroxyethyl vinyl ether (ethylene glycol monovinyl ether), 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl. Vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3-hydroxyisobutyl vinyl ether, 2-hydroxyisobutyl vinyl ether, 1-methyl-3-hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl Vinyl ether, 1-hydroxymethylpropyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, 1,6-hexa Diol monovinyl ether, 1,8-octanediol divinyl ether, 1,4-cyclohexanedimethanol monovinyl ether, 1,3-cyclohexanedimethanol monovinyl ether, 1,2-cyclohexanedimethanol monovinyl ether, p-xylene glycol monovinyl ether, m-xylene glycol monovinyl ether, o-xylene glycol monovinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, pentaethylene glycol monovinyl ether, oligoethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, tripropylene glycol Monovinyl ether, tetra B propylene glycol monomethyl ether, pentaethylene glycol monomethyl ether, oligo propylene glycol monomethyl ether, polypropylene glycol monovinyl ether, pentaerythritol trivinyl ether, dipentaerythritol penta vinyl ether.

  The content (blending amount) of the other cationic curable compound in the curable composition of the present invention is not particularly limited, but the total amount of the silsesquioxane of the present invention and the other cationic curable compound (100% by weight; cation) 50% by weight or less (for example, 0 to 50% by weight), preferably 30% by weight or less (for example, 0 to 30% by weight), more preferably 10% by weight or less, based on the total amount of the curable compound. It is. By setting the content of other cationic curable compounds to 50% by weight or less (particularly 10% by weight or less), the scratch resistance of the cured product tends to be further improved. On the other hand, by setting the content of the other cationic curable compound to more than 10% by weight, desired performance for the curable composition and the cured product (for example, quick curability and viscosity adjustment for the curable composition). May be granted.

  The content (blending amount) of the vinyl ether compound (particularly, the vinyl ether compound having one or more hydroxyl groups in the molecule) in the curable composition of the present invention is not particularly limited, but the silsesquioxane of the present invention and other The amount is preferably 0.01 to 10% by weight, more preferably 0.05 to 9% by weight, still more preferably 1 to 8% by weight based on the total amount of the cationic curable compound (100% by weight; the total amount of the cationic curable compound). %. By controlling the content of the vinyl ether compound within the above range, the surface hardness of the cured product becomes higher, and the surface hardness is extremely high even when the irradiation amount of active energy rays (for example, ultraviolet rays) is lowered. There is a tendency to get things. In particular, by controlling the content of the vinyl ether compound having one or more hydroxyl groups in the molecule within the above range, in addition to particularly high surface hardness of the cured product, there is a tendency to further improve its heat-resistant yellowing. is there.

  The curable composition of the present invention further includes, as other optional components, precipitated silica, wet silica, fumed silica, calcined silica, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate. Inorganic fillers such as carbon black, silicon carbide, silicon nitride and boron nitride, inorganic fillers obtained by treating these fillers with organosilicon compounds such as organohalosilanes, organoalkoxysilanes and organosilazanes; silicone resins, epoxy resins , Organic resin fine powder such as fluororesin; filler such as conductive metal powder such as silver and copper, curing agent (amine curing agent, polyaminoamide curing agent, acid anhydride curing agent, phenol curing agent, etc. ), Curing aids, curing accelerators (imidazoles, alkali metal or alkaline earth metal alkoxides, Fins, amide compounds, Lewis acid complex compounds, sulfur compounds, boron compounds, condensable organometallic compounds, etc.), solvents (water, organic solvents, etc.), stabilizers (antioxidants, UV absorbers, light stabilizers, Heat stabilizers, heavy metal deactivators, etc.), flame retardants (phosphorous flame retardants, halogen flame retardants, inorganic flame retardants, etc.), flame retardant aids, reinforcing materials (other fillers, etc.), nucleating agents , Coupling agents (silane coupling agents, etc.), lubricants, waxes, plasticizers, mold release agents, impact modifiers, hue modifiers, clearing agents, rheology modifiers (fluidity modifiers, etc.), processability improvement Agents, colorants (dyes, pigments, etc.), antistatic agents, dispersants, surface conditioners (leveling agents, anti-waxing agents, etc.), surface modifiers (slip agents, etc.), matting agents, antifoaming agents, suppression Foaming agent, defoaming agent, antibacterial agent, preservative, viscosity modifier, thickener, photosensitizer, foaming agent, heavy It may contain conventional additives such as stabilizers. These additives can be used individually by 1 type or in combination of 2 or more types. Although the content (blending amount) of the additive is not particularly limited, it is preferably 100 parts by weight or less, more preferably 30 parts by weight or less (for example, 0.00%) with respect to 100 parts by weight of the silsesquioxane of the present invention. 01 to 30 parts by weight), more preferably 10 parts by weight or less (for example, 0.1 to 10 parts by weight).

  Although the curable composition of this invention is not specifically limited, It can prepare by stirring and mixing each said component, heating at room temperature or as needed. In addition, the curable composition of the present invention can be used as a one-component composition in which each component is mixed in advance, for example, two or more components stored separately. Can be used as a multi-liquid composition (for example, a two-liquid system) used by mixing them at a predetermined ratio before use.

  Although the curable composition of this invention is not specifically limited, It is preferable that it is a liquid at normal temperature (about 25 degreeC). More specifically, the curable composition of the present invention has a viscosity at 25 ° C. of a liquid diluted to 20% of a solvent [particularly, a curable composition (solution) in which the proportion of methyl isobutyl ketone is 20% by weight]. 10 to 20000 mPa · s, more preferably 50 to 10000 mPa · s, and still more preferably 100 to 8000 mPa · s. There exists a tendency for applicability | paintability to improve by making the said viscosity into 10 mPa * s or more. On the other hand, when the viscosity is 20000 mPa · s or less, preparation and handling of the curable composition are facilitated, and air bubbles tend not to remain in the cured product. The viscosity of the curable composition of the present invention was measured using a viscometer (trade name “MCR301”, manufactured by Anton Paar Co., Ltd.) with a swing angle of 5%, a frequency of 0.1 to 100 (1 / s), and temperature: It is measured at 25 ° C.

[Cured product]
By proceeding the polymerization reaction of the cationic curable compound (such as silsesquioxane of the present invention) in the curable composition of the present invention, the curable composition can be cured, May be referred to as a “cured product”. The curing method can be appropriately selected from well-known methods and is not particularly limited, and examples thereof include a method of irradiation with active energy rays and / or heating. As the active energy ray, for example, any of infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, α rays, β rays, γ rays and the like can be used. Among these, ultraviolet rays are preferable in terms of excellent handleability.

Conditions for curing the curable composition of the present invention by irradiation with active energy rays (irradiation conditions for active energy rays, etc.) depend on the type and energy of the active energy rays to be irradiated, the shape and size of the cured product, etc. Although it can adjust suitably and it is not specifically limited, When irradiating an ultraviolet-ray, it is preferable to set it as about 1-1000 mJ / cm < ² >, for example. For irradiation with active energy rays, for example, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, sunlight, an LED lamp, a laser, or the like can be used. After the irradiation with the active energy ray, a heating treatment (annealing and aging) can be further performed to further advance the curing reaction.

  On the other hand, conditions for curing the curable composition of the present invention by heating are not particularly limited, but for example, 30 to 200 ° C is preferable, and 50 to 190 ° C is more preferable. The curing time can be appropriately set.

  As described above, the curable composition of the present invention can be cured to form a cured product having a high surface hardness. Accordingly, the curable composition of the present invention particularly includes a “curable composition for forming a hard coat layer” (“hard coat liquid”, “hard coat agent” and the like for forming a hard coat layer in a hard coat film. And may be particularly preferably used.

[Hard coat film]
The hard coat film of the present invention is a film having a substrate and a hard coat layer formed on at least one surface of the substrate, wherein the hard coat layer is a curable composition (hard It is a hard coat layer (a layer of a cured product of the curable composition of the present invention) formed by a curable composition for forming a coat layer). In the present specification, the hard coat layer formed of the curable composition of the present invention may be referred to as “the hard coat layer of the present invention”.

  In addition, the hard coat layer of the present invention in the hard coat film of the present invention may be formed only on one surface (one surface) of the substrate, or may be formed on both surfaces (both surfaces). .

  In addition, the hard coat layer of the present invention in the hard coat film of the present invention may be formed on only a part or on the entire surface of each surface of the substrate.

  The base material in the hard coat film of the present invention is a base material of the hard coat film and refers to a part constituting other than the hard coat layer of the present invention. As said base material, well-known, such as a plastic base material, a metal base material, a ceramic base material, a semiconductor base material, a glass base material, a paper base material, a wood base material (wood base material), and the base material whose surface is a coating surface Thru | or a usual base material can be used and it does not specifically limit. Among these, a plastic substrate (a substrate made of a plastic material) is preferable.

  Although the plastic material which comprises the said plastic base material is not specifically limited, For example, Polyester such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN); Polyimide; Polycarbonate; Polyamide; Polyacetal; Polyphenylene oxide; Polyphenylene sulfide; Polyether Sulfone; Polyetheretherketone; Norbornene monomer homopolymer (addition polymer, ring-opening polymer, etc.), Norbornene monomer and olefin monomer copolymer (addition polymer, such as norbornene and ethylene copolymer) And cyclic olefin copolymers such as ring-opening polymers), cyclic polyolefins such as derivatives thereof; vinyl polymers (for example, acrylic resins such as polymethyl methacrylate (PMMA), polystyrene , Polyvinyl chloride, acrylonitrile-styrene-butadiene resin (ABS resin, etc.); vinylidene polymers (eg, polyvinylidene chloride, etc.); cellulose resins such as triacetyl cellulose (TAC); epoxy resins; phenol resins; Various plastic materials such as melamine resin; urea resin; maleimide resin; The plastic substrate may be composed of only one kind of plastic material or may be composed of two or more kinds of plastic materials.

  Above all, as the plastic substrate, when the purpose is to obtain a hard coat film excellent in transparency as the hard coat film of the present invention, a substrate excellent in transparency (transparent substrate) is used. And more preferably a polyester film (particularly PET, PEN), a cyclic polyolefin film, a polycarbonate film, a TAC film, and a PMMA film.

  If necessary, the plastic substrate is made of an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a crystal nucleating agent, a flame retardant, a flame retardant aid, a filler, a plasticizer, and an impact modifier. , Other additives such as reinforcing agents, dispersants, antistatic agents, foaming agents, antibacterial agents and the like may be included. In addition, an additive can also be used individually by 1 type and can also be used in combination of 2 or more type.

  The plastic substrate may have a single-layer configuration or a multilayer (lamination) configuration, and the configuration (structure) is not particularly limited. For example, the above-mentioned plastic substrate is “plastic film / other layer” in which a layer other than the hard coat layer of the present invention (sometimes referred to as “other layer”) is formed on at least one surface of the plastic film. Alternatively, it may be a plastic substrate having a laminated structure such as “other layer / plastic film / other layer”. Examples of the other layers include hard coat layers other than the hard coat layer of the present invention. In addition, as a material which comprises the said other layer, the above-mentioned plastic material etc. are mentioned, for example.

  Roughening treatment, easy adhesion treatment, antistatic treatment, sandblast treatment (sand mat treatment), corona discharge treatment, plasma treatment, chemical etching treatment, water mat treatment, flame are applied to part or all of the surface of the plastic substrate. Known or conventional surface treatments such as treatment, acid treatment, alkali treatment, oxidation treatment, ultraviolet irradiation treatment, silane coupling agent treatment, etc. may be applied. The plastic substrate may be an unstretched film or a stretched film (uniaxially stretched film, biaxially stretched film, etc.).

  The plastic base material is, for example, a method of forming the above plastic material into a film shape to form a plastic base material (plastic film), and if necessary, an appropriate layer (for example, the above-mentioned other layers) with respect to the plastic film. For example, a layer or the like, or an appropriate surface treatment. In addition, a commercial item can also be used as said plastic base material.

  Although the thickness of the said base material is not specifically limited, For example, it can select suitably from the range of 0.01-10000 micrometers.

  The hard coat layer of the present invention in the hard coat film of the present invention is a layer constituting at least one surface layer in the hard coat film of the present invention, and the curable composition of the present invention (curable composition for forming a hard coat layer). It is a layer (cured product layer) formed by a cured product (resin cured product) obtained by curing the product.

  The thickness of the hard coat layer of the present invention (in the case of having the hard coat layer of the present invention on both surfaces of the substrate) is not particularly limited, but is preferably 1 to 200 μm, more preferably Is 3 to 150 μm, more preferably 4 to 50 μm. In particular, even when the hard coat layer of the present invention is thin (for example, when the thickness is 10 μm or less), it is possible to maintain a high surface hardness (for example, a pencil hardness of 2H or more). is there. In addition, even when it is thick (for example, when the thickness is 50 μm or more), it is difficult to cause defects such as cracks due to curing shrinkage, etc., so that the pencil hardness is significantly increased by increasing the film thickness (for example, pencil hardness) Can be 9H or more).

  The haze of the hard coat layer of the present invention is not particularly limited, but is preferably 1.5% or less, more preferably 1.0% or less in the case of a thickness of 50 μm. The lower limit of haze is not particularly limited, but is 0.1%, for example. By setting the haze to 1.0% or less, for example, the haze tends to be suitable for use in applications that require very high transparency (for example, surface protection sheets for displays such as touch panels). The haze of the hard coat layer of the present invention can be measured according to JIS K7136.

  The total light transmittance of the hard coat layer of the present invention is not particularly limited, but is preferably 85% or more, more preferably 90% or more in the case of a thickness of 50 μm. The upper limit of the total light transmittance is not particularly limited, but is 99%, for example. By setting the total light transmittance to 85% or more, for example, it tends to be suitable for use in applications that require extremely high transparency (for example, surface protection sheets for displays such as touch panels). The total light transmittance of the hard coat layer of the present invention can be measured according to JIS K7361-1.

  The hard coat film of the present invention may further have a surface protective film on the surface of the hard coat layer of the present invention. When the hard coat film of the present invention has a surface protective film, the punchability of the hard coat film tends to be further improved. In the case of having a surface protective film in this way, for example, even if the hardness of the hard coat layer is very high and peeling or cracking from the base material is likely to occur at the time of punching, such a problem occurs. It is possible to perform punching using a Thomson blade without causing it to occur.

  As the surface protective film, a known or conventional surface protective film can be used, and is not particularly limited. For example, a film having a pressure-sensitive adhesive layer on the surface of a plastic film can be used. Examples of the plastic film include polyester (polyethylene terephthalate, polyethylene naphthalate, etc.), polyolefin (polyethylene, polypropylene, cyclic polyolefin, etc.), polystyrene, acrylic resin, polycarbonate, epoxy resin, fluorine resin, silicone resin, diacetate resin, Examples thereof include plastic films formed from plastic materials such as triacetate resin, polyarylate, polyvinyl chloride, polysulfone, polyethersulfone, polyetheretherimide, polyimide, and polyamide. Examples of the adhesive layer include an acrylic adhesive, a natural rubber adhesive, a synthetic rubber adhesive, an ethylene-vinyl acetate copolymer adhesive, an ethylene- (meth) acrylate copolymer adhesive, Examples thereof include a pressure-sensitive adhesive layer formed from one or more known or common pressure-sensitive adhesives such as a styrene-isoprene block copolymer pressure-sensitive adhesive and a styrene-butadiene block copolymer pressure-sensitive adhesive. In the pressure-sensitive adhesive layer, various additives (for example, an antistatic agent, a slip agent, etc.) may be contained. In addition, the plastic film and the pressure-sensitive adhesive layer may each have a single layer configuration, or may have a multilayer (multi-layer) configuration. Further, the thickness of the surface protective film is not particularly limited and can be appropriately selected.

  Examples of the surface protective film include the product name “Sanitek” series (manufactured by Sanei Kaken Co., Ltd.), the product name “E-MASK” series (manufactured by Nitto Denko Corporation), and the product name “Mastak” series (Fujimori Industry ( Commercially available products such as the product name “Hitarex” series (manufactured by Hitachi Chemical Co., Ltd.) and the product name “Alphan” series (manufactured by Oji F-Tex Co., Ltd.) are available from the market.

  The hard coat film of the present invention can be produced in accordance with a known or commonly used method for producing a hard coat film, and the production method is not particularly limited. For example, the hard coat film of the present invention is applied to at least one surface of the substrate. It can be produced by applying a curable composition (a curable composition for forming a hard coat layer), removing the solvent by drying as necessary, and then curing the curable composition (curable composition layer). . The conditions for curing the curable composition are not particularly limited, and can be appropriately selected from, for example, the conditions for forming the cured product described above.

  The thickness of the hard coat film of this invention is not specifically limited, It can select from the range of 1-10000 micrometers suitably.

  The pencil hardness of the hard coat layer surface of the present invention of the hard coat film of the present invention is not particularly limited, but is preferably H or more, more preferably 2H or more when the thickness of the hard coat layer is 10 μm. The pencil hardness can be evaluated according to the method described in JIS K5600-5-4.

  The haze of the hard coat film of the present invention is not particularly limited, but is preferably 1.5% or less, more preferably 1.0% or less. The lower limit of haze is not particularly limited, but is 0.1%, for example. By setting the haze to 1.0% or less, for example, the haze tends to be suitable for use in applications that require very high transparency (for example, surface protection sheets for displays such as touch panels). The haze of the hard coat film of the present invention can be easily controlled within the above range by using, for example, the above-mentioned transparent substrate as a substrate. The haze can be measured according to JIS K7136.

  Although the total light transmittance of the hard coat film of this invention is not specifically limited, 85% or more is preferable, More preferably, it is 90% or more. The upper limit of the total light transmittance is not particularly limited, but is 99%, for example. By setting the total light transmittance to 90% or more in particular, for example, there is a tendency to be suitable for use in applications that require very high transparency (for example, surface protection sheets for displays such as touch panels). The total light transmittance of the hard coat film of the present invention can be easily controlled within the above range by using, for example, the above-mentioned transparent substrate as the substrate. The total light transmittance can be measured according to JIS K7361-1.

  The hard coat film of the present invention has high quality because of its high surface hardness. In particular, when the surface protective film is provided on the surface of the hard coat layer of the present invention, the punching processability is also excellent. For this reason, it can be preferably used for any application that requires such characteristics. The hard coat film of the present invention can be used as, for example, a surface protective film for various products, a surface protective film for various product members or parts, and also used as a constituent material for various products, members or parts thereof. You can also Examples of the products include display devices such as liquid crystal displays and organic EL displays; input devices such as touch panels: solar cells; various home appliances; various electric and electronic products; portable electronic terminals (for example, game machines, personal computers, tablets, Smartphones, mobile phones, etc.) and various electrical and electronic products; various optical devices. Moreover, as an aspect in which the hard coat film of the present invention is used as a constituent material of various products and its members or parts, for example, an aspect used in a laminate of a hard coat film and a transparent conductive film in a touch panel, etc. It is done.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The molecular weight of the product was measured by Alliance HPLC system 2695 (manufactured by Waters), Refractive Index Detector 2414 (manufactured by Waters), column: Tskel GMH _HR- M × 2 (manufactured by Tosoh Corp.), guard column: Tskel guard column H _HR L (manufactured by Tosoh Corp.), column oven: COLUMN HEATER U-620 (manufactured by Sugai), solvent: THF, measurement conditions: 40 ° C. Moreover, the measurement of the ratio [T3 body / T2 body] of T2 body and T3 body in a product was performed by ²⁹ Si-NMR spectrum measurement by JEOL ECA500 (500 MHz).

Synthesis example 1
(Preparation of monohydrosilylation product)
(1R, 4S, 5S) -5-vinylbicyclo [2.2.1] hept-2 under a nitrogen stream in a flask (reaction vessel) equipped with a thermometer, stirrer, reflux condenser, and nitrogen inlet tube -520 g of ene, 3 L of toluene, 2.2 g of H ₂ PtCl ₆ · 6H ₂ O, and 26 g of acetic acid were charged and the temperature was raised to 100 ° C. Trimethoxysilane 528.6g was dripped at the mixture obtained in this way, and it heat-stirred for 16 hours.
After completion of the stirring, the reaction solution was cooled, the solvent was distilled off by an evaporator, and 508.6 g (yield 48%) of a colorless transparent liquid monohydrosilylation product (compound represented by the following formula) was obtained by distillation. . The measurement result of the ¹ H-NMR spectrum of the obtained monohydrosilylation product is shown in FIG.

Synthesis example 2
(Preparation of double bond-containing polyorganosilsesquioxane)
In a flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen introduction tube, 50 g of the monohydrosilylation product obtained in Synthesis Example 1, THF 500 mL, sodium hydroxide 3. 3 g and 4.8 g of water were charged. The mixture thus obtained was stirred for 5 hours while refluxing.
After completion of the stirring, the reaction solution was cooled and extracted with ethyl acetate (300 mL × 3 times). Thereafter, the combined organic phases were washed with water (500 mL × 5 times). After distilling off the solvent using an evaporator, a light yellow liquid double bond-containing polyorganosilsesquioxane (the structural unit represented by the following formula (A ′) and the structural unit represented by the following formula (B ′) Compound 50) was obtained. The measurement result of the ¹ H-NMR spectrum of the obtained polyorganosilsesquioxane is shown in FIG.
[R ³ SiO _3/2 ] (A ′)
[R ³ SiO _2/2 (OR ^d )] (B ′)
[Wherein, R ³ represents a group represented by the following formula, and R ^d represents a methyl group. ]

Synthesis example 3
(Preparation of epoxybicyclo [2.2.1] heptanyl group-containing polyorganosilsesquioxane)
A flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube was charged with 50 g of the polyorganosilsesquioxane obtained in Synthesis Example 2 and 500 mL of ethyl acetate under a nitrogen stream. It is. To the mixture thus obtained, 42.8 g of mCPBA was added, and the mixture was stirred at room temperature for 16 hours.
After the stirring was completed, 100 mL of a 10 wt% aqueous sodium thiosulfate solution was added to the reaction solution, and the presence or absence of unreacted peroxide was confirmed. After confirming that no peroxide remained, 500 mL of 1M aqueous sodium hydroxide solution was added, and after washing, washing was performed with water until the lower layer solution became neutral (500 mL × 10 times). Thereafter, the solvent was distilled off with an evaporator, and a yellow and liquid polyorganosilsesquioxane containing 14.9% by weight of ethyl acetate (the structural unit represented by the following formula (A) and the following formula (B) 42.7 g of a compound having a structural unit represented by
When the product was analyzed, the number average molecular weight was 1226, the molecular weight dispersity was 1.18, and the epoxy equivalent was 720 g / eq. The molar ratio [T3 isomer / T2 isomer] of T2 isomer and T3 isomer calculated from the ²⁹ Si-NMR spectrum of the above product was 3.3. The measurement result of ¹ H-NMR spectrum and the measurement result of ²⁹ Si-NMR spectrum of the obtained polyorganosilsesquioxane are shown in FIGS. 3 and 4, respectively. Note that “T ² ” and “T ³ ” in FIG. 4 indicate T2 body and T3 body, respectively.
[R ⁴ SiO _3/2 ] (A)
[R ⁴ SiO _2/2 (OR ^d )] (B)
[Wherein, R ⁴ represents a group represented by the following formula, and R ^d represents a methyl group. ]

Synthesis example 4
(Preparation of monohydrosilylation product)
A flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen introduction tube was charged with 500 g of dicyclopentadiene, 3 L of toluene, 1.96 g of H ₂ PtCl ₆ .6H ₂ O, and acetic acid 22 under a nitrogen stream. 0.7 g was charged and the temperature was raised to 80 ° C. 1386 g of trimethoxysilane was added dropwise to the mixture thus obtained, and the mixture was heated and stirred for 16 hours.
After completion of the stirring, the reaction solution was cooled, the solvent was distilled off with an evaporator, and then, a colorless, transparent and liquid monohydrosilylation product (compound represented by the following formula) (349.7 g, yield 36%) was obtained by distillation. . The measurement result of the ¹ H-NMR spectrum of the obtained monohydrosilylation product is shown in FIG.

Synthesis example 5
(Preparation of double bond-containing polyorganosilsesquioxane)
In a flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube, 72 g of the monohydrosilylation product obtained in Synthesis Example 4, THF 720 mL, sodium hydroxide 4. 54 g and 6.63 g of water were charged. The mixture thus obtained was stirred for 5 hours while refluxing.
After completion of stirring, the reaction solution was cooled and extracted with ethyl acetate (500 mL × 3 times). Thereafter, the combined organic phases were washed with water (500 mL × 3 times). After distilling off the solvent with an evaporator, a yellow and liquid double bond-containing polyorganosilsesquioxane (the structural unit represented by the following formula (C ′) and the structural unit represented by the following formula (D ′) Compound 72) was obtained. The measurement result of the ¹ H-NMR spectrum of the obtained polyorganosilsesquioxane is shown in FIG.
[R ⁵ SiO _3/2 ] (C ′)
[R ⁵ SiO _2/2 (OR ^d )] (D ′)
[Wherein, R ⁵ represents a group represented by the following formula, and R ^d represents a methyl group. ]

Synthesis Example 6
(Preparation of epoxy tricyclo [5.2.1.0 ^2,6 ] decanyl group-containing polyorganosilsesquioxane)
A flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube was charged with 72 g of the polyorganosilsesquioxane obtained in Synthesis Example 5 and 720 mL of ethyl acetate under a nitrogen stream. It is. 49 g of mCPBA was added to the mixture thus obtained, and the mixture was stirred at room temperature for 5 hours.
After the stirring was completed, 100 mL of a 10 wt% aqueous sodium thiosulfate solution was added to the reaction solution, and the presence or absence of unreacted peroxide was confirmed. After confirming that no peroxide remained, 1000 mL of 1 M aqueous sodium hydroxide solution was added, and after washing, washing was performed with water until the lower layer solution became neutral (1000 mL × 5 times). Thereafter, the solvent was distilled off with an evaporator, and a yellow and liquid polyorganosilsesquioxane containing 26.0% by weight of ethyl acetate (the structural unit represented by the following formula (C) and the following formula (D) Compound having a structural unit represented by 52.9 g was obtained.
When the product was analyzed, the number average molecular weight was 730, the molecular weight dispersity was 1.02, and the epoxy equivalent was 256 g / eq. The molar ratio [T3 body / T2 body] of T2 body and T3 body calculated from the ²⁹ Si-NMR spectrum of the product was 1.4. The measurement result of ¹ H-NMR spectrum and the measurement result of ²⁹ Si-NMR spectrum of the obtained polyorganosilsesquioxane are shown in FIGS. 7 and 8, respectively. In addition, “T ² ” and “T ³ ” in FIG. 8 indicate T2 body and T3 body, respectively.
[R ⁶ SiO _3/2 ] (C)
[R ⁶ SiO _2/2 (OR ^d )] (D)
[Wherein, R ⁶ represents a group represented by the following formula, and R ^d represents a methyl group. ]

Example 1
In a 6 cc brown sample bottle, 2 g of polyorganosilsesquioxane obtained in Synthesis Example 3 (2 g as MIBK 14.9 wt% content), trade name “WPI-124” (manufactured by Wako Pure Chemical Industries, Ltd., Photoacid generator 50 wt% solution) 34.0 mg (34.0 mg as 50 wt% solution), trade name “S-243” (AGC Seimi Chemical Co., Ltd., leveling agent) 8.5 mg, and MIBK 0. 837 g was added and stirred and mixed with a vibrator to prepare a curable composition (hard coat liquid).
The wire coat is used on the PET film (trade name “KEB03W”, manufactured by Teijin DuPont Films Ltd.) so that the thickness of the hard coat layer after curing is 10 μm. Then, it was allowed to stand (pre-bake) for 10 minutes in an oven at 120 ° C. and then irradiated with ultraviolet rays (irradiation conditions (irradiation amount): 430 mJ / cm ² , irradiation intensity: 120 W / cm ² ). Finally, the coating film of the hard coat liquid was cured by heat treatment (aging) at 80 ° C. for 2 hours to produce a hard coat film having a hard coat layer.
It was 2H as a result of evaluating the pencil hardness of the hard coat layer surface in the hard coat film obtained above according to JIS K5600-5-4.

Example 2
In a 6 cc brown sample bottle, 2 g of polyorganosilsesquioxane obtained in Synthesis Example 6 (2 g as MIBK 26.0 wt% content), trade name “WPI-124” (manufactured by Wako Pure Chemical Industries, Ltd., 29.6 mg (29.6 mg as a 50 wt% solution), a trade name “S-243” (manufactured by AGC Seimi Chemical Co., Ltd., leveling agent), 7.4 mg, and MIBK 0. 467 g was added and stirred and mixed with a vibrator to prepare a curable composition (hard coat liquid).
The wire coat is used on the PET film (trade name “KEB03W”, manufactured by Teijin DuPont Films Ltd.) so that the thickness of the hard coat layer after curing is 10 μm. Then, it was allowed to stand (pre-bake) for 10 minutes in an oven at 120 ° C. and then irradiated with ultraviolet rays (irradiation conditions (irradiation amount): 430 mJ / cm ² , irradiation intensity: 120 W / cm ² ). Finally, the coating film of the hard coat liquid was cured by heat treatment (aging) at 80 ° C. for 2 hours to produce a hard coat film having a hard coat layer.
It was 2H as a result of evaluating the pencil hardness of the hard coat layer surface in the hard coat film obtained above according to JIS K5600-5-4.

Comparative Example 1
The product name “Glycidyl POSS Cage Mixture” (manufactured by Hybrid Plastics Co., Ltd., polyorganosilsesquioxane containing glycidyl group) 3 g, product name “WPI-124” (manufactured by Wako Pure Chemical Industries, Ltd.) , Photoacid generator 50 wt% solution) 60.0 mg (60.0 mg as a 50 wt% solution), trade name “BYK-307” (Bick Chemie, leveling agent) 6.0 mg, and MIBK 2.0 g The mixture was stirred and mixed with a vibrator to prepare a curable composition (hard coat liquid).
The wire coat is used on the PET film (trade name “KEB03W”, manufactured by Teijin DuPont Films Ltd.) so that the thickness of the hard coat layer after curing is 40 μm. Then, it was allowed to stand (pre-bake) for 10 minutes in an oven at 120 ° C., and then irradiated with ultraviolet rays (irradiation conditions (irradiation amount): 434 mJ / cm ² , irradiation intensity: 120 W / cm ² ). Finally, the coating film of the hard coat liquid was cured by heat treatment (aging) at 80 ° C. for 2 hours to produce a hard coat film having a hard coat layer.
It was F as a result of evaluating the pencil hardness of the hard coat layer surface in the hard coat film obtained above according to JIS K5600-5-4.

  As can be seen from the above Examples and Comparative Examples, the hard coat layer of Comparative Example 1 has a pencil hardness F at a thickness of 40 μm, whereas the hard coat layer of the Example is a thin film with a thickness of 10 μm. However, the pencil hardness was 2H, and the surface hardness was remarkably excellent.

Claims (10)

Following formula (1)
[R ¹ SiO _3/2 ] (1)
[In the formula (1), R ¹ represents a group containing an epoxy group composed of two adjacent carbon atoms and an oxygen atom on an alicyclic ring having a bicyclo [2.2.1] heptane skeleton. ]
The silsesquioxane characterized by having the structural unit represented by these.   The silsesquioxane of Claim 1 whose epoxy equivalent is 100-1000 g / eq.   The silsesquioxane of Claim 1 or 2 whose number average molecular weights of standard polystyrene conversion by gel permeation chromatography are 500-3000, and molecular weight dispersion degree are 1.0-2.0. R ¹ in the structural unit represented by the formula (1) is represented by the following formula (1a)

[In Formula (1a), R ^1a represents a single bond or a linear or branched alkylene group. However, a substituent may be bonded to one or more carbon atoms constituting the alicyclic ring. ]
And / or the following formula (1b)

[In Formula (1b), R ^1b represents a single bond or a linear or branched alkylene group. However, a substituent may be bonded to one or more carbon atoms constituting the alicyclic ring. ]
The silsesquioxane of any one of Claims 1-3 which is group represented by these. Formula (I)
[R ^a SiO _3/2 ] (I)
[In the formula (I), R ^a is a group containing a substituted or unsubstituted epoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, substituted or unsubstituted An unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom is shown. ]
And a structural unit represented by the following formula (II)
[R ^b SiO _2/2 (OR ^c )] (II)
[In the formula (II), R ^b represents a group containing a substituted or unsubstituted epoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, substituted or unsubstituted An unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a hydrogen atom is shown. R ^c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]
The ratio of the structural unit represented by [the structural unit represented by the formula (I) / the structural unit represented by the formula (II)] is 1 to 8, according to any one of claims 1 to 4. Silsesquioxane.   The curable composition containing the silsesquioxane of any one of Claims 1-5.   Furthermore, the curable composition of Claim 6 containing a curing catalyst.   The curable composition according to claim 6 or 7, which is a curable composition for forming a hard coat layer.   Hardened | cured material of the curable composition of any one of Claims 6-8.   A hard coat film comprising a base material and a hard coat layer formed on at least one surface of the base material, wherein the hard coat layer is a layer of a cured product of the curable composition according to claim 9. A hard coat film characterized by

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