JP6580878B2 - Polyorganosilsesquioxane, curable composition, hard coat film, and cured product - Google Patents

Description

  The present invention relates to a novel polyorganosilsesquioxane, a curable composition containing the polyorganosilsesquioxane, 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 polyorganosilsesquioxane.

  Conventionally, a hard coat film having a hard coat layer on one side or both sides of a substrate and having a hard hardness of about 3H on the surface of the hard coat layer 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

  However, it has not been said that the hard coat film using the above-mentioned UV acrylic monomer has sufficient surface hardness. In general, in order to increase the hardness, it is conceivable to use a polyfunctional UV acrylic monomer or to increase the thickness of the hard coat layer. When such a method is adopted, the hard coat layer is cured. There was a problem that the shrinkage increased, and as a result, the hard coat film was curled and cracked. Further, when nanoparticles are added to the hard coat layer, if the compatibility between the nanoparticles and the UV acrylic monomer is poor, there is a problem that the nanoparticles aggregate and the hard coat layer is whitened.

Accordingly, an object of the present invention is to provide a polyorganosilsesquioxane that can be cured to form a cured product having a high surface hardness.
Another object of the present invention is to provide a hard coat film which has flexibility and can be manufactured and processed by a roll-to-roll method while maintaining high surface hardness.
Furthermore, the other object of this invention is to provide the said hard coat film which can be further stamped.

  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 a silsesquioxane structural unit (unit structure) containing an epoxy group, and a specific structure ratio (Q unit, T3 body, and T2 body). According to the polyorganosilsesquioxane whose proportion and the proportion of silsesquioxane structural units containing epoxy groups) are controlled in a specific range, by curing the curable composition containing the polyorganosilsesquioxane It was found that a cured product having a high surface hardness can be formed. In addition, the inventors of the present invention have a hard coat film having a hard coat layer formed from a hard coat solution containing the polyorganosilsesquioxane having flexibility while maintaining high surface hardness. It was found that it is a hard coat film that can be manufactured and processed by the to-roll method. The present invention has been completed based on these findings.

［式（１）中、Ｒ¹は、エポキシ基を含有する基を示す。］
で表される構成単位を有し、下記式（Ｉ）

［式（Ｉ）中、Ｒ^aは、エポキシ基を含有する基、置換若しくは無置換のアリール基、置換若しくは無置換のアラルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルケニル基、又は水素原子を示す。］
で表される構成単位と、下記式（II）

［式（II）中、Ｒ^bは、エポキシ基を含有する基、置換若しくは無置換のアリール基、置換若しくは無置換のアラルキル基、置換若しくは無置換のシクロアルキル基、置換若しくは無置換のアルキル基、置換若しくは無置換のアルケニル基、又は水素原子を示す。Ｒ^cは、水素原子又は炭素数１〜４のアルキル基を示す。］
で表される構成単位の割合［式（Ｉ）で表される構成単位／式（II）で表される構成単位］が５以上であり、上記式（Ｉ）で表される構成単位及び上記式（II）で表される構成単位の合計と、下記式（４）

で表される構成単位の割合［｛式（Ｉ）で表される構成単位及び式（II）で表される構成単位の合計｝／式（４）で表される構成単位］が１〜３０であり、シロキサン構成単位の全量に対する上記式（１）で表される構成単位及び下記式（５）

［式（５）中、Ｒ¹は、式（１）におけるものと同じ。Ｒ^cは、式（II）におけるものと同じ。］
で表される構成単位の割合が５０〜９９モル％であることを特徴とするポリオルガノシルセスキオキサンを提供する。 That is, the present invention provides the following formula (1):

[In Formula (1), R < ¹ > shows group containing an epoxy group. ]
Having a structural unit represented by the following formula (I)

[In the formula (I), R ^a is a group containing an epoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group. Represents a substituted or unsubstituted alkenyl group or a hydrogen atom. ]
And a structural unit represented by the following formula (II)

[In the formula (II), R ^b represents an epoxy group-containing group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group. Represents a substituted or unsubstituted alkenyl group or a hydrogen atom. 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 5 or more, the structural unit represented by the above formula (I), and the above The sum of the structural units represented by formula (II) and the following formula (4)

The ratio of the structural unit represented by [{the total of the structural unit represented by formula (I) and the structural unit represented by formula (II)} / the structural unit represented by formula (4)] is 1 to 30 The structural unit represented by the above formula (1) with respect to the total amount of the siloxane structural unit and the following formula (5)

[In formula (5), R ¹ is the same as that in formula (1). R ^c is the same as in formula (II). ]
The ratio of the structural unit represented by this is 50-99 mol%, The polyorgano silsesquioxane characterized by the above-mentioned is provided.

  Further, the polyorganosilsesquioxane has a number average molecular weight in terms of standard polystyrene by gel permeation chromatography of 500 to 6000, and a molecular weight dispersity (weight average molecular weight / number average molecular weight) of 1.0 to 3. The polyorganosilsesquioxane is provided as 0.

［式（１ａ）中、Ｒ^1aは、直鎖又は分岐鎖状のアルキレン基を示す。］
で表される基、下記式（１ｂ）

［式（１ｂ）中、Ｒ^1bは、直鎖又は分岐鎖状のアルキレン基を示す。］
で表される基、下記式（１ｃ）

［式（１ｃ）中、Ｒ^1cは、直鎖又は分岐鎖状のアルキレン基を示す。］
で表される基、及び、下記式（１ｄ）

［式（１ｄ）中、Ｒ^1dは、直鎖又は分岐鎖状のアルキレン基を示す。］
で表される基からなる群より選択される１種以上の基である前記のポリオルガノシルセスキオキサンを提供する。 Further, the R ¹ is represented by the following formula (1a)

Wherein (1a), R ^1a represents a linear or branched alkylene group. ]
A group represented by formula (1b):

[In formula (1b), R ^1b represents a linear or branched alkylene group. ]
A group represented by formula (1c):

[In Formula (1c), R ^1c represents a linear or branched alkylene group. ]
And a group represented by the following formula (1d):

[In formula (1d), R ^1d represents a linear or branched alkylene group. ]
The polyorganosilsesquioxane is provided as one or more groups selected from the group consisting of groups represented by:

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

  Furthermore, the said curable composition containing a curing catalyst is provided.

  Furthermore, the said curable composition whose said curing catalyst is a photocationic polymerization initiator is provided.

  Furthermore, the curable composition is provided wherein the curing catalyst is a thermal cationic polymerization initiator.

  Furthermore, the said curable composition containing a vinyl ether compound is provided.

  Furthermore, the said curable composition containing the vinyl ether compound which has a hydroxyl group in a molecule | numerator is provided.

  Furthermore, the said curable composition which is a curable composition for hard-coat layer formation is provided.

  Moreover, this invention provides the hardened | cured material obtained by hardening the said curable composition.

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

  Furthermore, the hard coat film has a thickness of 1 to 200 μm.

  Furthermore, the said hard coat film which can be manufactured by a roll to roll system is provided.

  Furthermore, the hard coat film having a surface protective film on the surface of the hard coat layer is provided.

  Moreover, this invention applies the said curable composition to the process A which draws out the base material wound by roll shape, and at least one surface of the drawn-out base material, and then hardens this curable composition. A hard coat film comprising a step B of forming a hard coat layer by the step C, and a step C after which the obtained hard coat film is wound around a roll again. A manufacturing method is provided.

  Since the polyorganosilsesquioxane of this invention has the said structure, the hardened | cured material which has high surface hardness can be formed by hardening | curing the curable composition which contains this polyorganosilsesquioxane as an essential component. Moreover, since the hard coat film of this invention has the said structure, it has a flexibility, maintaining high surface hardness, and manufacture and a process by roll to roll are possible. For this reason, the hard coat film of the present invention is excellent in both quality and cost.

FIG. 1 is a view showing ¹ H-NMR measurement results of the polyorganosilsesquioxane obtained in Example 1. FIG. FIG. 2 is a diagram showing the ²⁹ Si-NMR measurement result of the polyorganosilsesquioxane obtained in Example 1. FIG. 3 is a graph showing the results of FT-IR spectrum measurement of the polyorganosilsesquioxane obtained in Example 1. FIG. 4 is a view showing ¹ H-NMR measurement results of the polyorganosilsesquioxane obtained in Example 2. FIG. 5 shows the results of ²⁹ Si-NMR measurement of the polyorganosilsesquioxane obtained in Example 2. 6 is a graph showing the results of FT-IR spectrum measurement of the polyorganosilsesquioxane obtained in Example 2. FIG. FIG. 7 shows the ¹ H-NMR measurement result of the polyorganosilsesquioxane obtained in Example 3. FIG. 8 shows the results of ²⁹ Si-NMR measurement of the polyorganosilsesquioxane obtained in Example 3. FIG. 9 is a graph showing the results of FT-IR spectrum measurement of the polyorganosilsesquioxane obtained in Example 3.

[Polyorganosilsesquioxane]
The polyorganosilsesquioxane (silsesquioxane) of the present invention has a structural unit represented by the following formula (1); a structural unit represented by the following formula (I) (referred to as “T3 body”). The molar ratio of the structural unit represented by the following formula (II) (sometimes referred to as “T2 form”) [the structural unit represented by the formula (I) / the formula (II) The structural unit; “may be described as“ T3 body / T2 body ”] is 5 or more; the sum of the structural unit represented by formula (I) and the structural unit represented by formula (II); Molar ratio of structural unit represented by formula (4) (sometimes referred to as “Q unit”) [{total of structural unit represented by formula (I) and structural unit represented by formula (II)} / Constituent unit represented by formula (4); “may be described as (T3 body + T2 body) / Q unit”] is 1 to 30; The ratio (total amount) of the structural unit represented by the following formula (1) and the structural unit represented by the following formula (5) with respect to the total amount (100 mol%) of the unit is 50 to 99 mol%. To do.

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 formed by hydrolysis and condensation reaction of a corresponding hydrolyzable trifunctional silane compound (specifically, for example, a compound represented by the following formula (a)). Is done.

R ¹ in the formula (1) represents a group (monovalent group) containing an epoxy group. That is, the polyorganosilsesquioxane of the present invention is a cationic curable compound (cationic polymerizable compound) having at least an epoxy group in the molecule. Examples of the group containing an epoxy group include known or commonly used groups having an oxirane ring, and are not particularly limited. However, from the viewpoint of curability of the curable composition and heat resistance of the cured product, the following formula (1a) Group represented by the following formula (1b), a group represented by the following formula (1c), and a group represented by the following formula (1d) are preferable, and more preferably the following formula (1a): A group represented by the following formula (1c), more preferably a group represented by the following formula (1a).

In the above formula (1a), R ^1a represents 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 or a branched alkylene group having 3 or 4 carbon atoms, more preferably from the viewpoint of the surface hardness or curability of the cured product. An ethylene group, a trimethylene group, and a propylene group, and more preferably an ethylene group and a trimethylene group.

In the above formula (1b), R ^1b represents a linear or branched alkylene group, and examples thereof include the same groups as R ^1a . Among them, R ^1b is preferably a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms, more preferably, from the viewpoint of the surface hardness or curability of the cured product. An ethylene group, a trimethylene group, and a propylene group, and more preferably an ethylene group and a trimethylene group.

In said formula (1c), R ^<1c> shows a linear or branched alkylene group, and the group similar to R ^<1a> is illustrated. Among these, R ^1c is preferably a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms, more preferably from the viewpoint of the surface hardness or curability of the cured product. An ethylene group, a trimethylene group, and a propylene group, and more preferably an ethylene group and a trimethylene group.

In the above formula (1d), R ^1d represents a linear or branched alkylene group, and examples thereof include the same groups as R ^1a . Among these, R ^1d is preferably a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms, more preferably from the viewpoint of the surface hardness or curability of the cured product. An ethylene group, a trimethylene group, and a propylene group, and more preferably an ethylene group and a trimethylene group.

R ¹ in formula (1) is particularly a group represented by the above formula (1a), in which R ^1a is an ethylene group [in particular, a 2- (3,4-epoxycyclohexyl) ethyl group. ] Is preferable.

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

The polyorganosilsesquioxane of this invention has further a structural unit represented by following formula (4) as a siloxane structural unit.

  The structural unit represented by the above formula (4) is a so-called Q unit. That is, the structural unit represented by the above formula (4) is a hydrolysis and condensation reaction of a corresponding hydrolyzable tetrafunctional silane compound (specifically, for example, a compound represented by the following formula (d)). It is formed by.

The polyorganosilsesquioxane of the present invention has a constitution represented by the above formula (1) in addition to the constitutional unit represented by the above formula (1) and the constitutional unit represented by the above formula (4). Silsesquioxane units other than the units [RSiO _3/2 ], units represented by [R ₃ SiO _1/2 ] (so-called M units), and units represented by [R ₂ SiO _2/2 ] You may have at least 1 type of siloxane structural unit selected from the group which consists of a unit (what is called D unit). Examples of the silsesquioxane structural unit other than the structural unit represented by the above formula (1) include a structural unit represented by the following formula (2), a structural unit represented by the following formula (3), and the like. Is mentioned.

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)). It is formed by.

In formula (2), R ² represents a substituted or 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 group An alkenyl group is shown. 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 above-mentioned substituted aryl group, substituted aralkyl group, substituted cycloalkyl group, substituted alkyl group, and substituted alkenyl group, the above-mentioned aryl group, aralkyl group, cycloalkyl group, alkyl group, and alkenyl group are each a hydrogen atom or main chain. Part or all of the case is an ether group, ester group, carbonyl group, siloxane group, halogen atom (fluorine atom, etc.), acrylic group, methacryl group, mercapto group, amino group, and hydroxy group (hydroxyl group). And a group substituted with at least one selected.

Among them, R ² is preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, more preferably a substituted or unsubstituted aryl group, more preferably a phenyl group. is there.

  In the polyorganosilsesquioxane of the present invention, the proportion of each of the above siloxane structural units (for example, the structural units represented by the formulas (1) to (4)) is determined as a raw material (hydrolysate) for forming these structural units. It is possible to adjust appropriately according to the composition of degradable trifunctional silane, hydrolyzable tetrafunctional silane and the like.

  Ratio 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 polyorganosilsesquioxane of the present invention [T3 body / T2 body] ] Is 5 or more as described above, preferably 5 to 18, more preferably 6 to 16, and still more preferably 7 to 14. By setting the ratio [T3 body / T2 body] to 5 or more, the surface hardness of the cured product or the hard coat layer is remarkably improved.

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, an epoxy group A group containing, substituted or unsubstituted aryl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, or hydrogen atom Show. 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 the formula (I) and R ^b in the formula (II) were bonded to silicon atoms in the hydrolyzable trifunctional silane compound used as a raw material of the polyorganosilsesquioxane of the present invention, respectively. It is derived from a group (a group other than an alkoxy group and a halogen atom; for example, R ¹ , R ² and a hydrogen atom in the formulas (a) to (c) described later).

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. . In general, the alkyl group in R ^c in the formula (II) is generally an alkoxy group (for example, X ^{1 to} X ³ described later) in the hydrolyzable silane compound used as a raw material of the polyorganosilsesquioxane of the present invention. Derived from an alkyl group forming an alkoxy group or the like.

  In the polyorganosilsesquioxane of the present invention, the total of the structural unit (T3 form) represented by the above formula (I) and the structural unit (T2 form) represented by the above formula (II), and the above formula (4) The ratio [(T3 body + T2 body) / Q unit] of the structural unit (Q unit) represented by is 1 to 30, as described above, preferably 1.2 to 25, more preferably 1.5 to 23, more preferably 2-20. By setting the ratio [(T3 body + T2 body) / Q unit] within the above range, the surface hardness of the cured product and the hard coat layer is remarkably improved.

In addition, when the structural unit represented by the above formula (4) is described in more detail, it is represented by the following formula (4 ′). Each of the four oxygen atoms bonded to the silicon atom shown in the structure represented by the following formula (4 ′) is bonded to another silicon atom (a silicon atom not shown in the formula (4 ′)). . That is, the Q unit is a structural unit formed by hydrolysis and condensation reaction of a hydrolyzable tetrafunctional silane compound.

The ratio [T3 body / T2 body] and the ratio [(T3 body + T2 body) / Q unit] in the polyorganosilsesquioxane of the present invention can be determined by, for example, ²⁹ Si-NMR spectrum measurement. ^{In the 29} Si-NMR spectrum, the silicon atom in the structural unit (T3 form) represented by the above formula (I), the silicon atom in the structural unit (T2 form) represented by the above formula (II), and the above formula ( 4) In order to show a signal (peak) at a position (chemical shift) different from the silicon atom in the structural unit (Q unit) represented by 4), the above ratio [T3 Body / T2 body] and the above ratio [(T3 body + T2 body) / Q unit]. Specifically, for example, when the polyorganosilsesquioxane of the present invention has a structural unit represented by the above formula (1) and R ¹ is a 2- (3,4-epoxycyclohexyl) ethyl group. The silicon atom signal in the structure (T3 form) represented by the above formula (I) appears at −64 to −70 ppm, and the silicon atom signal in the structure (T2 form) represented by the above formula (II) is It appears at −54 to −60 ppm, and the signal of the silicon atom in the structure (Q unit) represented by the above formula (4) appears at −100 to −120 ppm. 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. In addition, by calculating an integration ratio of a signal (T3 body) of −64 to −70 ppm, a signal (T2 body) of −54 to −60 ppm and a signal (Q unit) of −100 to −120 ppm, the above ratio [ (T3 body + T2 body) / Q unit] can be obtained.

The ²⁹ Si-NMR spectrum of the polyorganosilsesquioxane of the present invention can be measured, for example, with 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

The ratio [T3 body / T2 body] of the polyorganosilsesquioxane of the present invention is 5 or more. In the polyorganosilsesquioxane of the present invention, a certain amount or more of T2 bodies exist with respect to the T3 body. Means that Examples of such a T2 body include a structural unit represented by the following formula (5), a structural unit represented by the following formula (6), a structural unit represented by the following formula (7), and the like. R ² in R ¹ and the following formula (6) in the following equation (5) is the same as R ² in R ¹ and the formula in the formula (1) (2). R ^c in the formula (5) to (7), like the R ^c in Formula (II), a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In general, a complete cage silsesquioxane is a polyorganosilsesquioxane composed only of a T3 form, and no T2 form exists in the molecule. That is, the polyorganosilsesquioxane of the present invention when the above ratio [T3 / T2] is 5 or more and further has one intrinsic absorption peak in the vicinity of 1100 cm ⁻¹ in the FT-IR spectrum as described later. Is suggested to have an incomplete cage silsesquioxane structure.

In addition, the ratio [(T3 body + T2 body) / Q unit] of the polyorganosilsesquioxane of the present invention is 1 to 30 in the polyorganosilsesquioxane of the present invention in the T3 body and the T2 body. On the other hand, it means that there is a certain Q unit or more. The ratio [T3 body / T2 body] is 5 or more, and has one intrinsic absorption peak in the vicinity of 1100 cm ⁻¹ in the FT-IR spectrum as described later. Further, the ratio [(T3 body + T2 body) ) / Q unit] is 1 to 30, and in the ²⁹ Si-NMR spectrum, the polyorganosilsesquioxane of the present invention having one intrinsic absorption peak in the vicinity of −110 ppm is an incomplete cage silsesquioxane. It is suggested that the structure has a structure in which a plurality of (for example, two) structures are combined.

The polyorganosilsesquioxane of the present invention has a cage-type (incomplete cage-type) silsesquioxane structure. The polyorganosilsesquioxane of the present invention has a FT-IR spectrum of around 1050 cm ⁻¹ and 1150 cm. respectively in the vicinity of ^-1 it does not have a specific absorption peak is confirmed by the fact that with a single specific absorption peak in the vicinity of 1100 cm ^-1 [ref: 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. In addition, the FT-IR spectrum of the polyorganosilsesquioxane 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 polyorganosilsesquioxane of the present invention [total siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%). The proportion (total amount) of the structural unit represented by formula (5) is 50 to 99 mol%, preferably 55 to 98 mol%, more preferably 60 to 95, as described above. Mol%. By making the said ratio 50 mol% or more, the sclerosis | hardenability of a curable composition improves and the surface hardness of hardened | cured material becomes remarkably high. In addition, the ratio of each siloxane structural unit in the polyorganosilsesquioxane of this invention is computable by the composition of a raw material, NMR spectrum measurement, etc., for example.

  The total amount of siloxane structural units in the polyorganosilsesquioxane of the present invention [total siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%). The proportion (total amount) of the structural units to be formed is not particularly limited, but is preferably 1 to 50 mol%, more preferably 2 to 45 mol%, still more preferably 5 to 40 mol%. By setting the ratio to 1 mol% or more, the surface hardness of the cured product is remarkably increased.

  The total amount of siloxane structural units in the polyorganosilsesquioxane of the present invention [total siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%). Although the ratio (total amount) of the structural unit represented and the structural unit represented by said Formula (6) is not specifically limited, 0-70 mol% is preferable, More preferably, it is 0-60 mol%, More preferably, it is 0- It is 40 mol%, particularly preferably 1 to 15 mol%. By making the ratio 70 mol% or less, the proportion of the structural unit represented by the formula (1), the structural unit represented by the formula (5), and the structural unit represented by the formula (4) Therefore, the curability of the curable composition tends to be further improved. 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 polyorganosilsesquioxane of the present invention [total siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%). The ratio (total amount) of the structural unit represented by the structural unit represented by the formula (2), the structural unit represented by the formula (5), and the structural unit represented by the formula (6) is particularly limited. Although it is not, 55 to 99 mol% is preferable, More preferably, it is 60 to 99 mol%, More preferably, it is 65 to 99 mol%. When the ratio is 55 mol% or more, the surface hardness of the cured product tends to be higher.

  The total amount of siloxane structural units in the polyorganosilsesquioxane of the present invention [total siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%). The structural unit represented by the above formula (2), the structural unit represented by the above formula (4), the structural unit represented by the above formula (5), and the above formula (6). The proportion (total amount) of structural units is not particularly limited, but is preferably 60 mol% or more (for example, 60 to 100 mol%), more preferably 70 mol% or more, still more preferably 80 mol% or more, particularly preferably. It is 90 mol% or more. When the ratio is 60 mol% or more, the surface hardness of the cured product tends to be higher.

  The number average molecular weight (Mn) in terms of standard polystyrene by gel permeation chromatography of the polyorganosilsesquioxane of the present invention is not particularly limited, but is preferably 500 to 6000, more preferably 1000 to 5500, and still more preferably 1100. ~ 5000. When the number average molecular weight is 500 or more, the heat resistance and scratch resistance of the cured product are further improved. On the other hand, when the number average molecular weight is 6000 or less, the compatibility with other components in the curable composition is improved, and the heat resistance of the cured product is further improved.

  The molecular weight dispersity (Mw / Mn) in terms of standard polystyrene by gel permeation chromatography of the polyorganosilsesquioxane of the present invention is not particularly limited, but is preferably 1.0 to 3.0, more preferably 1. It is 1 to 2.6, more preferably 1.2 to 2.5, and particularly preferably 1.45 to 1.80. When the molecular weight dispersity is 3.0 or less, the surface hardness of the cured product becomes higher. On the other hand, when the molecular weight dispersity is 1.0 or more (particularly 1.1 or more), it tends to be in a liquid state and the handleability tends to be improved.

In addition, the number average molecular weight and molecular weight dispersity of the polyorganosilsesquioxane 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 polyorganosilsesquioxane 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 It can be produced by a method of condensation. However, as the hydrolyzable silane compound, a hydrolyzable trifunctional silane compound (compound represented by the following formula (a)) for forming the structural unit represented by the above formula (1) and the above described It is necessary to use a hydrolyzable tetrafunctional silane compound (compound represented by the following formula (d)) for forming the structural unit represented by the formula (4) as an essential hydrolyzable silane compound.

More specifically, for example, a compound represented by the following formula (a) which is a hydrolyzable silane compound for forming a silsesquioxane structural unit (T unit) in the polyorganosilsesquioxane of the present invention. , A compound represented by the following formula (d) which is a hydrolyzable silane compound for forming the Q unit, a compound represented by the following formula (b), if necessary, a formula represented by the following formula (c) The polyorganosilsesquioxane of this invention can be manufactured by the method of hydrolyzing and condensing the compound made.

The compound represented by the above formula (a) is a compound that forms the structural unit represented by the formula (1) in the polyorganosilsesquioxane of the present invention. R ¹ in the formula (a), like that of R ¹ in the formula (1), a group containing an epoxy group. That is, R ¹ in the formula (a) is a group represented by the above formula (1a), a group represented by the above formula (1b), a group represented by the above formula (1c), or the above formula (1d). The group represented by the above formula (1a), the group represented by the above formula (1c), more preferably the group represented by the above formula (1a), particularly preferably Is a group represented by the above formula (1a), and R ^1a is an ethylene group [in particular, a 2- (3,4-epoxycyclohexyl) ethyl group].

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 polyorganosilsesquioxane of the present invention. R ² in formula (b), like the R ² in the formula (2), a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted An alkyl group, or a substituted or unsubstituted alkenyl group. That is, R ² in formula (b) is preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, more preferably a substituted or unsubstituted aryl group, More preferred is a phenyl group.

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 polyorganosilsesquioxane 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.

The compound represented by the above formula (d) is a compound that forms the structural unit represented by the formula (4) in the polyorganosilsesquioxane of the present invention. X ⁴ in the above formula (d) represents an alkoxy group or a halogen atom. Specific examples of X ⁴ include those exemplified as X ¹ . Among them, X ⁴ is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. The four X ^{4 s} may be the same or different.

  As said hydrolysable silane compound, you may use together hydrolysable silane compounds other than the compound represented by said formula (a)-(d). 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 Compounds and the like.

  The amount and composition of the hydrolyzable silane compound can be appropriately adjusted according to the desired structure of the polyorganosilsesquioxane of the present invention. For example, although the usage-amount of the compound represented by the said formula (a) is not specifically limited, 50-99 mol% is preferable with respect to the whole quantity (100 mol%) of the hydrolysable silane compound to be used, More preferably Is 55 to 98 mol%, more preferably 60 to 95 mol%.

  The amount of the compound represented by the formula (b) is not particularly limited, but is preferably 0 to 70 mol%, more preferably based on the total amount (100 mol%) of the hydrolyzable silane compound to be used. Is 0 to 60 mol%, more preferably 0 to 40 mol%, particularly preferably 1 to 15 mol%.

  Moreover, the usage-amount of the compound represented by the said Formula (d) is although it does not specifically limit, 1-50 mol% is preferable with respect to the whole quantity (100 mol%) of the hydrolysable silane compound to be used, More preferably Is 2 to 45 mol%, more preferably 5 to 40 mol%, particularly preferably 5 to 30 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. 50-99 mol% is preferable, More preferably, it is 55-98 mol%, More preferably, it is 60-95 mol%, Most preferably, it is 70-95 mol%.

  Furthermore, the ratio of the compound represented by the formula (a), the compound represented by the formula (b), and the compound represented by the formula (d) to the total amount (100 mol%) of the hydrolyzable silane compound to be used ( The ratio of the total amount is not particularly limited, but is preferably 60 mol% or more (for example, 60 to 100 mol%), more preferably 70 mol% or more, still more preferably 80 mol% or more, and particularly preferably 90 mol% or more. It is.

  In addition, the hydrolysis and condensation reaction of the hydrolyzable silane compound can be performed simultaneously or 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 and dioxane; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; methyl acetate and ethyl acetate. , Esters such as isopropyl acetate and butyl acetate; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; nitriles such as acetonitrile, propionitrile and benzonitrile; alcohols such as methanol, ethanol, isopropyl alcohol and butanol Etc. 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.

  As the reaction conditions for carrying out the hydrolysis and condensation reaction of the hydrolyzable silane compound, in particular, the reaction in which the ratio [T3 body / T2 body] in the polyorganosilsesquioxane of the present invention is 5 or more. It is important to select the conditions. Although the reaction temperature of the said hydrolysis and condensation reaction is not specifically limited, 5-100 degreeC is preferable, More preferably, it is 25-80 degreeC. By controlling the reaction temperature within the above range, the ratio [T3 body / T2 body] tends to be more efficiently controlled to 5 or more. Moreover, the reaction time of the said hydrolysis and condensation reaction is although it does not specifically limit, 0.1 to 10 hours are preferable, More preferably, it is 1.5 to 8 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.

  The polyorganosilsesquioxane of the present invention is obtained by hydrolysis and condensation reaction of the hydrolyzable silane compound. After completion of the hydrolysis and condensation reaction, it is preferable to neutralize the catalyst in order to suppress the ring opening of the epoxy group. In addition, the polyorganosilsesquioxane of the present invention can be combined with, for example, separation means such as water washing, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, and the like. Separation and purification may be performed by separation means or the like.

  Since the polyorganosilsesquioxane of the present invention has the above-described configuration, a cured product having high surface hardness can be formed by curing a curable composition containing the polyorganosilsesquioxane as an essential component. In addition, a cured product having high heat resistance and excellent flexibility and workability can be formed.

[Curable composition]
The curable composition of the present invention is a curable composition (curable resin composition) containing the polyorganosilsesquioxane 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 the present invention, the polyorganosilsesquioxane of the present invention can be used alone or in combination of two or more.

  The content (blending amount) of the polyorganosilsesquioxane of the present invention in the curable composition of the present invention is not particularly limited, but is 70 with respect to the total amount (100% by weight) of the curable composition excluding the solvent. It is preferably not less than 100% by weight and more preferably less than 100% by weight, more preferably 80 to 99.8% by weight, and still more preferably 90 to 99.5% by weight. By setting the content of the polyorganosilsesquioxane 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, by setting the content of the polyorganosilsesquioxane of the present invention to less than 100% by weight, it is possible to contain a curing catalyst, thereby allowing the curing of the curable composition to proceed more efficiently. There is a tendency to be able to.

  The ratio of the polyorganosilsesquioxane of the present invention to the total amount (100% by weight) of the cationic curable compound contained in the curable composition of the present invention is not particularly limited, but is preferably 70 to 100% by weight, more preferably. Is 75 to 98% by weight, more preferably 80 to 95% by weight. By setting the content of the polyorganosilsesquioxane 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 cation polymerization reaction of cationic curable compounds, such as the polyorgano 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 0.01 to 3.0 parts by weight with respect to 100 parts by weight of the polyorganosilsesquioxane of the present invention. Is more preferably 0.05 to 3.0 parts by weight, still more preferably 0.1 to 1.0 parts by weight (for example, 0.3 to 1.0 parts by weight). 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 polyorganosilsesquioxane of the present invention (sometimes referred to as “other cationic curable compounds”). As other cationic curable compounds, known or conventional cationic curable compounds can be used, and are not particularly limited. For example, epoxy compounds other than the polyorganosilsesquioxane 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.

  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] Compound obtained by hydrogenating bisphenol F-type epoxy compound such as methane (hydrogenated bisphenol F-type epoxy compound) Hydrogenated biphenol type epoxy compound; hydrogenated phenol novolak type epoxy compound; hydrogenated cresol novolak type epoxy compound; hydrogenated cresol novolak type epoxy compound of bisphenol A; hydrogenated naphthalene type epoxy compound; epoxy compound obtained from trisphenolmethane And hydrogenated epoxy compounds of the following aromatic epoxy compounds.

  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, it is preferable to use a vinyl ether compound in combination with the polyorganosilsesquioxane of the present invention as another cationic curable compound. This tends to increase the polymerization 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 polymerization rate increases, and heat 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 polyorganosilsesquioxane of the present invention and the other cationic curable compound (100% by weight). Preferably 50% by weight or less (for example, 0 to 50% by weight), more preferably 30% by weight or less (for example, 0 to 30% by weight), and further preferably 10% by weight, based on the total amount of the cationic curable compound. % Or less. 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 other cationic curable compounds to 10% by weight or more, desired performance for the curable composition or the cured product (for example, quick curability or 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 polyorganosilsesquioxane of the present invention and The amount is preferably 0.01 to 10% by weight, more preferably 0.05 to 9% by weight, still more preferably 1 to 1%, based on the total amount of other cationic curable compounds (100% by weight; the total amount of the cationic curable compound). 8% by weight. 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. These additives can be used individually by 1 type or in combination of 2 or more types. The content (blending amount) of the additive is not particularly limited, but is preferably 100 parts by weight or less, more preferably 30 parts by weight or less (for example, for 100 parts by weight of the polyorganosilsesquioxane of the present invention (for example, 0.01 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 100 to 10000 mPa · s, and still more preferably 300 to 8000 mPa · s. There exists a tendency for applicability | paintability to improve more 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 the polyorganosilsesquioxane of the present invention) in the curable composition of the present invention, the curable composition can be cured, and the cured product ("present" May be referred to as “the cured product of the invention”). 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. Further, glass is known as a material having a very high surface hardness, and in particular, glass having a surface pencil hardness of up to 9H by an alkali ion exchange treatment is known. However, flexibility and workability are known. Therefore, it is impossible to manufacture and process by roll-to-roll method, and it is necessary to manufacture and process by a single wafer, which requires high production cost. On the other hand, the hardened | cured material of this invention can form the hardened | cured material excellent in the flexibility and workability compared with glass. 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. The curable composition of the present invention is used as a curable composition for forming a hard coat layer, and a hard coat film having a hard coat layer formed from the composition has flexibility while maintaining high hardness. Can be manufactured and processed by roll-to-roll.

[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 (cured product layer 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 where the hard coat layer of the present invention is provided on both surfaces of the substrate) is not particularly limited, but is preferably 1 to 200 μm, more preferably 3 ~ 150 μm. In particular, even when the hard coat layer of the present invention is thin (for example, when the thickness is 5 μm or less), it is possible to maintain a high surface hardness (for example, the pencil hardness is set to H or more). . In addition, even when the thickness 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. 9H or higher).

  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. Moreover, the thickness of a surface protection film is not specifically limited, It can select suitably.

  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.

  In particular, the hard coat layer of the present invention in the hard coat film of the present invention is a hard coat layer formed from the curable composition of the present invention (the curable composition for forming a hard coat layer). The coat film can be manufactured by a roll-to-roll method. By producing the hard coat film of the present invention by a roll-to-roll method, the productivity can be remarkably increased. As a method for producing the hard coat film of the present invention by a roll-to-roll method, a known or conventional roll-to-roll method can be adopted, and is not particularly limited. For example, a base material wound in a roll shape And applying the curable composition of the present invention (a curable composition for forming a hard coat layer) to at least one surface of the fed substrate, and then drying the solvent as necessary. After removing by step, the step of forming the hard coat layer of the present invention by curing the curable composition (curable composition layer) (step B), and then the obtained hard coat film again in a roll The method of including the process (process C) to wind up as an essential process, and implementing these processes (process AC) continuously is mentioned. In addition, the said method may include processes other than process AC.

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

  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, and further preferably 6H or more. 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 flexibility while maintaining high hardness, and can be manufactured and processed by a roll-to-roll method. Therefore, the hard coat film has high quality and excellent productivity. 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 using Alliance HPLC system 2695 (manufactured by Waters), Refractive Index Detector 2414 (manufactured by Waters), column: Tskel GMH _HR- M × 2 (manufactured by Tosoh Corporation), 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 of T2 body, T3 body, and Q unit [(T3 body + T2 body) / Q unit] in the product was performed by ²⁹ Si-NMR spectrum measurement with JEOL ECA500 (500 MHz).

Example 1
A 1000 ml flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube was charged with 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (hereinafter, “EMS” under a nitrogen stream. ) 380.0 mmol (93.62 g), tetraethoxysilane (hereinafter referred to as “TEOS”) 20.2 mmol (4.17 g), and acetone 391.2 g, and the temperature was raised to 50 ° C. . To the mixture thus obtained, 11.06 g of 5% aqueous potassium carbonate solution (4.0 mmol as potassium carbonate) was added dropwise over 5 minutes, and then 4000.0 mmol (72.00 g) of water was added over 20 minutes. It was dripped. Note that no significant temperature increase occurred during the dropping. Thereafter, the polycondensation reaction was carried out under a nitrogen stream for 5 hours while maintaining at 50 ° C.
Thereafter, simultaneously with cooling the reaction solution, 195.6 g of methyl isobutyl ketone (MIBK) and 143.0 g of 5% saline were added. This solution was transferred to a 1-liter separatory funnel, and 195.6 g of MIBK was added again, followed by washing with water. Washing with water until the lower layer solution (aqueous layer) becomes neutral, and after separating the upper layer solution (organic layer solution), the organic layer solution is concentrated under the conditions of 1 mmHg and 50 ° C., and MIBK is 24.41% by weight. A colorless and transparent liquid product (epoxy group-containing polyorganosilsesquioxane) was obtained.
When the product was analyzed, the number average molecular weight was 1830 and the molecular weight dispersity was 1.74. Moreover, as a result of ¹ H-NMR measurement, a peak derived from an epoxy group (3.15 ppm, broad singlet), a peak derived from a cyclohexyl group (0.87 to 2.31 ppm), a peak derived from a methylene group adjacent to Si. (0.52 ppm, broad singlet) was confirmed (FIG. 1). Furthermore, as a result of ²⁹ Si-NMR measurement, a peak derived from the T2 body in the vicinity of −55 to −60 ppm, a peak derived from the T3 body in the vicinity of −65 to −70 ppm, and a peak derived from the Q unit in the vicinity of −105 to −120 ppm. Was confirmed (FIG. 2). The ratio [(T3 body + T2 body) / Q unit] of T2 body, T3 body, and Q unit calculated from the integrated value was 14.7. Moreover, the measurement result of the FT-IR spectrum of the said product was shown in FIG.

Example 2
An epoxy group-containing polyorganosilsesquioxane was produced in the same manner as in Example 1 except that the amounts of raw materials (EMS and TEOS) used and the amount of solvent used were changed as shown in Table 1.
As a result of ¹ H-NMR measurement of the epoxy group-containing polyorganosilsesquioxane, a peak derived from an epoxy group (3.15 ppm, broad singlet), a peak derived from a cyclohexyl group (0.91 to 2.31 ppm), A peak (0.51 ppm, broad singlet) derived from a methylene group adjacent to Si was confirmed (FIG. 4). Furthermore, as a result of ²⁹ Si-NMR measurement, a peak derived from the T2 body in the vicinity of −55 to −60 ppm, a peak derived from the T3 body in the vicinity of −65 to −70 ppm, and a peak derived from the Q unit in the vicinity of −105 to −120 ppm. Was confirmed (FIG. 5). Moreover, the measurement result of the FT-IR spectrum of the said epoxy group containing polyorgano silsesquioxane was shown in FIG.

Example 3
An epoxy group-containing polyorganosilsesquioxane was produced in the same manner as in Example 1 except that the amounts of raw materials (EMS and TEOS) used and the amount of solvent used were changed as shown in Table 1.
As a result of ¹ H-NMR measurement of the epoxy group-containing polyorganosilsesquioxane, a peak derived from an epoxy group (3.16 ppm, broad singlet), a peak derived from a cyclohexyl group (0.92 to 2.31 ppm), A peak (0.55 ppm, broad singlet) derived from a methylene group adjacent to Si was confirmed (FIG. 7). Furthermore, as a result of ²⁹ Si-NMR measurement, a peak derived from the T2 body in the vicinity of −55 to −60 ppm, a peak derived from the T3 body in the vicinity of −65 to −70 ppm, and a peak derived from the Q unit in the vicinity of −105 to −120 ppm. Was confirmed (FIG. 8). Moreover, the measurement result of the FT-IR spectrum of the said epoxy group containing polyorgano silsesquioxane was shown in FIG.

  Number average molecular weight (Mn), molecular weight dispersity, T2 form, T3 form, and Q unit ratio of epoxy group-containing polyorganosilsesquioxane obtained in each example [(T3 form + T2 form) / Q unit] Are shown in Table 1.

The FT-IR spectrum of the epoxy group-containing polyorganosilsesquioxane obtained in each example was measured by the following apparatus and conditions.
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

Example 4
In a 6 cc brown sample bottle, a MIBK solution of the epoxy group-containing polyorganosilsesquioxane (S-1) obtained in Example 1 (solution containing 24.41% by weight of MIBK; epoxy group-containing polyorganosilsesquioxane) 3 g of oxane), trade name “WPI-124” (manufactured by Wako Pure Chemical Industries, Ltd., 50% solution of photoacid generator) 45.4 mg [45.4 mg as a 50% solution], trade name “ BYK-307 "(Bick Chemie Co., Ltd., leveling agent) 4.5mg and MIBK0.78g were put, and it stirred and mixed with the vibrator, and produced the 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 30 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.

Examples 5 and 6
A hard coat solution was prepared in the same manner as in Example 4 except that the composition of the hard coat solution (curable composition) and the thickness of the hard coat layer were changed as shown in Table 2. The epoxy group-containing polyorganosilsesquioxane obtained in Example 2 is referred to as “S-2”, and the epoxy group-containing polyorganosilsesquioxane obtained in Example 3 is referred to as “S-3”. .

(Evaluation)
The hard coat films obtained in Examples 4 to 6 were evaluated by the following methods. The results are shown in Table 2. In addition, the unit of the compounding quantity of the raw material of the curable composition of Table 2 is a weight part.

(1) Surface hardness (pencil hardness)
The pencil hardness of the hard coat layer surface in the hard coat films obtained in Examples 4 to 6 was evaluated according to JIS K5600-5-4.

  As shown in Table 2, the hard coat films of the present invention (Examples 4 to 6) all had high surface hardness.

Claims (14)

Following formula (1)

[In Formula (1), R < ¹ > shows group containing an epoxy group. ]
Having a structural unit represented by the following formula (I)

[In the formula (I), R ^a is a group containing an epoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group. Represents a substituted or unsubstituted alkenyl group or a hydrogen atom. ]
And a structural unit represented by the following formula (II)

[In the formula (II), R ^b represents an epoxy group-containing group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group. Represents a substituted or unsubstituted alkenyl group or a hydrogen atom. 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 5 or more, the structural unit represented by the above formula (I), and the above The sum of the structural units represented by formula (II) and the following formula (4)

The ratio of the structural unit represented by [{the total of the structural unit represented by formula (I) and the structural unit represented by formula (II)} / the structural unit represented by formula (4)] is 1 to 30 The structural unit represented by the above formula (1) with respect to the total amount of the siloxane structural unit and the following formula (5)

[In formula (5), R ¹ is the same as that in formula (1). R ^c is the same as in formula (II). ]
Hard coat layer forming curable composition in the proportion of a structural unit represented by (total) is characterized in that it comprises a polyorganosilsesquioxane Ru 50-99 mol% der. The polyorganosilsesquioxane has a number average molecular weight in terms of standard polystyrene by gel permeation chromatography of 500 to 6000, and a molecular weight dispersity (weight average molecular weight / number average molecular weight) of 1.0 to 3.0. The curable composition for forming a hard coat layer according to claim 1. R ¹ is represented by the following formula (1a)

[In Formula (1a), R ^1a represents a linear or branched alkylene group. ]
A group represented by formula (1b):

[In formula (1b), R ^1b represents a linear or branched alkylene group. ]
A group represented by formula (1c):

[In Formula (1c), R ^1c represents a linear or branched alkylene group. ]
And a group represented by the following formula (1d):

[In formula (1d), R ^1d represents a linear or branched alkylene group. ]
The curable composition for forming a hard coat layer according to claim 1, which is one or more groups selected from the group consisting of groups represented by the formula: Furthermore, the curable composition for hard-coat layer formation of any one of Claims 1-3 containing a curing catalyst. The curable composition for forming a hard coat layer according to claim 4 , wherein the curing catalyst is a cationic photopolymerization initiator. The curable composition for forming a hard coat layer according to claim 4 , wherein the curing catalyst is a thermal cationic polymerization initiator. Further, a hard coat layer forming curable composition according to any one of claims 1 to 6, comprising a vinyl ether compound. Further, a hard coat layer forming curable composition according to any one of claims 1 to 7 including a vinyl ether compound having a hydroxyl group in the molecule. Cured product of a hard coat layer forming curable composition according to any one of claims 1-8. A hard coat film having a substrate and a hard coating layer formed on at least one surface of the substrate, the hard coat layer, a hard coat according to any one of claims 1 to 8 A hard coat film, which is a layer of a cured product formed from a curable composition for layer formation . The hard coat film according to claim 10 , wherein the hard coat layer has a thickness of 1 to 200 μm. The hard coat film according to claim 10 or 11 , which can be produced by a roll-to-roll method. Further, a hard coat film according to any one of claims 10 to 12 having a surface protective film on the hard coat layer surface. Applying the curable composition for forming a hard coat layer according to any one of claims 1 to 8 on the surface A of the rolled-out substrate A and at least one surface of the rolled-out substrate; comprises a step B of forming a hard coat layer by curing the hard coat layer forming curable composition, then a step C wound into a hard coat film obtained again roll, step A~C Is carried out continuously. A method for producing a hard coat film, comprising:

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