JP2018189800A - Hard coat film for curved surface display, transparent substrate with hard coat film, and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hard coat film for a curved surface display which has a hard coat layer that has high surface hardness while having scattering prevention, has excellent scratch resistance, is soft and is excellent in flexibility and workability, and is easily bent and can be stuck to a display surface having a curved shape.SOLUTION: A hard coat film for a curved surface display includes a hard coat layer, a base material and an adhesive layer, has the hard coat layer adjacent to one surface of the base material, has the adhesive layer at the other surface side of the base material, the hard coat layer is a cured product layer of a curable composition containing at least one additive selected from the group consisting of polyorganosilsesquioxane, silica particles having a group containing a (meth)acryloyl group thereon and silicon acrylate. The polyorganosilsesquioxane is described in the present specification.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a hard coat film for curved display, a transparent substrate with a hard coat film, and a display device.

  Conventionally, a glass material such as a cover glass is mainly used on the outermost surface of a device including a touch panel display such as a smartphone, a tablet terminal, or a car navigation system. In recent years, some devices equipped with a display such as a smartphone have a curved shape in part or in whole, and the outermost glass material also has a curved shape. Glass materials are generally scattered when broken by impacts from the outside. Glass materials with curved surfaces are more likely to break than when they are flat, and the risk of glass scattering is particularly high. ing. In order to prevent such scattering when the glass is broken and to protect the display surface from scratches, a hard coat film (scattering prevention film) having a hard coat layer may be applied on the glass material. .

  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).

JP 2009-279840 A

  However, the hard coat layer using the above-mentioned conventional UV acrylic monomer has a pencil hardness of about 2H, and has not yet been said to have a sufficient surface hardness. There is a demand for a hard coat layer having a pencil hardness of about 4H and a higher surface hardness. In addition, the hard coat film is also required to be hard to be scratched on the surface. Furthermore, the above-mentioned conventional hard coat film cannot be easily bent because the hard coat layer is inflexible and hard even if the conventional hard coat film is applied to a curved display surface. The coat film may not be attached in accordance with the curved shape. Moreover, even if a conventional hard coat film is attached to a display surface having a curved shape, the hard coat layer may not follow the curved shape of the display, and the hard coat layer may be broken. In recent years, a display having a curved surface with a small R (radius) has been demanded, and it has become more difficult to follow the curved surface shape of a display with a conventional hard coat film.

  Therefore, an object of the present invention is to have a hard coat layer having anti-scattering properties, high surface hardness, excellent scratch resistance and softness, and excellent flexibility and workability. An object of the present invention is to provide a hard coat film for curved display that can be easily bent and attached to a display surface having a curved shape.

  The inventor has anti-scattering properties by forming a hard coat layer using a curable composition containing a polyorganosilsesquioxane having a silsesquioxane structural unit (unit structure) containing an epoxy group. However, the present inventors have found that a hard coat film for curved display having a hard coat layer having a high surface hardness and softness and excellent flexibility and workability can be obtained.

［式（１）中、Ｒ¹は、エポキシ基を含有する基を示す。］

［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。］

［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。］

［式（４）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。］ That is, the present invention is a hard coat film for curved display including a hard coat layer, a base material, and an adhesive layer, the hard coat layer adjacent to one surface of the base material, and the base material The other side of the adhesive layer has the adhesive layer, and the hard coat layer comprises the following polyorganosilsesquioxane, silica particles having a group containing a (meth) acryloyl group on the surface, and silicon acrylate. Provided is a hard coat film for curved display, which is a cured layer of a curable composition containing at least one additive selected.
Polyorganosilsesquioxane: having a structural unit represented by the following formula (1), a molar ratio of the structural unit represented by the following formula (I) and the structural unit represented by the following formula (II) [ The structural unit represented by the formula (I) / the structural unit represented by the formula (II)] is 5 or more, and the structural unit represented by the following formula (1) and the following formula ( 4) The total proportion of the structural units represented by 55) is from 55 to 100 mol%, the number average molecular weight is 1000 to 3000, and the molecular weight dispersity (weight average molecular weight / number average molecular weight) is 1.0 to 3.0. A hard coat film for a curved display is provided.

[In Formula (1), R < ¹ > shows group containing an epoxy group. ]

[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. ]

[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. ]

[In formula (4), R ¹ is the same as that in formula (1). R ^c is the same as in formula (II). ]

［式（２）中、Ｒ²は、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、又は、置換若しくは無置換のアルケニル基を示す。］ In the present invention, it is preferable that the polyorganosilsesquioxane further has a structural unit represented by the following formula (2).

[In the 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 of ]

In the present invention, it is preferable that in the polyorganosilsesquioxane, R ² is a substituted or unsubstituted aryl group.

［式（１ａ）中、Ｒ^1aは、直鎖又は分岐鎖状のアルキレン基を示す。］

［式（１ｂ）中、Ｒ^1bは、直鎖又は分岐鎖状のアルキレン基を示す。］

［式（１ｃ）中、Ｒ^1cは、直鎖又は分岐鎖状のアルキレン基を示す。］

［式（１ｄ）中、Ｒ^1dは、直鎖又は分岐鎖状のアルキレン基を示す。］ Further, in the present invention, in the polyorganosilsesquioxane, R ¹ is represented by a group represented by the following formula (1a), a group represented by the following formula (1b), or the following formula (1c). It is preferably a group or a group represented by the following formula (1d).

[In Formula (1a), R ^1a represents a linear or branched alkylene group. ]

[In formula (1b), R ^1b represents a linear or branched alkylene group. ]

[In Formula (1c), R ^1c represents a linear or branched alkylene group. ]

[In formula (1d), R ^1d represents a linear or branched alkylene group. ]

  Moreover, it is preferable that this invention contains epoxy compounds other than the said polyorgano silsesquioxane.

  Moreover, it is preferable that this invention contains a photocationic polymerization initiator.

  In the present invention, the thickness of the hard coat layer is preferably 1 to 100 μm.

  In the present invention, the total thickness is preferably 10 to 1000 μm.

  The present invention also provides a transparent substrate with a hard coat film, comprising the hard coat film for curved display, and a transparent substrate having a curved surface, which is attached to the adhesive layer side surface of the hard coat film for curved display. To do.

  Moreover, this invention provides the display apparatus provided with the said hard coat film for curved displays, the transparent substrate which has a curved surface, and a display panel structural member.

  The hard coat film for curved display according to the present invention has a hard coat layer having high surface hardness, excellent scratch resistance, and softness while having anti-scattering properties and excellent flexibility and workability. Therefore, it can be easily bent and attached to a display surface having a curved surface shape. Further, the hard coat film for curved display of the present invention has good appearance such as smoothness (thickness uniformity) on the surface of the hard coat layer, and is excellent in scratch resistance of the bent portion (curved surface). Moreover, since the hard coat film for curved displays of the present invention has a hard coat layer excellent in flexibility and processability, it can be manufactured and processed by roll-to-roll, and is excellent in cost.

It is a cross-sectional schematic diagram which shows an example of the preferable aspect of the hard coat film for curved surface displays of this invention. It is a cross-sectional schematic diagram which shows an example of the preferable aspect of the transparent substrate with a hard coat film of this invention. It is a cross-sectional schematic diagram which shows an example of the preferable aspect of the display apparatus of this invention.

  The hard coat film for curved display of the present invention (hereinafter also referred to as “hard coat film of the present invention” or “present invention”) includes a hard coat layer, a substrate, and an adhesive layer. A coated film having the hard coat layer adjacent to one surface of the substrate and the adhesive layer on the other surface side of the substrate; A cured product layer of a curable composition comprising an organosilsesquioxane, silica particles having a group containing a (meth) acryloyl group on the surface, and at least one additive selected from the group consisting of silicon acrylate It is characterized by that. FIG. 1 shows a schematic cross-sectional view (hard coat layer 4 / base material 5 / adhesive layer 6) as an example of a preferred embodiment of the hard coat film for curved display of the present invention.

(Curable composition)
The curable composition includes polyorganosilsesquioxane described later, silica particles having a group containing a (meth) acryloyl group on the surface, and at least one additive selected from the group consisting of silicon acrylate. . As described later, the curable composition may further contain other components such as a cationic photopolymerization initiator, a leveling agent, and a cationically curable compound other than polyorganosilsesquioxane.

(Polyorganosilsesquioxane)
The polyorganosilsesquioxane (silsesquioxane) has a structural unit represented by the following formula (1), and is represented by a structural unit represented by the following formula (I) (sometimes referred to as “T3 body”). And 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 structure represented by the formula (II) The unit: “may be described as“ T3 body / T2 body ”] is 5 or more, and the structural unit represented by the following formula (1) and the following formula (with respect to the total amount (100 mol%) of the siloxane structural unit ( 4) The total ratio (total amount) of the structural units represented by 55 to 100 mol%, the number average molecular weight is 1000 to 3000, and the molecular weight dispersity [weight average molecular weight / number average molecular weight] is 1.0 to 3 0.0.

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 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 conventional groups having an oxirane ring, and are not particularly limited, but in terms of curability of the curable composition, surface hardness and heat resistance of the hard coat layer, A group represented by the formula (1a), a 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 preferred, and more preferably the following formula: A group represented by (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, and more preferably, from the viewpoint of the surface hardness and curability of the hard coat layer. Is an ethylene group, trimethylene group, propylene group, more preferably an ethylene group or 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 these, 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 hard coat layer. Is an ethylene group, trimethylene group, propylene group, more preferably an ethylene group or 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 hard coat layer. Is an ethylene group, trimethylene group, propylene group, more preferably an ethylene group or 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, and more preferably, from the viewpoint of the surface hardness and curability of the hard coat layer. Is an ethylene group, trimethylene group, propylene group, more preferably an ethylene group or trimethylene group.

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

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

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

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.

R ² in the above formula (2) is 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 of 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.

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

In addition to the structural unit represented by the formula (1) and the structural unit represented by the formula (2), the polyorganosilsesquioxane is further represented by the structural unit and formula represented by the formula (1). Other than the structural unit represented by (2), the structural unit represented by [RSiO _3/2 ], [R ₃ SiO _1/2 ] (so-called M unit), [R ₂ SiO] It may have at least one siloxane structural unit selected from the group consisting of a structural unit represented (so-called D unit) and a structural unit represented by [SiO ₂ ] (so-called Q unit). In addition, as a silsesquioxane structural unit other than the structural unit represented by the said Formula (1) and the structural unit represented by Formula (2), the structural unit etc. which are represented by following formula (3) etc. are mentioned, for example. Can be mentioned.

  The ratio [T3 body / T2 body] of the structural unit (T3 body) represented by the above formula (I) and the structural unit (T2 body) represented by the above formula (II) in the polyorganosilsesquioxane is 5 or more (for example, 5 to 500), and the lower limit of the ratio is preferably 6, more preferably 7, even more preferably 8, and particularly preferably 10. The upper limit of the above ratio is preferably 50, more preferably 20, still more preferably 18, and particularly preferably 16. By setting the ratio [T3 body / T2 body] to 5 or more, the surface hardness of 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 ′). Moreover, 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 each replaced with another silicon atom (a silicon atom 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) are groups bonded to silicon atoms in the hydrolyzable trifunctional silane compound used as a raw material for the polyorganosilsesquioxane ( A group other than an alkoxy group and a halogen atom; for example, R ¹ , R ² and a hydrogen atom in the following formulas (a) to (c).

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 in the hydrolyzable silane compound used as a raw material of the polyorganosilsesquioxane (for example, as X ^{1 to} X ³ described later). Derived from an alkyl group forming an alkoxy group or the like.

The said ratio [T3 body / T2 body] in the said polyorgano silsesquioxane can be calculated | required by ²⁹ Si-NMR spectrum measurement, for example. ^{29 In the} Si-NMR spectrum, the silicon atom in the structural unit (T3 form) represented by the above formula (I) is different from the silicon atom in the structural unit (T2 form) represented by the above formula (II). In order to show a signal (peak) in (chemical shift), the ratio [T3 body / T2 body] can be obtained by calculating the integration ratio of these respective peaks. Specifically, for example, when the polyorganosilsesquioxane 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 Appears at -54 to -60 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.

The ²⁹ Si-NMR spectrum of the polyorganosilsesquioxane 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 being 5 or more means that the polyorganosilsesquioxane has a certain amount of T2 body with respect to the T3 body. To do. Examples of such a T2 body include a structural unit represented by the following formula (4), a structural unit represented by the following formula (5), a structural unit represented by the following formula (6), and the like. R ² in R ¹ and the following formula (5) in the following equation (4) is the same as R ² in R ¹ and the formula in the formula (1) (2). R ^c in the formula (4) to (6), like the R ^c in Formula (II), a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

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 ratio [T3 body / T2 body] is 5 or more, the number average molecular weight is 1000 to 3000, the molecular weight dispersity is 1.0 to 3.0, and in the FT-IR spectrum as described later. It is suggested that the polyorganosilsesquioxane having one intrinsic absorption peak near 1100 cm ⁻¹ has an incomplete cage silsesquioxane structure.

To have the polyorganosilsesquioxane cage (incomplete cage) silsesquioxane structure, it said polyorganosilsesquioxane, the FT-IR spectrum in the vicinity of 1050 cm ^-1 and around 1150 cm ^-1 Each has no intrinsic absorption peak, and is confirmed by having one intrinsic absorption peak in the vicinity of 1100 cm ⁻¹ [reference: R.R. H. Raney, M.M. Itoh, A.D. Sakakibara and T. Suzuki, Chem. Rev. 95, 1409 (1995)]. On the other hand, in general, when the FT-IR spectrum has intrinsic absorption peaks near 1050 cm ⁻¹ and 1150 cm ⁻¹ , it is identified as having a ladder-type silsesquioxane structure. In addition, the FT-IR spectrum of polyorganosilsesquioxane 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 [total siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%) is represented by the above formula (1). The proportion (total amount) of the structural unit and the structural unit represented by the above formula (4) is 55 to 100 mol%, preferably 65 to 100 mol%, more preferably 80 to 99 mol%, as described above. It is. When the ratio is 55 mol% or more, the curability of the curable composition is improved and the surface hardness of the hard coat layer is remarkably increased. In addition, the ratio of each siloxane structural unit in the said polyorgano silsesquioxane 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 [total siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%) is represented by the above formula (2). The proportion (total amount) of the structural unit and the structural unit represented by the above formula (5) is not particularly limited, but is preferably 0 to 70 mol%, more preferably 0 to 60 mol%, and still more preferably 0 to 40 mol. %, Particularly preferably 1 to 15 mol%. Since the ratio of the structural unit represented by the formula (1) and the structural unit represented by the formula (4) can be relatively increased by setting the ratio to 70 mol% or less, the curable composition There is a tendency that the surface hardness when the hard coat layer is made higher is improved. On the other hand, by setting the above ratio to 1 mol% or more, gas barrier properties when used as a hard coat layer tend to be improved.

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

  The number average molecular weight (Mn) in terms of standard polystyrene by gel permeation chromatography of the polyorganosilsesquioxane is 1000 to 3000 as described above, preferably 1000 to 2800, more preferably 1100 to 2600. is there. By setting the number average molecular weight to 1000 or more, the heat resistance, scratch resistance and adhesion of the hard coat layer are further improved. On the other hand, by setting the number average molecular weight to 3000 or less, compatibility with other components in the curable composition is improved, and heat resistance when the hard coat layer is obtained is further improved.

  As described above, the molecular weight dispersity (Mw / Mn) in terms of standard polystyrene by gel permeation chromatography of the polyorganosilsesquioxane is 1.0 to 3.0, preferably 1.1 to 2. 0.0, more preferably 1.2 to 1.9. By setting the molecular weight dispersity to 3.0 or less, the surface hardness when the hard coat layer is formed becomes higher. On the other hand, when the molecular weight dispersity is 1.1 or more, it tends to be liquid, and the handleability tends to be improved.

The number average molecular weight and molecular weight dispersity of the polyorganosilsesquioxane can be measured by 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 5% weight loss temperature (T _d5 ) in the air atmosphere of the polyorganosilsesquioxane is preferably 330 ° C. or higher (for example, 330 to 450 ° C.), more preferably 340 ° C. or higher, further preferably 350 ° C. or higher. It is. When the 5% weight loss temperature is 330 ° C. or higher, the heat resistance of the hard coat layer tends to be further improved. In particular, the polyorganosilsesquioxane has a ratio [T3 / T2] of 5 or more, a number average molecular weight of 1000 to 3000, a molecular weight dispersity of 1.0 to 3.0, FT By having one intrinsic peak in the vicinity of 1100 cm ⁻¹ in the -IR spectrum, the 5% weight loss temperature is controlled to 330 ° C. or higher. The 5% weight reduction temperature is a temperature at the time when 5% of the weight before heating is reduced when heated at a constant rate of temperature increase, and serves as an index of heat resistance. The 5% weight loss temperature can be measured by TGA (thermogravimetric analysis) under an air atmosphere at a temperature rising rate of 5 ° C./min.

  The polyorganosilsesquioxane can be produced by a known or commonly used production method of polysiloxane, for example, by a method of hydrolyzing and condensing one or more hydrolyzable silane compounds. 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) is essential. It is necessary to use it as a 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, Depending on the above, the polyorganosilsesquioxane can be produced by a method of hydrolyzing and condensing the compound represented by the following formula (b) and the compound represented by the following formula (c).

The compound represented by the formula (a) is a compound that forms the structural unit represented by the formula (1) in the polyorganosilsesquioxane. 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), wherein 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 said Formula (b) is a compound which forms the structural unit represented by Formula (2) in the said polyorgano silsesquioxane. 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. X ³ in the above formula (c) represents an alkoxy group or a halogen atom. Specific examples of X ³ include those exemplified as X ¹ . Among them, X ³ is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group. The three X ³ may be the same or different.

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

  The amount and composition of the hydrolyzable silane compound can be adjusted as appropriate according to the desired polyorganosilsesquioxane structure. For example, although the usage-amount of the compound represented by the said formula (a) is not specifically limited, 55-100 mol% is preferable with respect to the whole quantity (100 mol%) of the hydrolysable silane compound to be used, More preferably Is 65 to 100 mol%, more preferably 80 to 99 mol%.

  The amount of the compound represented by the formula (b) is preferably 0 to 70 mol%, more preferably 0 to 60 mol, based on the total amount (100 mol%) of the hydrolyzable silane compound used. %, More preferably 0 to 40 mol%, particularly preferably 1 to 15 mol%.

  Furthermore, the ratio (total ratio) of the compound represented by the formula (a) and the compound represented by the formula (b) to the total amount (100 mol%) of the hydrolyzable silane compound used is 60 to 100 mol%. Is more preferable, 70-100 mol% is more preferable, More preferably, it is 80-100 mol%.

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

  The hydrolysis and condensation reaction of the hydrolyzable silane compound can be performed in the presence of a solvent or in the absence. Among these, it is preferable to perform 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.

  The reaction conditions for the hydrolysis and condensation reaction of the hydrolyzable silane compound are, in particular, the reaction conditions such that the ratio [T3 / T2] in the polyorganosilsesquioxane is 5 or more. It is important to choose. Although the reaction temperature of the said hydrolysis and condensation reaction is not specifically limited, 40-100 degreeC is preferable, More preferably, it is 45-80 degreeC. By controlling the reaction temperature within the above range, the ratio [T3 / T2] 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.

  A polyorganosilsesquioxane 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 is separated into, for example, water washing, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination of these. It may be separated and purified by, for example.

  The content (blending amount) of the polyorganosilsesquioxane is preferably 70% by weight or more and less than 100% by weight, more preferably 80%, based on the total amount (100% by weight) of the curable composition excluding the solvent. To 99.8% by weight, more preferably 90 to 99.5% by weight. By setting the content of the polyorganosilsesquioxane to 70% by weight or more, the surface hardness and adhesiveness of the hard coat layer tend to be further improved. On the other hand, by setting the content of the polyorganosilsesquioxane to less than 100% by weight, a curing catalyst can be contained, whereby the curing of the curable composition tends to proceed more efficiently. There is.

  The ratio of the polyorganosilsesquioxane to the total amount (100% by weight) of the cationic curable compound is preferably 70 to 100% by weight, more preferably 75 to 98% by weight, and still more preferably 80 to 95% by weight. . By setting the content of the polyorganosilsesquioxane to 70% by weight or more, the surface hardness of the hard coat layer tends to be further improved.

  The polyorganosilsesquioxane has high surface hardness and heat resistance by curing a curable composition containing the polyorganosilsesquioxane as an essential component, and has excellent flexibility and workability. A hard coat layer can be formed.

(Silica particles having a group containing a (meth) acryloyl group on the surface)
Silica particles having a group containing a (meth) acryloyl group on the surface have innumerable hydroxyl groups (Si-OH groups) on the surface of the silica particles, and the hydroxyl groups react with the polyorganosilsesquioxane during curing. Thereby, the crosslinking density after hardening of polyorganosilsesquioxane improves. Moreover, the crosslink density after hardening improves because the (meth) acryloyl group in the said several silica particle couple | bonds at the time of hardening. Thus, the abrasion resistance in a hard-coat layer improves because the crosslinking density after hardening improves. Also, if a layer (functional layer) having functions such as antifouling property and low reflectivity is provided on the hard coat layer, the adhesion between the hard coat layer and the functional layer is weak, and the functional layer may peel off. Yes, there is no so-called recoatability. However, when the silica particles are used, recoatability can be imparted, and processability (workability) when the functional layer is provided on the hardcoat layer surface can be improved.

Furthermore, it is thought that the said silica particle can provide the stability in a curable composition by having a (meth) acryloyl group on the surface. The above-mentioned stability means that in the preparation stage of a curable composition before curing, the silica particles and polyorganosilsesquioxane react to increase the viscosity of the curable composition (gelation). Say, don't solidify. When normal silica particles (SiO ₂ particles) having no functional group such as a group containing a (meth) acryloyl group are used, the silica particles may aggregate and the curable composition may be gelled. . The silica particles may have a functional group other than the (meth) acryloyl group (for example, a silicone-modified group). The (meth) acryloyl group is a general term for an acryloyl group (acrylic group) and a methacryloyl group (methacrylic group).

  As the silica particles, a dispersion liquid (dispersion) in a state of being dispersed in a known or commonly used general dispersion medium such as water or an organic solvent may be used. Moreover, you may use what made the silica particle react with the silane coupling agent which has group containing a (meth) acryloyl group as said silica particle. As the silica particles, for example, trade names “BYK-LPX 22699”, “NANOBYK-3650”, “NANOBYK-3651”, “NANOBYK-3652” (above, manufactured by BYK Japan Japan Co., Ltd.) can be used. .

  The particle size of the silica particles is, for example, 1 to 100 nm, preferably 3 to 50 nm, more preferably 5 to 30 nm.

  The ratio of the silica particles having a group containing a (meth) acryloyl group on the surface is, for example, 0.01 to 20 parts by weight, preferably 0.05 to 15 parts by weight with respect to 100 parts by weight of the polyorganosilsesquioxane. More preferably, it is 0.01-10 weight part, More preferably, it is 0.2-5 weight part. By making the ratio of the silica particles 0.01 parts by weight or more, the appearance of the hard coat layer surface can be improved and sufficient recoatability can be imparted. Moreover, the surface hardness of a hard-coat layer can be made high by the ratio of a silica particle being 20 weight part or less.

(Silicon acrylate)
The silicon acrylate (silicone acrylate) is a kind of additive having at least a silicon atom and a (meth) acryloyl group. The silicon acrylate may have a functional group (for example, a hydroxyl group) other than the (meth) acryloyl group. The silicon acrylate may be silicon diacrylate, silicon triacrylate, silicon tetraacrylate, silicon pentaacrylate, silicon hexaacrylate, silicon heptaacrylate, or silicon octaacrylate. By using the silicon acrylate together with the polyorganosilsesquioxane in the curable composition, it is possible to effectively increase the crosslink density of the hard coat layer surface when the hard coat layer is formed. It has the property of improving the appearance such as smoothness and improving the surface hardness, scratch resistance and antifouling property. The (meth) acryloyl group is a general term for an acryloyl group (acrylic group) and a methacryloyl group (methacrylic group).

  As the silicon acrylate, a dispersion (dispersion) in a state of being dispersed in a known or common general dispersion medium such as an organic solvent (for example, acetone, toluene, methanol, ethanol) may be used. As the silicon acrylate, for example, trade names “KRM8479”, “EBECRYL 350”, “EBECRYL 1360” (manufactured by Daicel Ornex Co., Ltd.) can be used.

  The ratio of the silicon acrylate is, for example, 0.01 to 15 parts by weight, preferably 0.05 to 10 parts by weight, more preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the polyorganosilsesquioxane. More preferably, it is 0.2 to 3 parts by weight. By setting the ratio of the silicon acrylate to 0.01 parts by weight or more, it is possible to improve the scratch resistance and antifouling property when the hard coat layer is formed. Moreover, the surface hardness when it is set as a hard-coat layer can be made higher by making the ratio of silicon acrylate 15 weight part or less.

  It is possible to use both silicon acrylate and silica particles having a group containing a (meth) acryloyl group on the surface in terms of further improving the appearance of the hard coat layer, increasing the surface hardness, and improving the scratch resistance. preferable. When the silicon acrylate and the silica particles are both included, the total ratio of the silicon acrylate and the silica particles is, for example, 0.01 to 20 parts by weight, preferably 0. 0 parts by weight with respect to 100 parts by weight of the polyorganosilsesquioxane. It is 05-15 weight part, More preferably, it is 0.01-10 weight part, More preferably, it is 0.2-5 weight part. By setting the ratio to 0.01 parts by weight or more, the scratch resistance when the hard coat layer is formed can be improved. Moreover, the surface hardness when it is set as a hard-coat layer can be made higher by making the said ratio into 20 weight part or less.

(Photocationic polymerization initiator)
The curable composition preferably contains a cationic photopolymerization initiator as a curing catalyst in that the curing time until tack-free can be shortened.

  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 sulfonium salt include trade name “HS-1PC” (manufactured by San Apro Co., Ltd.), trade name “LW-S1” (manufactured by San Apro Co., Ltd.), triphenylsulfonium salt, and tri-p-tolylsulfonium salt. , Tri-o-tolylsulfonium salt, tris (4-methoxyphenyl) sulfonium salt, 1-naphthyldiphenylsulfonium salt, 2-naphthyldiphenylsulfonium 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, 4- (p-tolylthio) phenyldi- (p-phenyl) sulfonium salt Reel sulfonium salt; diphenyl Diarylsulfonium salts such as enacilsulfonium salt, diphenyl 4-nitrophenacylsulfonium salt, diphenylbenzylsulfonium salt, diphenylmethylsulfonium salt; phenylmethylbenzylsulfonium salt, 4-hydroxyphenylmethylbenzylsulfonium salt, 4-methoxyphenylmethylbenzyl Examples thereof include monoarylsulfonium salts such as sulfonium salts; trialkylsulfonium salts such as dimethylphenacylsulfonium salts, phenacyltetrahydrothiophenium salts, and dimethylbenzylsulfonium salts.

  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. Moreover, as said triarylsulfonium salt, you may use commercial items, such as a brand name "K1-S" (San Apro Co., Ltd. product, non-antimony type triarylsulfonium salt), for example.

  Examples of the iodonium salt include, for example, trade name “UV9380C” (Momentive Performance Materials Japan GK, bis (4-dodecylphenyl) iodonium = hexafluoroantimonate 45% alkyl glycidyl ether solution), trade name “ RHODORSIL PHOTOINITIATOR 2074 "(manufactured by Rhodia Japan Ltd., 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; .

  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 -Diethylmorpholinium salt Morpholinium salts such as N, N-dimethylpiperidinium salt, piperidinium salts such as N, N-diethylpiperidinium salt; pyridinium salts such as N-methylpyridinium salt and N-ethylpyridinium salt; N, N′- Imidazolium salts such as dimethylimidazolium salt; quinolinium salts such as N-methylquinolium salt; isoquinolium salts such as N-methylisoquinolium salt; thiazonium salts such as benzylbenzothiazonium salt; Examples include an acridium salt.

  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 salts of chromium complex cations such as (η5-cyclopentadienyl) (η6-toluene) Cr ⁺ and (η5-cyclopentadienyl) (η6-xylene) Cr ^+. And salts of iron complex cations such as (η5-cyclopentadienyl) (η6-toluene) Fe ⁺ and (η5-cyclopentadienyl) (η6-xylene) Fe ⁺ .

Examples of the anion constituting the above-described salt include SbF ₆ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , (CF ₃ CF ₂ ) ₃ PF ₃ ⁻ , (CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , (C ₆ F ₅ ) ₄ Ga ⁻ , sulfonate anion (trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion, nonafluorobutanesulfonate anion, methanesulfonate anion, benzenesulfonate Anion, p-toluenesulfonic acid 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 acid ion, carboxylate ion, arylborate ion, thiocyanate ion, nitrate ion and the like.

  The content (blending amount) of the cationic photopolymerization initiator is preferably 0.01 to 3.0 parts by weight, more preferably 0.05 to 3.0 parts with respect to 100 parts by weight of the polyorganosilsesquioxane. Parts by weight, 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 hard coat layer tends to be further improved. On the other hand, when the content of the cationic photopolymerization initiator is 3.0 parts by weight or less, the storability of the curable composition is further improved, or coloring when the hard coat layer is formed tends to be suppressed. .

  The curable composition may further contain a cationic curable compound other than the polyorganosilsesquioxane (sometimes referred to as “other cationic curable compounds”). As other cationic curable compounds, known or commonly used cationic curable compounds can be used, and are not particularly limited. For example, epoxy compounds other than the polyorganosilsesquioxane ("other epoxy compounds" and Oxetane compounds, vinyl ether compounds, and the like. In addition, in the said curable composition, 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′-diepoxy) bicyclohexyl, the following formulas (i-1) to (i-10). ) And the like. 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 obtained by removing p hydroxyl groups (—OH) from the structural formula of p-valent alcohol (p-valent organic group), and p and n each represent a natural number. P 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 glycidyl ether of q-valent alcohol (q is a natural number) having no cyclic structure; 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 q-valent alcohol having no 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, xylylenebisoxetane, 3-ethyl-3-{[3- (triethoxysilyl) propoxy] methyl} oxetane, oxetanylsilsesquioxane, Phenol novolac oxetane etc. are mentioned.

  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.

  The content (blending amount) of other epoxy compounds (especially the alicyclic epoxy compound) is not particularly limited, but is the total amount (100% by weight; cation) of the polyorganosilsesquioxane and other cation curable compounds. The total amount of the curable compound is preferably 0.01 to 10% by weight, more preferably 0.05 to 9% by weight, and still more preferably 1 to 8% by weight. In addition, the said polyorgano silsesquioxane is not contained in the said other epoxy compound.

  The content (blending amount) of the other cationic curable compound is not particularly limited, but is based on the total amount of the polyorganosilsesquioxane and the other cationic curable compound (100% by weight; the total amount of the cationic curable compound). 50% by weight or less (for example, 0 to 50% by weight) is preferable, more preferably 30% by weight or less (for example, 0 to 30% by weight), and still more preferably 10% by weight or less. By setting the content of the other cationic curable compound to 50% by weight or less (particularly 10% by weight or less), the scratch resistance of the hard coat layer 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 example, rapid curability and viscosity adjustment for the curable composition) is imparted to the curable composition. There are cases where it is possible.

  The curable composition may have a leveling agent. Examples of the leveling agent include silicone leveling agents, fluorine leveling agents, and silicone leveling agents having a hydroxyl group.

  As the silicone leveling agent, commercially available silicone leveling agents can be used. For example, trade names “BYK-300”, “BYK-301 / 302”, “BYK-306”, “BYK-307”, “BYK” -310 "," BYK-315 "," BYK-313 "," BYK-320 "," BYK-322 "," BYK-323 "," BYK-325 "," BYK-330 "," BYK-331 " ”,“ BYK-333 ”,“ BYK-337 ”,“ BYK-341 ”,“ BYK-344 ”,“ BYK-345 / 346 ”,“ BYK-347 ”,“ BYK-348 ”,“ BYK-349 ” ”,“ BYK-370 ”,“ BYK-375 ”,“ BYK-377 ”,“ BYK-378 ”,“ BYK-UV3500 ”,“ BYK-UV3510 ”,“ B "K-UV3570", "BYK-3550", "BYK-SILCLEAN3700", "BYK-SILCLEAN3720" (above, manufactured by Big Chemie Japan); trade names "AC FS 180", "AC FS 360", "AC S 20 ”(manufactured by Algin Chemie); trade names“ Polyflow KL-400X ”,“ Polyflow KL-400HF ”,“ Polyflow KL-401 ”,“ Polyflow KL-402 ”,“ Polyflow KL-403 ”,“ Polyflow ” KL-404 "(manufactured by Kyoeisha Chemical Co., Ltd.); trade names" KP-323 "," KP-326 "," KP-341 "," KP-104 "," KP-110 "," KP- " 112 ”(above, manufactured by Shin-Etsu Chemical Co., Ltd.); trade names“ LP-7001 ”,“ LP-7002 ”,“ 803 ” ADDITIVE, 57 ADDITIVE, L-7604, FZ-2110, FZ-2105, 67 ADDITIVE, 8618 ADDITIVE, 3 ADDITIVE, 56 ADDITIVE (above, Toray Commercial products such as Dow Corning Co., Ltd. can be used.

  As the fluorine leveling agent, commercially available fluorine leveling agents can be used. For example, trade names “OPTOOL DSX” and “OPTOOL DAC-HP” (manufactured by Daikin Industries, Ltd.); trade names “Surflon S-” 242 ”,“ Surflon S-243 ”,“ Surflon S-420 ”,“ Surflon S-611 ”,“ Surflon S-651 ”,“ Surflon S-386 ”(above, manufactured by AGC Seimi Chemical Co., Ltd.); Name “BYK-340” (BIC Chemie Japan Co., Ltd.); Trade names “AC 110a”, “AC 100a” (above, made by Algin Chemie); Trade names “Mega Fuck F-114”, “Mega Fuck F-” "410", "Megafuck F-444", "Megafuck EXP TP-2066", "Megafuck F-430", "Mega Fuck F-472SF, Mega Fuck F-477, Mega Fuck F-552, Mega Fuck F-553, Mega Fuck F-554, Mega Fuck F-555, Mega Fuck R -94 "," Megafuck RS-72-K "," Megafuck RS-75 "," Megafuck F-556 "," Megafuck EXP TF-1367 "," Megafuck EXP TF-1437 "," Mega "Fuck F-558", "Megafuck EXP TF-1537" (manufactured by DIC Corporation); product names "FC-4430", "FC-4432" (manufactured by Sumitomo 3M Corporation); “Furgent 100”, “Furgent 100C”, “Furgent 110”, “Furgent 150”, “Furgent 150C” "," Factent AK "," Factent 501 "," Factent 250 "," Factent 251 "," Factent 222F "," Factent 208G "," Factent 300 "," Factent 310 " ”,“ Factent 400SW ”(manufactured by Neos Co., Ltd.); trade names“ PF-136A ”,“ PF-156A ”,“ PF-151N ”,“ PF-636 ”,“ PF-6320 ”,“ Commercial products such as “PF-656”, “PF-6520”, “PF-651”, “PF-652”, and “PF-3320” (above, manufactured by Kitamura Chemical Industry Co., Ltd.) can be used.

  Examples of the silicone-based leveling agent having a hydroxyl group include a polyether-modified polyorganosiloxane in which a polyether group is introduced into the main chain or side chain of a polyorganosiloxane skeleton (polydimethylsiloxane, etc.), and a polyorganosiloxane skeleton. Examples thereof include a polyester-modified polyorganosiloxane having a polyester group introduced into a chain or a side chain, and a silicone-modified (meth) acrylic resin having a polyorganosiloxane introduced into a (meth) acrylic resin. In these leveling agents, the hydroxyl group may have a polyorganosiloxane skeleton, or may have a polyether group or a polyester group. As a commercial product of such a leveling agent, for example, trade names “BYK-370”, “BYK-SILCLEAN3700”, “BYK-SILCLEAN3720”, and the like can be used.

  The ratio of the leveling agent is, for example, 0.01 to 20 parts by weight, preferably 0.05 to 15 parts by weight, more preferably 0.01 to 100 parts by weight of the polyorganosilsesquioxane. -10 parts by weight, more preferably 0.2-5 parts by weight. If the ratio of the leveling agent is too small, the surface smoothness of the hard coat layer may be reduced, and if too high, the surface hardness of the hard coat layer may be reduced.

  The curable composition further includes precipitated silica, wet silica, fumed silica, calcined silica, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate, carbon as other optional components. Inorganic fillers such as black, silicon carbide, silicon nitride, boron nitride, etc., inorganic fillers obtained by treating these fillers with organosilicon compounds such as organohalosilanes, organoalkoxysilanes, organosilazanes; silicone resins, epoxy resins, fluorine Organic resin fine powders such as resins; fillers such as conductive metal powders such as silver and copper, curing aids, solvents (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 improvers, clearing agents, rheology adjustment Agents (fluidity improvers, etc.), processability improvers, colorants (dyes, pigments, etc.), antistatic agents, dispersants, antifoaming agents, anti-waxing agents, surface modifiers (slip agents, etc.), matte Conventional additives such as an agent, an antifoaming agent, an antifoaming agent, a defoaming agent, an antibacterial agent, an antiseptic, a viscosity modifier, a thickener, a photosensitizer, and a foaming agent may be included. These additives can be used individually by 1 type or in combination of 2 or more types.

  Although the said curable composition is not specifically limited, It can prepare by stirring and mixing each said component, heating at room temperature or as needed. The curable composition can also be used as a one-component composition in which components are mixed in advance, for example, two or more components stored separately before use. It can also be used as a multi-component (for example, two-component) composition used by mixing at a predetermined ratio.

  Although the said curable composition is not specifically limited, It is preferable that it is a liquid at normal temperature (about 25 degreeC). More specifically, the curable composition has a viscosity at 300C 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]. To 20000 mPa · s, more preferably 500 to 10000 mPa · s, and still more preferably 1000 to 8000 mPa · s. There exists a tendency for the heat resistance of a hard-coat layer to improve more by making the said viscosity into 300 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 bubbles tend not to remain in the hard coat layer. In addition, the viscosity of the curable composition 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 a temperature of 25 ° C. Measured at conditions.

(Hard coat layer)
The hard coat layer in the present invention can be obtained by causing a polymerization reaction of a cationic curable compound (such as polyorganosilsesquioxane) contained in the curable composition to proceed and curing.

  In order to further improve the recoatability of the hard coat layer, the surface of the hard coat layer may be subjected to surface treatment such as corona discharge treatment, plasma discharge treatment, ozone exposure treatment, excimer treatment for modifying the surface by corona discharge irradiation. preferable. Among these, corona discharge treatment is more preferable from the viewpoint that the recoatability can be easily improved.

  The corona discharge treatment is a treatment for processing the surface of the hard coat layer by generating a non-uniform electric field around a sharp electrode (needle electrode) and generating a continuous discharge. The plasma discharge treatment is a treatment for processing the surface of the hard coat layer by generating positive and negative charged particles activated by discharging in the atmosphere. The ozone exposure treatment is, for example, a treatment for processing the surface of the hard coat layer by generating ozone by ultraviolet irradiation using a low-pressure mercury lamp or the like in the presence of oxygen. The excimer process is a process for processing the hard coat layer surface by ultraviolet irradiation or laser irradiation using an excimer lamp in a vacuum state.

  The functional layer that can be provided on the hard coat layer has, for example, functions such as scratch resistance, abrasion resistance, antifouling property (contamination resistance), anti-fingerprint property, and antireflection property (low reflection property). Layer. The functional layer is a general known or commonly used functional layer having the above-described functions used in a hard coat layer in a display device such as a mobile phone or a smartphone. Examples of the material constituting the functional layer include acrylic materials, fluorine materials, and silicone materials. Examples of the method for providing the functional layer on the hard coat layer include a method by coating similar to the hard coat film described later, and a method by vapor deposition and sputtering.

  From the viewpoint of surface hardness and scratch resistance, the thickness of the hard coat layer is, for example, 1 to 100 μm, preferably 2 to 80 μm, more preferably 3 to 60 μm, and further preferably 5 to 50 μm.

(Base material)
As a base material in the present invention, 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), a base material whose surface is a painted surface, etc. The well-known thru | or usual base material can be used, and it does not specifically limit. Among these, a plastic substrate is preferable. The base material may have a single layer configuration or a multilayer (lamination) configuration, and the configuration (structure) is not particularly limited.

  Although the plastic material which comprises the said plastic base material is not specifically limited, Polyester, such as a polyethylene terephthalate (PET) and a polyethylene naphthalate (PEN); Polyimide; Polycarbonate; Polyamide; Polyacetal; Polyphenylene oxide; Polyphenylene sulfide; Polyethersulfone; Polyetheretherketone: Homopolymers of norbornene monomers (addition polymers and ring-opening polymers, etc.), norbornene monomers such as norbornene and ethylene copolymers, and copolymers of olefin monomers (addition polymers and open polymers). Cyclic olefin copolymers such as ring polymers), cyclic polyolefins such as derivatives thereof; vinyl polymers (for example, acrylic resins such as polymethyl methacrylate (PMMA), polystyrene, polyester Vinyl chloride, acrylonitrile-styrene-butadiene resin (ABS resin, etc.); vinylidene polymer (eg, polyvinylidene chloride, etc.); cellulose resin, such as triacetyl cellulose (TAC); epoxy resin; phenol resin; melamine resin; Examples include urea resins; maleimide resins; and various plastic materials such as silicone. 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.

  Among these, as the plastic substrate, when it is intended to obtain a hard coat film excellent in transparency, it is preferable to use a substrate excellent in transparency (transparent substrate), more preferably polyester. A film (especially PET, PEN), a cyclic polyolefin film, a polycarbonate film, a TAC film, and a PMMA film.

  The base material (particularly, plastic base material) may be an antioxidant, an ultraviolet absorber, a light-resistant stabilizer, a heat stabilizer, a crystal nucleating agent, a flame retardant, a flame retardant aid, a filler, or a plasticizer, if necessary. , Other additives such as impact resistance improvers, 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.

  Roughening treatment, easy adhesion treatment, antistatic treatment, sand blast treatment (sand mat treatment), corona discharge treatment, plasma treatment, chemical etching treatment are performed on part or all of the surface of the substrate (particularly plastic substrate). Further, known or conventional surface treatments such as water mat treatment, flame 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.). In addition, a commercial item can also be used as a base material.

  The thickness of the base material is, for example, about 1 to 1000 μm, preferably 5 to 500 μm.

(Adhesive layer)
Examples of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer include acrylic pressure-sensitive adhesives, silicon-based pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, natural rubber-based pressure-sensitive adhesives, synthetic rubber-based pressure-sensitive adhesives, ethylene-vinyl acetate copolymer-based pressure-sensitive adhesives, Examples thereof include an ethylene- (meth) acrylic ester copolymer-based adhesive, a styrene-isoprene block copolymer-based adhesive, and a styrene-butadiene block copolymer-based adhesive. The pressure-sensitive adhesive may contain various additives (for example, an antistatic agent and a slip agent) and a solvent. Among them, an acrylic pressure-sensitive adhesive, a silicon pressure-sensitive adhesive, and a urethane pressure-sensitive adhesive are preferable, and an acrylic pressure-sensitive adhesive is particularly preferable in that transparency is good and sufficient adhesive strength can be obtained even when it is thin. In addition, the said adhesive can also be used individually by 1 type, and can also be used in combination of 2 or more type.

  As the adhesive constituting the adhesive layer, a commercially available OCA (Optical Clear Adhesive) film (transparent optical adhesive film) adhesive may be used. Examples of the commercially available OCA film include LUCIACS (registered trademark) CS986 series (model numbers “CS9861US”, “CS9862UA”, “CS9863UA”, “CS9864UA”, manufactured by Nitto Denko Corporation).

  The thickness of the adhesive layer is not particularly limited as long as it has sufficient adhesiveness to be fixed to a curved display, but is, for example, 0.1 to 50 μm, preferably 1 to 45 μm, more preferably 2 to 40 μm, and still more preferably 5 ˜35 μm.

[Hard coat film for curved display]
The curved display in the hard coat film for curved display of the present invention means that at least a part thereof has a curved shape, the entire surface thereof may be a curved shape, and the curved surface is convex toward the surface. It may be curved into a shape or a concave shape, and the curved surface shape is not particularly limited. However, in the present invention, a curved surface shape having a particularly small R (radius) is preferable for obtaining the effects of the present invention. The R (radius) of the curved surface is, for example, 100 mm or less, preferably 50 mm or less, more preferably 30 mm or less, and still more preferably 10 mm or less.

  The thickness of the hard coat film of the present invention is, for example, 10 to 1000 μm, preferably 15 to 800 μm, more preferably 20 to 700 μm, and still more preferably 30 to 500 μm.

  The pencil hardness of the hard coat layer surface of the hard coat film of the present invention is, for example, H or more, preferably 2H or more, more preferably 3H or more, further preferably 4H or more, and most preferably 6H or more. The pencil hardness can be evaluated according to the method described in JIS K5600-5-4.

The scratch resistance of the hard coat layer surface of the hard coat film of the present invention was conspicuous even when the surface was reciprocated 100 times with steel wool # 0000 (rubbed) with a load of 1 kg / cm ² . Not scratched.

The hard coat film of the present invention is also excellent in the smoothness of the hard coat layer surface, and the arithmetic average roughness _Ra is, for example, 0.1 to 20 nm, preferably 0.1 to 0.1 nm in a method based on JIS B0601. The thickness is 10 nm, more preferably 0.1 to 5 nm.

  The hard coat film of the present invention is also excellent in the slip property (antifouling property) of the hard coat layer surface, and the water contact angle of the surface is, for example, 60 ° or more (for example, 60 to 110 °), preferably It is 70-110 degrees, More preferably, it is 80-110 degrees. When the water contact angle is 60 ° or more, the sliding property (antifouling property) is excellent and the scratch resistance is also excellent.

  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. In addition, the minimum of haze 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 is a layer other than the hard coat layer, the base material layer, and the adhesive layer, such as an anchor layer, an antireflection layer, an antifouling layer, a water repellent layer, an oil repellent layer, an antifogging layer, and a protective film layer. , A printing layer, a conductive layer, an electromagnetic wave shielding layer, an ultraviolet absorbing layer, an infrared absorbing layer, a blue light cut layer, and the like. Moreover, the hard coat layer may be formed only on a part of the hard coat film, or may be formed on the entire surface. The hard coat film of the present invention may use a surface protective film for the purpose of protecting the surface of the hard coat layer and facilitating punching. As the surface protective film, a known or commonly used surface protective film can be used.

  The display in the hard coat film for curved display according to the present invention is not particularly limited, but includes a smartphone, a tablet terminal, a wristwatch type terminal (smart watch), a portable game machine, a car navigation system, a notebook computer, a liquid crystal display, an organic EL display, and the like. The display with which the apparatus (display apparatus) is equipped is mentioned.

(Method for producing hard coat film for curved display)
The hard coat film of the present invention can be produced according to a known or commonly used method for producing a hard coat film, and the production method is not particularly limited, but the curable composition is applied to one surface of a substrate. And it can manufacture by forming a hard-coat layer by hardening a curable composition, apply | coating the said adhesive to the other surface side of a base material, and forming an adhesive layer.

  The curing method in the hard coat layer can be appropriately selected from known methods, and examples thereof include 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 by irradiation with active energy rays in the hard coat layer can be appropriately adjusted according to the type and energy of the active energy rays to be irradiated, the shape and size of the hard coat layer, and are not particularly limited. In the case of irradiating, for example, it is preferably about 1 to 1000 mJ / cm ² . 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.

  Although the conditions for curing by heating in the hard coat layer are not particularly limited, for example, 30 to 200 ° C is preferable, and 50 to 190 ° C is more preferable. The curing time can be appropriately set.

  Since the hard coat film of the present invention is composed of a hard coat layer excellent in flexibility and processability, it can be produced 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 the method is not particularly limited. Applying the curable composition to at least one surface of the step (step A) and the substrate that has been fed out, and then removing the solvent by drying as necessary, followed by curing the curable composition The process (process B) which forms a coat layer, and the process (process C) which winds up the obtained laminated product on a roll again is included as an essential process, and these processes (process AC) are continuously here. The method etc. to implement are mentioned. In addition, the said method may include processes other than process AC.

  The pressure-sensitive adhesive layer in the hard coat film of the present invention can also be provided by the same method as the hard coat layer. For example, the pressure-sensitive adhesive layer is provided by applying the pressure-sensitive adhesive composition to the hard coat layer and the other surface side of the substrate, and removing the solvent by drying and / or curing the pressure-sensitive adhesive composition as necessary. be able to. In addition to the method other than the above application, the adhesive layer is prepared by attaching a separately prepared adhesive layer (for example, the above-mentioned commercially available OCA film adhesive) to the hard coat layer of the substrate and the other surface side. May be provided.

[Transparent substrate with hard coat film]
The transparent substrate with a hard coat film of the present invention includes at least the hard coat film for curved display and the transparent substrate having a curved surface attached to the surface on the adhesive layer side of the hard coat film for curved display. FIG. 2 shows a schematic cross-sectional view (hard coat layer 4 / base material 5 / adhesive layer 6 / transparent substrate 7) as an example of a preferred embodiment of the transparent substrate with a hard coat film of the present invention. A transparent substrate having a curved surface is more likely to be broken by an external impact or the like than a flat transparent substrate, and glass is likely to be scattered. The transparent substrate with a hard coat film of the present invention is hard to break because the hard coat film for curved display is adhered, and can prevent scattering when broken.

  The transparent substrate has a curved surface at least partially, and the entire surface thereof may have a curved surface shape, and the curved surface may be curved in a convex shape or a concave shape toward the surface. Well, the curved surface shape is not particularly limited. Moreover, the said transparent substrate should just have transparency (for example, total light transmittance is 90% or more) of the grade used for a normal display use. In addition, the said transparent substrate is also called a cover glass, when a display is a display with a touch panel and it is a glass material.

  As a material which comprises the said transparent substrate, what is necessary is just used by the normal display use, Glass and resin are mentioned. Examples of the glass include soda glass, heat resistant glass, and tempered glass. Examples of the resin include polymethyl methacrylate (PMMA), polycarbonate (PC), polyethersulfone (PES), cyclic olefin, polyimide (PI), and polyamide (PA). It is preferable that the material which comprises a transparent substrate is glass from the point which is easy to acquire the effect excellent in the flexibility of the hard coat film of this invention. At present, glass is generally used as a transparent substrate.

  The thickness of the transparent substrate is, for example, about 10 to 1000 μm, preferably 20 to 500 μm. In addition, the R (radius) of the curved surface of the transparent substrate having the curved surface is the same as the R of the curved surface described in the hard coat film for curved display described above.

  The transparent substrate with a hard coat film can be obtained by sticking the adhesive layer side of the hard coat film on a transparent substrate having a curved surface. Although the said sticking method is not restrict | limited in particular, The method of sticking a hard-coat film and a transparent substrate is mentioned, applying moderate pressure to a hard-coat film so that a bubble may not enter. Since the transparent substrate with a hard coat film uses the hard coat film of the present invention, it is excellent in flexibility and workability, and even when R (radius) in the curved shape of the transparent substrate is small, It can be easily bent and followed.

[Display device]
The display device of the present invention comprises at least the hard coat film for curved display, the transparent substrate, and a display panel constituent member. FIG. 3 shows a cross-sectional schematic diagram (hard coat layer 4 / base material 5 / adhesive layer 6 / transparent substrate 7 / display panel constituent member 8) which is an example of a preferred embodiment of the display device of the present invention. When the display device of the present invention is a device with a touch panel such as a smartphone, a tablet terminal, or a portable game machine, the display device may have a touch panel constituent member in addition to the display panel constituent member. It may be integrated. Moreover, you may have other layers, such as an adhesion layer, an intermediate | middle layer, and undercoat, between these structural members.

  The display panel constituent member is a member constituting a general liquid crystal display, an organic EL display, or the like. When the display panel constituent member is a liquid crystal display, examples thereof include a polarizing plate, a color filter, an alignment film, a liquid crystal layer, a transparent electrode, an array substrate, a light guide plate, and a light source. Moreover, the said touch panel structural member is a structural member of a general touch panel, and an ITO layer, a wiring layer, a touch sensor layer, etc. are mentioned.

  The display device of the present invention is not particularly limited as long as it is a device provided with a display, but a smartphone, a tablet terminal, a wristwatch type terminal (smart watch), a portable game machine, a car navigation system, a notebook computer, a liquid crystal display, an organic EL. A display etc. are mentioned.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The molecular weight of the product was measured by Alliance HPLC system 2695 (manufactured by Waters), Refractive Index Detector 2414 (manufactured by Waters), column: Tskel GMH _HR- M × 2 (manufactured by Tosoh Corp.), guard column: Tskel guard column H _HR L (manufactured by Tosoh Corp.), column oven: COLUMN HEATER U-620 (manufactured by Sugai), solvent: THF, measurement conditions: 40 ° C. Moreover, the measurement of the ratio [T3 body / T2 body] of T2 body and T3 body in a product was performed by ²⁹ Si-NMR spectrum measurement by JEOL ECA500 (500 MHz). T _d5 (5% weight loss temperature) of the product was measured by TGA (thermogravimetric analysis) under an air atmosphere at a temperature rising rate of 5 ° C./min. The unit of the blending amount of the raw materials of the curable composition described in Table 1 is parts by weight.

Synthesis Example 1: Synthesis of curable resin A 2- (3,4-epoxycyclohexyl) in a 300 ml flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube under a nitrogen stream. ) Ethyltrimethoxysilane (hereinafter referred to as “EMS”) 161.5 mmol (39.79 g), phenyltrimethoxysilane (hereinafter referred to as “PMS”) 9 mmol (1.69 g), and acetone 165.9 g Was heated to 50 ° C. To the mixture thus obtained, 4.70 g of 5% aqueous potassium carbonate solution (1.7 mmol as potassium carbonate) was added dropwise over 5 minutes, and then 1700 mmol (30.60 g) of water was added dropwise over 20 minutes. . Note that no significant temperature increase occurred during the dropping. Thereafter, the polycondensation reaction was carried out for 4 hours under a nitrogen stream while maintaining the temperature at 50 ° C.
When the product in the reaction solution after the polycondensation reaction was analyzed, the number average molecular weight was 1911 and the molecular weight dispersity was 1.47. The ratio of T2 body and T3 body [T3 body / T2 body] calculated from the ²⁹ Si-NMR spectrum of the product was 10.3.
Thereafter, the reaction solution is cooled, washed with water until the lower layer solution becomes neutral, and after the upper layer solution is separated, the solvent is distilled off from the upper layer solution under conditions of 1 mmHg and 40 ° C. to produce a colorless transparent liquid The product (epoxy group-containing polyorganosilsesquioxane) was obtained. The product had a T _d5 of 370 ° C.

In addition, when the FT-IR spectrum of the curable resin A (polyorganosilsesquioxane) obtained in Synthesis Example 1 was measured by the above method, each had one intrinsic absorption peak in the vicinity of 1100 cm ^−1. Was confirmed.

Example 1
(Preparation of hard coat film)
61.6 parts by weight of curable resin A (polyorganosilsesquioxane) obtained in Synthesis Example 1, 6.9 parts by weight of a compound having an alicyclic epoxy group (trade name “EHPE3150” manufactured by Daicel Corporation), 30 parts by weight of methyl isobutyl ketone (MIBK) (manufactured by Kanto Chemical Co., Inc.), 1 part by weight of a cationic photopolymerization initiator (trade name “CPI-210S”, manufactured by San Apro Co., Ltd.), silicon acrylate (trade name “KRM8479”) , Manufactured by Daicel Ornex Co., Ltd.) 0.3 parts by weight, and silica particles having a group containing a (meth) acryloyl group on the surface (trade name “BYK-LPX 22699”, manufactured by Big Chemie Japan Co., Ltd.) 2 parts by weight of a mixed solution was prepared and used as a curable composition.
The curable composition obtained above was applied on a PEN (polyethylene naphthalate) film (trade name “Teonex” (registered trademark), manufactured by Teijin DuPont Films, Inc., thickness 50 μm) of the hard coat layer after curing. After cast coating using wire bar # 44 to a thickness of 40 μm, it was left in an oven at 80 ° C. for 1 minute (prebaked), and then irradiated with ultraviolet rays for 5 seconds (UV irradiation amount: 400 mJ / cm ² ). Finally, a film having a hard coat layer (hard coat layer / base material) was produced by heat treatment (aging) at 150 ° C. for 30 minutes.
Furthermore, an adhesive layer of an OCA film (trade name “LUCIACS (registered trademark) CS9861US”, manufactured by Nitto Denko Corporation, adhesive layer thickness 25 μm) is attached to the substrate side of the film having a hard coat layer, and hard A coated film was obtained.

Example 2 and Comparative Examples 1 and 2
A composition was prepared and a hard coat film was prepared in the same manner as in Example 1 except that the composition of the curable composition was changed as shown in Table 1 and the thickness of the hard coat layer was changed. The radical curable resin “PETIA” in the curable composition of Table 1 is pentaerythritol (tri / tetra) acrylate, trade name “PETIA” (manufactured by Daicel Ornex Co., Ltd.). The radical polymerization initiator “Irgcure 184” is 1-hydroxy-cyclohexyl-phenyl-ketone, trade name “IRGCURE 184” (manufactured by BASF).

[Evaluation]
The hard coat films of Examples 1 and 2 and Comparative Examples 1 and 2 obtained above or the hard coat film with glass were subjected to various evaluations by the following methods. The results are shown in Table 1.

(Bending resistance: Cylindrical mandrel method)
The bending resistance of the hard coat film obtained above was tested and evaluated according to JIS K5600-5-1 using a cylindrical mandrel. Tests were conducted using mandrels with diameters of 2, 3, 4, 5, and 6 mm so that the hard coat layer was on the outside. The test was performed using a mandrel having a smaller diameter in order from a mandrel having a diameter of 6 mm. Table 1 shows the minimum diameter at which the hard coat layer is not cracked by the mandrel. In Comparative Example 2, since the hard coat layer was cracked at a diameter of 6 mm, it was described as 6 mmNG.

(Pencil hardness)
The pencil hardness of the surface of the hard coat film obtained above (the surface of the hard coat layer) was evaluated according to JIS K5600-5-4. The load was 750 g.

(Spattering prevention: iron ball test)
Soda glass (manufactured by ASONE Co., Ltd., 50 × 50 × 3 mm) was attached to the adhesive layer surface of the hard coat film obtained above to prepare a hard coat film with glass. A 1 kg iron ball (diameter: about 62 mm) was dropped from a height of 50 cm onto the hard coat layer surface of the glass-coated hard coat film, a test was performed, and the following criteria were evaluated. In addition, when it tested about the said glass single-piece | unit, without sticking a hard coat film, glass broke and glass scattered (evaluation: x).
Evaluation criteria ○ (good scattering prevention): glass breaks but glass does not splash × (poor scattering prevention): glass breaks and glass scatters

(Abrasion resistance)
The hard coat film obtained above is attached to a molded body having a bent portion (curved radius: 5 mm) with the hard coat layer side as the surface, and a load of 1000 g / cm ^{2 is} applied to the bent portion (curved surface) of the hard coat layer. # 0000 steel wool was reciprocated 100 times. Based on the following criteria, the presence or absence of scratches on the surface was visually confirmed, and scratch resistance was evaluated.
Evaluation criteria ○ (good scratch resistance): no scratches observed × (poor scratch resistance): scratches visible

1 Hard Coat Film 2 Transparent Substrate with Hard Coat Film 3 Display Device 4 Hard Coat Layer 5 Base Material 6 Adhesive Layer 7 Transparent Substrate 8 Display Panel Component

Claims (10)

A hard coat film for curved display including a hard coat layer, a substrate, and an adhesive layer,
Having the hard coat layer adjacent to one surface of the substrate, and having the adhesive layer on the other surface side of the substrate;
The hard coat layer includes a polyorganosilsesquioxane below, curable silica containing at least one additive selected from the group consisting of silica particles having a group containing a (meth) acryloyl group on the surface, and silicon acrylate. A hard coat film for curved display which is a cured product layer of the composition.
Polyorganosilsesquioxane: having a structural unit represented by the following formula (1), a molar ratio of the structural unit represented by the following formula (I) and the structural unit represented by the following formula (II) [ The structural unit represented by the formula (I) / the structural unit represented by the formula (II)] is 5 or more, and the structural unit represented by the following formula (1) and the following formula ( 4) The total proportion of the structural units represented by 55) is from 55 to 100 mol%, the number average molecular weight is 1000 to 3000, and the molecular weight dispersity (weight average molecular weight / number average molecular weight) is 1.0 to 3.0. is there

[In Formula (1), R < ¹ > shows group containing an epoxy group. ]

[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. ]

[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. ]

[In formula (4), R ¹ is the same as that in formula (1). R ^c is the same as in formula (II). ] The hard coat film for curved display according to claim 1, wherein the polyorganosilsesquioxane further has a structural unit represented by the following formula (2).

[In the 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 of ] The hard coat film for curved display according to claim ² , wherein R ^{2 in the} polyorganosilsesquioxane is a substituted or unsubstituted aryl group. In the polyorganosilsesquioxane, R ¹ is a group represented by the following formula (1a), a group represented by the following formula (1b), a group represented by the following formula (1c), or the following formula The hard coat film for curved display according to any one of claims 1 to 3, which is a group represented by (1d).

[In Formula (1a), R ^1a represents a linear or branched alkylene group. ]

[In formula (1b), R ^1b represents a linear or branched alkylene group. ]

[In Formula (1c), R ^1c represents a linear or branched alkylene group. ]

[In formula (1d), R ^1d represents a linear or branched alkylene group. ]   The hard coat film for curved display according to any one of claims 1 to 4, comprising an epoxy compound other than the polyorganosilsesquioxane.   The hard coat film for curved display according to any one of claims 1 to 5, comprising a cationic photopolymerization initiator.   The thickness of the said hard-coat layer is 1-100 micrometers, The hard coat film for curved surfaces display of any one of Claims 1-6.   Total thickness is 10-1000 micrometers, The hard coat film for curved surface displays of any one of Claims 1-7.   A hard coat comprising the hard coat film for a curved display according to any one of claims 1 to 8 and a transparent substrate having a curved face, which is attached to a surface of the hard coat film for a curved display on the adhesive layer side. Transparent substrate with film.   A display device comprising: the hard coat film for curved display according to any one of claims 1 to 8, a transparent substrate having a curved surface, and a display panel constituent member.

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