Hard coat composition, hard coat film and method for producing the same

Abstract

To provide a hard coat composition capable of forming an excellent cured product having high surface hardness and bending resistance.SOLUTION: The hard coat composition contains: a silsesquioxane compound being a condensate of a silane compound which contains a silane compound containing an alicyclic epoxy group and a silane compound containing a (meth)acryloyl group; and a fluorine compound having a double bond. The weight average molecular weight of the silsesquioxane compound is 500-20,000. The silsesquioxane compound contains a T3 structure and a T2 structure. The content ratio T3 / T2 of the T3 structure to the T2 structure is less than 5.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a silsesquioxane compound having an alicyclic epoxy group and a (meth)acryloyl group, a fluorine compound having a double bond, and a hard coat composition containing the silsesquioxane compound and the fluorine compound. The present invention also relates to a hard coat film having a hard coat layer (first hard coat layer) formed from the hard coat composition containing the silsesquioxane compound and the fluorine compound, and a method for producing the same. [Background technology]

[0002] For cover window materials for foldable / flexible displays, it is necessary to develop new materials made of bendable plastic films instead of glass. Such cover window materials are required to have mechanical properties such as bending durability, transparency, surface hardness, scratch resistance, and impact resistance. However, since it is difficult to achieve surface hardness and scratch resistance with general-purpose plastic films, it is necessary to provide a hard coat layer on the surface.

[0003] As a material for forming the hard coat layer in such a hard coat film, Patent Document 1 discloses a UV-curable acrylic monomer, and Patent Document 2 discloses a polyorganosilsesquioxane resin. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2009-279840 [Patent Document 2] Japanese Patent Application Publication No. 2019-143161 Summary of the Invention [Problem to be solved by the invention]

[0005] However, hard coat films using UV-curable acrylic monomers still do not have sufficient surface hardness, and if they are made multifunctional or the hard coat layer is made thick to improve the surface hardness, there is a problem that the curing shrinkage of the material during UV curing increases, making them prone to cracking. Also, the hard coat film using the polyorganosilsesquioxane resin disclosed in Patent Document 2 cannot be said to have a sufficient balance of surface hardness and flexibility for use in cover windows, etc.

[0006] Therefore, an object of the present invention is to provide a hard coat composition capable of forming an excellent cured product having high surface hardness and flex resistance, and also to provide a hard coat film having high surface hardness and flex resistance, in which a cured product of the hard coat composition is formed on at least one surface of a transparent resin substrate. [Means for solving the problem]

[0007] As a result of extensive research, the present inventors have come to overcome the above-mentioned problems by providing the following configuration.

[0008] [1] A silsesquioxane compound which is a condensation product of a silane compound containing a silane compound represented by general formula (1) and a silane compound represented by general formula (2); A hard coat composition containing a fluorine compound having a double bond, [ka] [ka] The weight average molecular weight of the silsesquioxane compound is 500 to 20,000, The silsesquioxane compound includes a T3 structure represented by general formula (3) and a T2 structure represented by general formula (4), [ka] [ka] The ratio of the content of the T3 structure to the content of the T2 structure, T3 / T2, is less than 5; Hardcoat composition. (In general formula (1), X is a monovalent organic group containing an alicyclic epoxy group, In general formula (2), Y is a monovalent organic group containing a (meth)acryloyl group, In general formula (1) and general formula (2), R 1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 2 is a hydrogen atom or a monovalent organic group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms, and x is 2 or 3; In the general formula (3) and the general formula (4), Q is an arbitrary monovalent organic group, In general formula (4), Z is a hydrogen atom or a monovalent organic group selected from the group consisting of an alkoxy group having an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms.

[0009] [2] A hard coat film comprising a transparent resin substrate and a first hard coat layer formed on at least one surface thereof, the first hard coat layer being made of a cured product containing the hard coat composition according to [1].

[0010] [3] The hard coat film according to [2], wherein the thickness of the first hard coat layer is 0.5 to 100 μm.

[0011] [4] A second hard coat layer is further provided between the transparent resin substrate and the first hard coat layer, the second hard coat layer is a cured product of a hard coat composition containing a silsesquioxane compound which is a condensate of a silane compound including a silane compound represented by general formula (1), the weight average molecular weight of the silsesquioxane compound is 500 to 20,000, the silsesquioxane compound contains a T3 structure represented by general formula (3) and a T2 structure represented by general formula (4), and the ratio of the contents of the T3 structure and the T2 structure, T3 / T2, is less than 5; The hard coat film according to [2], wherein the first hard coat layer has a thickness of 0.5 to 100 μm, and the second hard coat layer has a thickness of 0.5 to 100 μm. [ka] [ka] [ka]

[0012] [5] The hard coat film according to any one of [2] to [4], wherein the transparent resin substrate contains one or more resin materials selected from the group consisting of polyester, polycarbonate, polyamide, polyimide, cyclic polyolefin, acrylic resin, and cellulose-based resin.

[0013] [6] A method for producing a hard coat film, comprising applying the hard coat composition according to [1] to a transparent resin substrate and curing the hard coat composition by irradiating it with active energy rays.

[0014] [7] A composition containing a silane compound condensate including a silane compound represented by general formula (1), a photocationic polymerization initiator, and a neutral salt in an amount of 1 ppm to 10,000 ppm is applied onto a transparent resin substrate, and the composition is cured by irradiating the substrate with active energy rays. A method for producing a hard coat film, comprising applying the hard coat composition according to [1] onto the hard coat film and curing the hard coat composition by irradiating it with active energy rays. (In general formula (1), X is a monovalent organic group containing an alicyclic epoxy group, and R 1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 2 is a hydrogen atom or a monovalent organic group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms, and x is 2 or 3. [ka] [Effects of the Invention]

[0015] The present invention provides a hard coat composition capable of forming an excellent cured product having high scratch resistance and flex resistance. Furthermore, by forming the cured product on at least one surface of a resin substrate, a hard coat film having high scratch resistance and flex resistance can be obtained. DETAILED DESCRIPTION OF THE INVENTION

[0016] In this specification, a silane compound condensate containing a silane compound represented by general formula (1) and a silane compound represented by general formula (2) and a silane compound condensate containing a silane compound represented by general formula (1) are also referred to as a silsesquioxane compound. Furthermore, the term "(meth)acryloyl group" is used to mean both an acryloyl group and a methacryloyl group.

[0017] [Silsesquioxane compounds] A silane compound condensate containing a silane compound represented by the following general formula (1) (also referred to as silane compound (1)) and a silane compound represented by the following general formula (2) (also referred to as silane compound (2)): The weight average molecular weight of the silsesquioxane compound is 500 to 20,000, The silsesquioxane compound includes a T3 structure represented by general formula (3) and a T2 structure represented by general formula (4), The ratio of the content of the T3 structure to the content of the T2 structure, T3 / T2, is less than 5; Silsesquioxane compounds. (In general formula (1), X is a monovalent organic group containing an alicyclic epoxy group, In general formula (2), Y is a monovalent organic group containing a (meth)acryloyl group, In general formula (1) and general formula (2), R 1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R 2 is a hydrogen atom or a monovalent organic group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms, and x is 2 or 3; In the general formula (3) and the general formula (4), Q is an arbitrary monovalent organic group, In general formula (4), Z is a hydrogen atom or a monovalent organic group selected from the group consisting of an alkoxy group having an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms. [ka] [ka] [ka] [ka]

[0018] In general formula (1), X represents a monovalent organic group containing an alicyclic epoxy group. Examples of the monovalent organic group containing an alicyclic epoxy group include an alicyclic epoxy group, an alkyl group having an alicyclic epoxy group as a substituent, and an ethylene glycol group having an alicyclic epoxy group as a substituent. From the viewpoints of heat resistance and flex resistance, an alkyl group having an alicyclic epoxy group as a substituent is preferred. Specific examples of such alkyl groups having an alicyclic epoxy group as a substituent include a (3,4-epoxycyclohexyl)methyl group, a 2-(3,4-epoxycyclohexyl)ethyl group, a 3-(3,4-epoxycyclohexyl)propyl group, a 4-(3,4-epoxycyclohexyl)butyl group, a 5-(3,4-epoxycyclohexyl)pentyl group, a 6-(3,4-epoxycyclohexyl)hexyl group, a 7-(3,4-epoxycyclohexyl)heptyl group, an 8-(3,4-epoxycyclohexyl)octyl group, a 9-(3,4-epoxycyclohexyl)nonyl group, a 10-(3,4-epoxycyclohexyl)butyl group, a 11-(3,4-epoxycyclohexyl)butyl group, a 12-(3,4-epoxycyclohexyl)butyl group, a 13-(3,4-epoxycyclohexyl)butyl group, a 14-(3,4-epoxycyclohexyl)butyl group, a 15-(3,4-epoxycyclohexyl)butyl group, a 16-(3,4-epoxycyclohexyl)butyl group, a 17-(3,4-epoxycyclohexyl)butyl group, a 18-(3,4-epoxycyclohexyl)butyl group, a 19-(3,4-epoxycyclohexyl)butyl group, a 20-(3,4-epoxycyclohexyl)butyl group, a 21-(3,4-epoxycyclohexyl)butyl group, a 22-(3,4-epoxycyclohexyl)butyl group, a 23-(3,4-epoxycyclohexyl)butyl group, a 24-(3,4-epoxycyclohexyl)butyl group, a 25-(3,4-epoxycyclohexyl)butyl group, a 26-(3,4-epoxycyclohexyl)butyl group, a 27

[0033] Examples of epoxycyclohexyl groups include 11-(3,4-epoxycyclohexyl)decyl group, 11-(3,4-epoxycyclohexyl)undecyl group, 12-(3,4-epoxycyclohexyl)dodecyl group, 13-(3,4-epoxycyclohexyl)tridecyl group, 14-(3,4-epoxycyclohexyl)tetradecyl group, 15-(3,4-epoxycyclohexyl)pentadecyl group, 16-(3,4-epoxycyclohexyl)hexadecyl group, 2-(3,4-epoxycyclohexyl)isopropyl group, 3-(3,4-epoxycyclohexyl)isobutyl group, and 6-(3,4-epoxycyclohexyl)ethylhexyl group.

[0019] In general formula (2), Y represents a monovalent organic group containing a (meth)acryloyl group. Examples of the monovalent organic group containing a (meth)acryloyl group include a substituted or unsubstituted (meth)acryloyl group-substituted alkyl group, a (meth)acryloyl group-substituted alkenyl group, and a (meth)acryloyl group-substituted aryl group. From the viewpoints of good storage stability, a fast curing rate upon irradiation with active energy rays, and suppression of cracking in the resulting coating film, a (meth)acryloyl group-substituted alkyl group is preferred. Specific examples of such (meth)acryloyl group-substituted alkyl groups include a 1-(meth)acryloyloxymethyl group, a 2-(meth)acryloyloxyethyl group, a 3-(meth)acryloyloxypropyl group, a 4-(meth)acryloyloxybutyl group, a 6-(meth)acryloyloxyhexyl group, and an 8-(meth)acryloyloxyoctyl group.

[0020] In general formula (1) and general formula (2), R 1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, and an ethylhexyl group. From the viewpoint of facilitating hydrolysis and condensation of a silane compound having a hydrolyzable silyl group, R 1 The alkyl group is preferably a methyl group, an ethyl group or a propyl group, and most preferably a methyl group.

[0021] In general formula (1) and general formula (2), R 2 represents a hydrogen atom or a monovalent hydrocarbon group selected from an alkyl group having 1 to 16 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms. Examples of such hydrocarbon groups include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, an ethylhexyl group, a benzyl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a phenethyl group.

[0022] In general formula (1) and general formula (2), x is an integer of 1 to 3, and is appropriately selected depending on the physical properties required for the hard coat.

[0023] Specific examples of the silane compound (1) include (3,4-epoxycyclohexyl)trimethoxysilane, (3,4-epoxycyclohexyl)methyldimethoxysilane, (3,4-epoxycyclohexyl)dimethylmethoxysilane, (3,4-epoxycyclohexyl)triethoxysilane, (3,4-epoxycyclohexyl)methyldiethoxysilane, (3,4-epoxycyclohexyl)dimethylethoxysilane, (3,4-epoxycyclohexyl)methyltrimethoxysilane, {(3,4-epoxycyclohexyl)methyl}methyl Dimethoxysilane, {(3,4-epoxycyclohexyl)methyl}dimethylmethoxysilane, (3,4-epoxycyclohexyl)methyltriethoxysilane, {(3,4-epoxycyclohexyl)methyl}methyldiethoxysilane, {(3,4-epoxycyclohexyl)methyl}dimethylethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, {2-(3,4-epoxycyclohexyl)ethyl}methyldimethoxysilane, {2-(3,4-epoxycyclohexyl)ethyl}dimethylmethoxysilane, 2- (3,4-epoxycyclohexyl)ethyltriethoxysilane, {2-(3,4-epoxycyclohexyl)ethyl}methyldiethoxysilane, {2-(3,4-epoxycyclohexyl)ethyl}dimethylethoxysilane, 3-(3,4-epoxycyclohexyl)propyltrimethoxysilane, {3-(3,4-epoxycyclohexyl)propyl}methyldimethoxysilane, {3-(3,4-epoxycyclohexyl)propyl}dimethylmethoxysilane, 3-(3,4-epoxycyclohexyl)propyltriethoxysilane, {3-(3 ,4-epoxycyclohexyl)propyl}methyldiethoxysilane, {3-(3,4-epoxycyclohexyl)propyl}dimethylethoxysilane, 4-(3,4-epoxycyclohexyl)butyltrimethoxysilane, {4-(3,4-epoxycyclohexyl)butyl}methyldimethoxysilane, {4-(3,4-epoxycyclohexyl)butyl}dimethylmethoxysilane, 4-(3,4-epoxycyclohexyl)butyltriethoxysilane, {4-(3,4-epoxycyclohexyl)butyl}methyldiethoxysilane, {4-(3,{5-(3,4-epoxycyclohexyl)butyl}dimethylethoxysilane, 5-(3,4-epoxycyclohexyl)pentyltrimethoxysilane, {5-(3,4-epoxycyclohexyl)pentyl}methyldimethoxysilane, {5-(3,4-epoxycyclohexyl)pentyl}dimethylmethoxysilane, 5-(3,4-epoxycyclohexyl)pentyltriethoxysilane, {5-(3,4-epoxycyclohexyl)pentyl}methyldiethoxysilane, {5-(3,4-epoxycyclohexyl)pentyl}dimethylethoxysilane Silane, 6-(3,4-epoxycyclohexyl)hexyltrimethoxysilane, {6-(3,4-epoxycyclohexyl)hexyl}methyldimethoxysilane, {6-(3,4-epoxycyclohexyl)hexyl}dimethylmethoxysilane, 6-(3,4-epoxycyclohexyl)hexyltriethoxysilane, {6-(3,4-epoxycyclohexyl)hexyl}methyldiethoxysilane, {6-(3,4-epoxycyclohexyl)hexyl}dimethylethoxysilane, 8-(3,4-epoxycyclohexyl)octyltriethoxysilane Trimethoxysilane, {8-(3,4-epoxycyclohexyl)octyl}methyldimethoxysilane, {8-(3,4-epoxycyclohexyl)octyl}dimethylmethoxysilane, 8-(3,4-epoxycyclohexyl)octyltriethoxysilane, {8-(3,4-epoxycyclohexyl)octyl}methyldiethoxysilane, {8-(3,4-epoxycyclohexyl)octyl}dimethylethoxysilane, 10-(3,4-epoxycyclohexyl)decyltrimethoxysilane, {10-(3,4-epoxycyclohexyl)decyltrimethoxysilane 10-(3,4-epoxycyclohexyl)decyl}methyldimethoxysilane, {10-(3,4-epoxycyclohexyl)decyl}dimethylmethoxysilane, 10-(3,4-epoxycyclohexyl)decyltriethoxysilane, {10-(3,4-epoxycyclohexyl)decyl}methyldiethoxysilane, {10-(3,4-epoxycyclohexyl)decyl}dimethylethoxysilane, 12-(3,4-epoxycyclohexyl)dodecyltrimethoxysilane, {12-(3,4-epoxycyclohexyl)dodecyl}methyldimethoxysilane, {12-(3,{12-(3,4-epoxycyclohexyl)dodecyl}dimethylmethoxysilane, 12-(3,4-epoxycyclohexyl)dodecyltriethoxysilane, {12-(3,4-epoxycyclohexyl)dodecyl}methyldiethoxysilane, {12-(3,4-epoxycyclohexyl)dodecyl}dimethylethoxysilane, 14-(3,4-epoxycyclohexyl)tetradecyltrimethoxysilane, {14-(3,4-epoxycyclohexyl)tetradecyl}methyldimethoxysilane, {14-(3,4-epoxycyclohexyl)tetradecyl}dimethylmethoxysilane, 14-(3,4-epoxycyclohexyl)tetradecyltriethoxysilane, {14-(3,4-epoxycyclohexyl )tetradecyl}methyldiethoxysilane, {14-(3,4-epoxycyclohexyl)tetradecyl}dimethylethoxysilane, 16-(3,4-epoxycyclohexyl)hexadecyltrimethoxysilane, {16-(3,4-epoxycyclohexyl)hexadecyl}methyldimethoxysilane, {16-(3,4-epoxycyclohexyl)hexadecyl}dimethylmethoxysilane, 16-(3,4-epoxycyclohexyl)hexadecyltriethoxysilane, {16-(3,4-epoxycyclohexyl)hexadecyl}methyldiethoxysilane, {16-(3,4-epoxycyclohexyl)hexadecyl}dimethylethoxysilane, etc.

[0024] Specific examples of the silane compound (2) include 1-(meth)acryloyloxymethyltrimethoxysilane, {1-(meth)acryloyloxymethyl}methyldimethoxysilane, 1-(meth)acryloyloxymethyltriethoxysilane, {1-(meth)acryloyloxymethyl}methyldiethoxysilane, 2-(meth)acryloyloxyethyltrimethoxysilane, {2-(meth)acryloyloxyethyl}methyldimethoxysilane, 2-(meth)acryloyloxyethyltriethoxysilane, {2-(meth)acryloyloxyethyl}methyldiethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, {3-(meth)acryloyloxypropyl}methyldimethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, {3-(meth)acryloyloxypropyl}methyldiethoxysilane Silane, 4-(meth)acryloyloxybutyltrimethoxysilane, {4-(meth)acryloyloxybutyl}methyldimethoxysilane, 4-(meth)acryloyloxybutyltriethoxysilane, {4-(meth)acryloyloxybutyl}methyldiethoxysilane, 6-(meth)acryloyloxyhexyltrimethoxysilane, {6-(meth)acryloyloxyhexyl}methyldimethoxysilane, 6-( Examples thereof include (meth)acryloyloxyhexyltriethoxysilane, {6-(meth)acryloyloxyhexyl}methyldiethoxysilane, 8-(meth)acryloyloxyoctyltrimethoxysilane, {8-(meth)acryloyloxyoctyl}methyldimethoxysilane, 8-(meth)acryloyloxyoctyltriethoxysilane, and {8-(meth)acryloyloxyoctyl}methyldiethoxysilane.

[0025] In general formula (3) and general formula (4), Q is the same as X in formula (1) or Y in formula (2).

[0026] In general formula (4), Z represents a hydroxyl group or an alkoxy group having an alkyl group of 1 to 10 carbon atoms. Examples of such an alkoxy group having an alkyl group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, and a decyloxy group.

[0027] The ratio of the structure represented by general formula (1) to the total number of Si atoms in the silsesquioxane compound of the present invention is preferably 0.05 or more, more preferably 0.1 or more, from the viewpoint of increasing the hardness of the cured product. The ratio of the structure represented by general formula (1) to the total number of Si atoms in the silsesquioxane compound is preferably 0.95 or less, more preferably 0.9 or less, even more preferably 0.8 or less, and particularly preferably 0.75 or less, from the viewpoint of increasing the outward bending resistance of the cured product.

[0028] The ratio of the structure represented by general formula (2) to the total number of Si atoms in the silsesquioxane compound of the present invention is preferably 0.05 or more, more preferably 0.1 or more, even more preferably 0.2 or more, and particularly preferably 0.25 or more, from the viewpoint of improving the flexibility of the cured product. From the viewpoint of reducing curling of the cured product, the ratio of the structure represented by general formula (2) to the total number of Si atoms in the silsesquioxane compound is preferably less than 0.95, more preferably 0.90 or less.

[0029] When a silsesquioxane compound is obtained by condensation of a silane compound, other silane compounds may be used in addition to the above-mentioned silane compounds (1) and (2). The other silane compound (i.e., a silane compound not containing an alicyclic epoxy group and a (meth)acryloyl group, hereinafter sometimes referred to as "silane compound (5)") is represented by the following general formula (5): [ka]

[0030] From the viewpoint of flex resistance and scratch resistance, the ratio of the silane compound represented by general formula (5) to the total number of Si atoms in the silsesquioxane compound of the present invention is preferably 0.5 or less, more preferably 0.4 or less, even more preferably 0.3 or less, and may be 0.

[0031] In general formula (5), R 1 , R 2 and x are the same as in general formula (1) and general formula (2). W is a monovalent organic group that does not contain an alicyclic epoxy group or a (meth)acryloyl group. W is a group containing a substituted or unsubstituted double bond, a group containing a substituted or unsubstituted cycloalkyl group, a group containing a substituted or unsubstituted aromatic ring, a substituted or unsubstituted alkyl group, a group containing a glycidyl group, a group containing an oxetanyl group, or a hydrogen atom.

[0032] Examples of groups containing a substituted or unsubstituted double bond include a vinyl group, an allyl group, and an isopropenyl group. Examples of groups containing a substituted or unsubstituted cycloalkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutylmethyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a cyclobutylethyl group, a cyclopentylethyl group, and a cyclohexylethyl group. Examples of groups containing a substituted or unsubstituted aromatic ring include a phenyl group, a 4-methylphenyl group, a tolyl group, and a naphthyl group. Examples of substituted or unsubstituted alkyl groups include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, and an ethylhexyl group. Examples of groups having a glycidyl group include a glycidyloxymethyl group, a 2-glycidyloxyethyl group, a 3-glycidyloxypropyl group, a 4-glycidyloxybutyl group, a 5-glycidyloxypentyl group, a 6-glycidyloxyhexyl group, a 7-glycidyloxyheptyl group, an 8-glycidyloxyoctyl group, a 9-glycidyloxynonyl group, a 10-glycidyloxydecyl group, an 11-glycidyloxyundecyl group, a 12-glycidyloxydodecyl group, a 14-glycidyloxytetradecyl group, and a 16-glycidyloxyhexadecyl group. Examples of groups having an oxetanyl group include an oxetanylmethyl group, a 3-methyl-3-oxetanylmethoxymethyl group, and a 3-ethyl-3-oxetanylmethoxymethyl group.

[0033] The weight-average molecular weight of the silsesquioxane compound of the present invention is preferably 500 or more from the viewpoint of increasing the hardness of the cured product. Furthermore, from the viewpoint of suppressing the volatilization of the siloxane compound, the weight-average molecular weight of the siloxane compound is preferably 500 or more. On the other hand, if the molecular weight is excessively large, cloudiness may occur due to reduced compatibility with other compositions. Therefore, the weight-average molecular weight of the siloxane compound is preferably 20,000 or less.

[0034] The weight-average molecular weight of the silsesquioxane compound of the present invention can be controlled by appropriately selecting the amount of water and the type and amount of catalyst used in the reaction. For example, the weight-average molecular weight can be increased by increasing the amount of water initially charged.

[0035] SiO contained in the silane compounds represented by general formula (1) and general formula (2) 3 / 2 (corresponding to x=3 in general formulas (1) and (2)), SiO 2 / 2 (corresponding to x=2 in general formulas (1) and (2)), SiO 1 / 2 When the structures (corresponding to x=1 in general formulas (1) and (2)) are respectively designated as T structure, D structure, and M structure, the ratio of [T structure] to [T structure] + [D structure] + [M structure] is preferably 0.2 or more and 1.0 or less, more preferably 0.4 or more and 1.0 or less, and even more preferably 0.6 or more and 1.0 or less. If the ratio of [T structure] is less than 0.2, sufficient pencil hardness may not be obtained. From the viewpoint of increasing the crosslinking density and improving the hardness of the cured product, it is preferable that the residual rate of epoxy structures in the silsesquioxane compounds obtained by hydrolysis and condensation of the silane compounds represented by general formula (1) and general formula (2) is high.

[0036] The silsesquioxane compound of the present invention is formed by hydrolysis and condensation of silane compounds represented by general formula (1) and general formula (2), and contains a structural unit represented by general formula (3) or general formula (4). The ratio [T3 isomer] / [T2 isomer] of the structural unit represented by formula (3) (a structure in which all three alkoxysilanes in a silane compound having a T unit structure where x = 3 in general formulas (1) and (2) have undergone a condensation reaction to form an Si-O-Si structure; hereinafter referred to as [T3 isomer]) to the structural unit represented by formula (4) (a structure in which two of the three alkoxysilanes in a silane compound having a T unit structure where x = 3 in general formulas (1) and (2) have undergone a condensation reaction to form an Si-O-Si structure; hereinafter referred to as [T2 isomer]) is preferably 0.8 or more and less than 5, more preferably 1 or more and less than 4, and even more preferably 1.5 or more and less than 3. A hard coat film having a hard coat layer made of a cured product of the silsesquioxane compound of the present invention exhibits excellent flex resistance by adjusting the ratio of the T3 isomer to the T2 isomer, [T3 isomer] / [T2 isomer], to less than 5. If the content of the T3 isomer in the condensate increases and the ratio [T3 isomer] / [T2 isomer] is 5 or more, the resulting condensate will have a dense structure and will have reduced flexibility, resulting in reduced flex resistance when formed into a hard coat film.

[0037] The contents and ratios of the T3 and T2 isomers in the silsesquioxane compound of the present invention are, for example, 29 It can be calculated by Si-NMR measurement. 29 In Si-NMR measurements, the chemical shift of the silicon atom in the T3 isomer is different from that in the T2 isomer, and signals are displayed at different positions in the spectrum. Therefore, the ratio [T3 isomer] / [T2 isomer] can be calculated by calculating the integral value of each signal.

[0038] The ratio of the T3 isomer to the T2 isomer in the silsesquioxane compound of the present invention, [T3 isomer] / [T2 isomer], can be controlled by appropriately selecting the amount of water and the type and amount of catalyst used in the reaction. For example, the ratio [T3 isomer] / [T2 isomer] can be increased by increasing the amount of catalyst initially charged.

[0039] The amount of water required for the hydrolysis and condensation reactions is determined by the amount of OR bonded directly to the silicon atom. 2 group (OR in general formula (1) and general formula (2) 2 The amount of water is preferably 0.3 to 10 equivalents, more preferably 0.5 to 5 equivalents, and even more preferably 1 to 3 equivalents, relative to 1 equivalent of the alkyl group. 2 If the amount exceeds 10 equivalents, the hydrolysis of the groups may not proceed sufficiently, which may reduce the surface hardness of the hard coat film.If the amount exceeds 10 equivalents, the reaction rate of the hydrolysis and condensation reaction may be too high, resulting in the formation of high molecular weight condensates, which may reduce the physical properties and transparency of the cured film.

[0040] The residual ratio of the epoxy structure, i.e., the ratio of the number of moles of the epoxy structure in the silsesquioxane compound obtained by condensation to the number of moles of the epoxy structure in the raw material silane compound (1), is preferably 20% or more, more preferably 40% or more, and even more preferably 60% or more. 1 It can be calculated by H-NMR measurement.

[0041] In the present invention, the hydrolysis and condensation reactions are carried out in the presence of a neutral salt catalyst. By carrying out the hydrolysis and condensation reactions in the presence of a neutral salt catalyst, a silsesquioxane compound can be obtained without deactivating the epoxy groups before, after, or during storage of the hydrolysis and condensation reactions.

[0042] Furthermore, because the neutral salt catalyst itself does not corrode the manufacturing or storage containers, it can be used without restrictions on the materials of the manufacturing or storage equipment. This is because, in general, acid and base catalysts react electrophilically or nucleophilically with various substances, or change the hydrogen ion or hydroxide ion concentration in the reaction solution, causing these ions to contribute to the reaction, whereas neutral salts have extremely low reactivity as described above.

[0043] Furthermore, when an acid or base catalyst is used in the hydrolysis and condensation reactions, it is necessary to go through an acid / base removal step or a neutralization step for the reasons mentioned above. These steps are undesirable because they are cumbersome and reduce the yield. To address these issues, the use of a neutral salt catalyst is preferable because it does not require these steps.

[0044] The neutral salt used in the present invention is a normal salt consisting of a strong acid and a strong base, and is a salt consisting of a combination of a cation selected from the group consisting of Group 1 element ions and Group 2 element ions and an anion selected from the group consisting of chloride ions, bromide ions, and iodide ions.

[0045] Specific examples of the neutral salt in the present invention include lithium chloride, sodium chloride, potassium chloride, beryllium chloride, magnesium chloride, calcium chloride, lithium bromide, sodium bromide, potassium bromide, beryllium bromide, magnesium bromide, calcium bromide, lithium iodide, sodium iodide, potassium iodide, beryllium iodide, magnesium iodide, and calcium iodide.

[0046] In the present invention, the greater the amount of neutral salt used, the more the hydrolysis and condensation reaction of the silane compound is accelerated. However, when the transparency of the condensate and the purification process are taken into consideration, the smaller the amount added, the better.

[0047] The amount of the neutral salt used in the present invention is preferably 0.000001 to 0.1 mol, particularly preferably 0.000005 to 0.01 mol, per mol of the hydrolyzable silyl group of the silane compound. The amount of the neutral salt remaining in the silsesquioxane compound is preferably 1 ppm to 10,000 ppm, more preferably 50 ppm to 5,000 ppm, and even more preferably 100 ppm to 1,000 ppm.

[0048] In the production of the silsesquioxane compound of the present invention, in consideration of safety during production, it is preferable to carry out the production while refluxing the dilution solvent, alcohol generated by hydrolysis, etc.

[0049] In producing the silsesquioxane compound of the present invention, the dilution solvent, reaction temperature, and reaction time can be selected appropriately. For example, the target compound can be obtained by using propylene glycol monomethyl ether and methanol as solvents and heating and stirring at 80°C for 6 hours.

[0050] [Fluorine compounds with double bonds] The hard coat composition of the present invention contains a fluorine compound having a double bond. By containing a fluorine compound having a double bond, it is possible to reduce the surface tension of the curable composition, improve surface smoothness, improve slipperiness, improve anti-fingerprint properties, and improve scratch resistance. The leveling agent preferably has a group reactive with an epoxy group and / or a hydrolytic condensation group. By containing a group reactive with an epoxy group and / or a hydrolytic condensation group, it is possible to obtain a hard coat layer with better scratch resistance.

[0051] The fluorine compound having a double bond may be any of a monomer, an oligomer, and a polymer, as long as it has a double bond. The fluorine compound having a double bond forms a chemical bond with the (meth)acryloyl group of the silsesquioxane compound in the hard coat layer by photoradical polymerization, and remains on the surface without being detached even after repeated rubbing, so that the scratch resistance can be maintained well. Preferred functional groups having a double bond include acryloyl, methacryloyl, vinyl, allyl, and cinnamoyl groups, with radically polymerizable groups being preferred, and acryloyl and methacryloyl groups being particularly preferred.

[0052] Preferably, 30% or more of the added amount of fluorine compound having a double bond segregates within 100 nm of the hard coat layer surface, more preferably 50% or more segregates within 100 nm of the hard coat layer surface, and even more preferably 80% or more segregates within 100 nm of the hard coat layer surface. The fluorine compound having a double bond may be a polymer or oligomer with a compound that does not contain a fluorine atom, but is preferably a monomer or oligomer from the viewpoint of ease of segregation on the hard coat layer surface and ease of forming a chemical bond by reaction with the (meth)acryloyl group of the silsesquioxane compound. The fluorine compound having a double bond segregates on the hard coat layer surface and forms a chemical bond with the (meth)acryloyl group of the silsesquioxane compound, thereby achieving excellent scratch resistance.

[0053] The fluorine compound having a double bond is preferably a fluorine-based compound represented by the following general formula (6): (wherein R f is a (per)fluoroalkyl group or a (per)fluoropolyether group, R 3 is a single bond or a linking group, R 4 represents a polymerizable unsaturated group. n represents an integer of 1 to 3. m represents an integer of 1 to 3. [ka]

[0054] In general formula (6), R 4 represents a double bond group. The double bond group is preferably a group having an unsaturated bond that can undergo a radical polymerization reaction when irradiated with active energy rays such as ultraviolet rays or electron beams (i.e., a radically polymerizable group), and examples thereof include a (meth)acryloyl group, a (meth)acryloyloxy group, a vinyl group, and an allyl group, with a (meth)acryloyl group, a (meth)acryloyloxy group, and groups in which any hydrogen atom in these groups has been substituted with a fluorine atom being preferred.

[0055] In general formula (6), R frepresents a (per)fluoroalkyl group or a (per)fluoropolyether group. Here, the (per)fluoroalkyl group represents at least one of a fluoroalkyl group and a perfluoroalkyl group, and the (per)fluoropolyether group represents at least one of a fluoropolyether group and a perfluoropolyether group. From the viewpoint of scratch resistance, R f The higher the fluorine content in the polymer, the more preferable.

[0056] The (per)fluoroalkyl group is preferably a group having 1 to 20 carbon atoms, more preferably a group having 1 to 10 carbon atoms. The (per)fluoroalkyl group may have a linear structure (e.g., -CF2CF3, -CH2(CF2)4H, -CH2(CF2)8CF3, -CH2CH2(CF2)4H), a branched structure (e.g., -CH(CF3)2, -CH2CF(CF3)2, -CH(CH3)CF2CF3, -CH(CH3)(CF2)5CF2H), or an alicyclic structure (preferably a 5- or 6-membered ring, such as a perfluorocyclohexyl group, a perfluorocyclopentyl group, or an alkyl group substituted with these groups).

[0057] The (per)fluoropolyether group refers to a (per)fluoroalkyl group having an ether bond, and may be a monovalent or divalent or higher valent group. Examples of the fluoropolyether group include -CH2OCH2CF2CF3, -CH2CH2OCH2C4F8H, -CH2CH2OCH2CH2C8F 17 , -CH2CH2OCF2CF2OCF2CF2H, and a fluorocycloalkyl group having 4 to 20 carbon atoms and 4 or more fluorine atoms. Examples of the perfluoropolyether group include, for example, -(CF2O) h -(CF2CF2O) k -, -[CF(CF3)CF2O] h -[CF(CF3)] k -, -(CF2CF2CF2O) h -, -(CF2CF2O) h-, etc. The above h and k each independently represent an integer of 0 to 20, provided that h+k is an integer of 1 or more. The total of h and k is preferably 1 to 83, more preferably 1 to 43, and even more preferably 5 to 23. From the viewpoint of excellent scratch resistance, the above fluorine compound having a double bond is -(CF2O) h -(CF2CF2O) k It is particularly preferred that the hydroxyl group has a perfluoropolyether group represented by the formula:

[0058] In the present invention, the fluorine compound having a double bond preferably has a perfluoropolyether group and a plurality of double bond groups in one molecule.

[0059] In general formula (6), R 3 represents a linking group. 3 Examples of R include alkylene groups, arylene groups, and heteroalkylene groups, as well as linking groups that are combinations of these groups. These linking groups may further have functional groups such as oxy groups, carbonyl groups, carbonyloxy groups, carbonylimino groups, and sulfonamide groups, as well as combinations of these groups. 3 is preferably an ethylene group, more preferably an ethylene group bonded to a carbonylimino group.

[0060] The fluorine atom content of the fluorine compound having a double bond is not particularly limited, but is preferably 20% by mass or more, more preferably 30 to 70% by mass, and even more preferably 40 to 70% by mass.

[0061] Preferred examples of fluorine compounds having a double bond include R-2020, M-2020, R-3833, M-3833, and Optool DAC (all trade names) manufactured by Daikin Chemical Industries, Ltd., and Megafac F-171, F-172, F-179A, RS-78, RS-90, Defensa MCF-300, and MCF-323 (all trade names) manufactured by DIC Corporation, but are not limited to these.

[0062] In view of scratch resistance, the product of n and m (n×m) in general formula (6) is preferably 2 or greater, and more preferably 4 or greater.

[0063] (Molecular weight of fluorine compound having double bond) The weight average molecular weight (Mw) of the fluorine compound having a double bond with a polymerizable unsaturated group can be measured by molecular exclusion chromatography, for example, gel permeation chromatography (GPC). The Mw of the fluorine compound having a double bond used in the present invention is preferably 400 or more and less than 50,000, more preferably 400 or more and less than 30,000, and even more preferably 400 or more and less than 25,000.

[0064] (Amount of fluorine compound having a double bond added) The amount of the fluorine compound having a double bond added is preferably 0.1 to 10 mass %, more preferably 0.3 to 8 mass %, and particularly preferably 0.5 to 5 mass %, relative to 100 parts by weight of the silsesquioxane compound.

[0065] [Hard Coat Composition] The hard coat composition of the present invention is a hard coat composition containing a silsesquioxane compound, which is a condensate of a silane compound containing a silane compound represented by general formula (1) and a silane compound represented by general formula (2), and a fluorine compound having a double bond. The hard coat composition of the present invention may further contain other components such as a photocationic polymerization initiator, a photoradical polymerization initiator, a surface conditioner, or a surface modifier. From the viewpoint of forming a hard coat cured film having excellent mechanical strength, the content of the silsesquioxane compound in the hard coat composition is preferably 40 parts by weight or more, more preferably 50 parts by weight or more, and even more preferably 60 parts by weight or more, per 100 parts by weight of the total solid content.

[0066] [Cationic polymerization initiator] The hard coat composition preferably contains a thermal cationic polymerization initiator or a photo-cationic polymerization initiator as a curing catalyst. The thermal cationic polymerization initiator is a compound that generates an acid upon heating (thermal acid generator), and the photo-cationic polymerization initiator is a compound that generates an acid upon irradiation with active energy rays (photo-acid generator). The acid generated by heat and the photo-acid generator promotes a ring-opening reaction and a polymerization reaction of the epoxy groups contained in the silsesquioxane compound, forming intermolecular crosslinks and curing the hard coat material.

[0067] Examples of the photocationic polymerization initiator include onium salts that combine anions (strong acids) such as antimony hexafluoride, boron tetrafluoride, phosphorus hexafluoride, fluoroalkyl phosphorus fluoride, and fluoroalkyl gallium fluoride with cations such as sulfonium, ammonium, phosphonium, iodonium, and selenium; iron-arene complexes; silanol-metal chelate complexes; sulfonic acid derivatives such as disulfones, disulfonyldiazomethanes, disulfonylmethanes, sulfonylbenzoylmethanes, imide sulfonates, and benzoin sulfonates; and organic halogen compounds.

[0068] Among the above-mentioned cationic photopolymerization initiators, aromatic sulfonium or aromatic iodonium is preferred as the cation because it has high stability in the hard coat composition containing the silsesquioxane compound having an epoxy group. Among the above-mentioned cationic photopolymerization initiators, fluoroantimonate-based anion, fluoroborate-based anion, fluorophosphate-based anion, fluorogallium-based anion, etc. are preferred as the anion because they have strong acid strength and therefore tend to easily obtain a hard coat that is excellent in surface hardness and adhesion to the resin substrate.

[0069] Among these, fluorophosphate-based anions, fluoroborate-based anions, fluorogallium-based anions, and the like are more preferred as counter anions that have a low environmental impact and are highly safe for the environment and the human body.

[0070] Specific examples of such photocationic polymerization initiators include CPI-100P, CPI-101A, CPI-200K, CPI-210S, CPI-310B, CPI-310FG, CPI-410S, IK-1, and IK-1FG manufactured by San-Apro Co., Ltd.; WPI-113, WPI-116, WPI-170, and WPI-124 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; and Bluesil PI2074 and Silicolyse UVCATA243 manufactured by Arakawa Chemical Industries, Ltd., but are not limited to products of these manufacturers.

[0071] The content of the photocationic polymerization initiator in the hard coat composition is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and even more preferably 0.2 to 2 parts by weight, relative to 100 parts by weight of the silsesquioxane compound.

[0072] <Photoradical polymerization initiator> The hard coat composition preferably contains a photoradical polymerization initiator as a curing catalyst. The photoradical polymerization initiator is a compound that generates radical species upon irradiation with active energy rays. The radical species generated from the photoradical polymerization initiator cause a reaction between the (meth)acryloyl group of the silsesquioxane compound and the fluorine compound having a double bond, and the fluorine compound having a double bond is fixed to the hard coat surface.

[0073] The photoradical initiator may be any one that can generate radicals as active species when irradiated with active energy rays, and known photoradical initiators may be used without any particular limitation.Specific examples include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer ... acetophenones such as -hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]phenyl}-2-methylpropan-1-one; oxime esters such as 1-[4-(phenylthio)-,2-(O-benzoyloxime)], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl], 1-(O-acetyloxime); benzoins such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, Benzophenones such as methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenyloxy)ethyl]benzenemethananium bromide, and (4-benzoylbenzyl)trimethylammonium chloride; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethyl Examples of the thioxanthones include thioxanthones such as rudioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H-thioxanthone-9-one mesochloride; and acylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide.

[0074] The content of the photoradical polymerization initiator in the hard coat composition is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and even more preferably 0.2 to 3 parts by weight, relative to 100 parts by weight of the silsesquioxane compound.

[0075] <Reactive additives> The hard coat composition may further contain, as a reactive additive, a cationically polymerizable compound other than the above-mentioned silsesquioxane compound or a radically polymerizable compound. As the reactive additive for photocationic polymerization, a compound having a cationically polymerizable functional group such as an epoxy group, a vinyl ether group, an oxetane group, or an alkoxysilyl group is used. Among these, a reactive additive having an epoxy group is preferred due to its high reactivity with the epoxy group of the silsesquioxane compound. Furthermore, as the reactive additive for photoradical polymerization, a compound having a radically polymerizable functional group such as a (meth)acryloyl group, a vinyl group, an allyl group, or a cinnamoyl group is used. Among these, a reactive additive having a (meth)acryloyl group is preferred due to its high reactivity with the (meth)acryloyl group of the silsesquioxane compound.

[0076] Examples of reactive additives having a glycidyl group include hydrogenated compounds of bisphenol A type epoxy compounds such as 2,2-bis[4-(2,3-epoxypropoxy)cyclohexyl]propane and 2,2-bis[3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]propane (hydrogenated bisphenol A type epoxy compounds); 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]methane and the like (hydrogenated bisphenol F epoxy compounds); hydrogenated biphenol epoxy compounds; hydrogenated phenol novolac epoxy compounds; hydrogenated cresol novolac epoxy compounds; hydrogenated cresol novolac epoxy compounds of bisphenol A; hydrogenated naphthalene epoxy compounds; hydrogenated epoxy compounds of epoxy compounds obtained from trisphenolmethane; and hydrogenated epoxy compounds of the aromatic epoxy compounds listed below.

[0077] Examples of reactive additives for aromatic epoxy systems include epibis-type glycidyl ether epoxy resins obtained by the condensation reaction of bisphenols [e.g., bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, etc.] with epihalohydrin; high molecular weight epibis-type glycidyl ether epoxy resins obtained by further addition reaction of these epibis-type glycidyl ether epoxy resins with the above-mentioned bisphenols; phenols [e.g., phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol A]; Examples include novolak alkyl type glycidyl ether epoxy resins obtained by condensing polyhydric alcohols obtained by the condensation reaction of an aldehyde (e.g., formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, salicylaldehyde, etc.) with an epihalohydrin; and epoxy compounds in which two phenolic skeletons are bonded to the 9-position of the fluorene ring, and a glycidyl group is bonded to each of the oxygen atoms obtained by removing the hydrogen atom from the hydroxyl group of each of the phenolic skeletons, either directly or via an alkyleneoxy group.

[0078] Examples of aliphatic epoxy reactive additives include Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-211, Denacol EX-212, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-411, Denacol EX-421, Denacol EX-512, Denacol EX-521, and Denacol E X-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX-851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841, Denacol EX-861, Denacol EX-911, Denacol EX-941 , Denacol EX-920, Denacol EX-931 (manufactured by Nagase ChemteX Corporation); Epolite M-1230, Epolite 40E, Epolite 100E, Epolite 200E, Epolite 400E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF (manufactured by Kyoeisha Chemical Co., Ltd.), Adeka Glysilol ED-503, Adeka Glysilol ED-503G, Adeka Glysilol ED-506, Adeka Glysilol ED-523T (manufactured by ADEKA Corporation), and acrylic rubbers having only epoxy groups as functional groups include Teisan Resin SG-P3, Teisan Resin SG-80H, Teisan Resin SG-28GL (manufactured by Nagase ChemteX Corporation, epoxy group-containing acrylic rubber).

[0079] Examples of reactive additives for alicyclic epoxy systems include 3,4,3',4'-diepoxybicyclohexane, 2,2-bis(3,4-epoxycyclohexyl)propane, 1,2-bis(3,4-epoxycyclohexyl)ethane, 2,3-bis(3,4-epoxycyclohexyl)oxirane, bis(3,4-epoxycyclohexylmethyl)ether, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate (Daicel's "Celloxide 2021P"), ε-caprolactone-modified 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (Daicel's "Celloxide 2081"), ε-caprolactone dimer-modified 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (Daicel's "Celloxide 2083"), and JIANGSU TETRA NEW MATERIAL Examples of epoxy-modified cyclohexylmethyl acrylate include tetramethyl acrylate (manufactured by Daicel Chemical Industry under the trade name "TTA2083"), CELLOXIDE 2085 manufactured by DAICEL, bis(3,4-epoxycyclohexylmethyl)adipate (manufactured by JIANGSU TETRA NEW MATERIAL TECHNOLOGY under the trade name "TTA26"), 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol [for example, trade name "EHPE3150" manufactured by Daicel Corporation], (3,4-epoxycyclohexyl)methyl acrylate, (3,4-epoxycyclohexyl)methyl methacrylate, an epoxy-modified linear siloxane compound (manufactured by Shin-Etsu Chemical Industry under the trade name "X-40-2669"), and an epoxy-modified cyclic siloxane compound (manufactured by Shin-Etsu Chemical Industry under the trade name "KR-470").

[0080] Examples of reactive additives having a (meth)acryloyl group include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, Isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxyoligoethyleneglycol (meth)acrylate, methoxypolyethyleneglycol (meth)acrylate, ethoxyoligoethyleneglycol (meth)acrylate, ethoxypolyethyleneglycol (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate monofunctional (meth)acrylates such as 1,4-(bis(meth)acryloyloxy)butane, 1,6 ...

[0033] Examples of the difunctional (meth)acrylate include difunctional (meth)acrylates such as 1-(acryloyloxy)-3-(methacryloyloxy)-2-propanol, 1,10-(bis(meth)acryloyloxy)hexane, 1,10-(bis(meth)acryloyloxy)decane, glycerol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol (meth)acrylate, neopentyl glycol (meth)acrylate, 1-(acryloyloxy)-3-(methacryloyloxy)-2-propanol, and 1,3-butanediol di(meth)acrylate.

[0081] The content of the cationically polymerizable or radically polymerizable reactive additive in the hard coat composition is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, and even more preferably 10 parts by weight or less, per 100 parts by weight of the silsesquioxane compound, and may be 0. Addition of more than 50 parts by weight is undesirable because it reduces the crosslink density of the hard coat layer and decreases the surface hardness and scratch resistance.

[0082] <Photosensitizer> In the hard coat composition of the present invention, a photosensitizer may be used for the purpose of improving the photosensitivity of the photopolymerization initiator. As the photosensitizer, either a type that improves the photosensitivity of the photopolymerization initiator by absorbing light in a wavelength range that cannot be absorbed by the photopolymerization initiator used, or a type that improves the photosensitivity of the photopolymerization initiator while having a wavelength range that is not significantly different from that of the photopolymerization initiator may be used. When using a type that absorbs light in a wavelength range that cannot be absorbed by the photopolymerization initiator used, it is preferable that the photosensitizer has a strong absorption in a wavelength range different from the absorption wavelength range of the photopolymerization initiator.

[0083] The photosensitizer is not particularly limited, but examples thereof include anthracene derivatives, benzophenone derivatives, thioxanthone derivatives, anthraquinone derivatives, benzoyl derivatives, and naphthalene derivatives. Specifically, anthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dimethylanthracene, 9,10-dibutoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diethoxyanthracene, 1,4-dimethoxyanthracene, 9-methylanthracene, 2-ethylanthracene, 2-tert-butylanthracene, 2,6-di-tert-butylanthracene, 9,10-diphenyl-2,6-di-tert-butylanthracene, 9,10-bis(isopropoxycarbonylmethoxy)anthracene, 9,10-dioctanoyloxyanthracene, 1,4-diethoxynaphthalene, 1,4-dimethoxynaphthalene, 1,4-dipropoxynaphthalene, 1,4-dibutoxynaphthalene, benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone , 4-benzoyl-4'-methyldiphenyl sulfide, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, thioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 3-acetylcoumarin, 3-acetyl-7-diethylaminocoumarin, 3-benzoylcoumarin, 3-benzoyl-7-diethylaminocoumarin, 3-benzoyl-7-methoxycoumarin, 3,3'-carbonylbiscoumarin, 3,3'-carbonylbis(7-methoxycoumarin), 3,3'-carbonylbis(5,7-dimethoxycoumarin), and the like.

[0084] The content of the photosensitizer in the hard coat composition of the present invention is preferably 500 parts by weight or less, more preferably 100 parts by weight or less, and even more preferably 50 parts by weight or less, per 100 parts by weight of the photopolymerization initiator.

[0085] <particle> The hard coat composition of the present invention may contain particles for the purpose of adjusting film properties (surface hardness and flex resistance) and suppressing cure shrinkage. The particles may be appropriately selected from organic particles, inorganic particles, organic-inorganic composite particles, etc. Examples of organic particle materials include poly(meth)acrylic acid alkyl esters, crosslinked poly(meth)acrylic acid alkyl esters, crosslinked styrene, nylon, silicone, crosslinked silicone, crosslinked urethane, and crosslinked butadiene. Examples of inorganic particle materials include metal oxides such as silica, titania, alumina, tin oxide, zirconia, zinc oxide, and antimony oxide; metal nitrides such as silicon nitride and boron nitride; and metal salts such as calcium carbonate, calcium hydrogen phosphate, calcium phosphate, and aluminum phosphate. Examples of organic-inorganic composite fillers include organic particles having an inorganic layer formed on the surface thereof, and inorganic particles having an organic layer or organic fine particles formed on the surface thereof.

[0086] Examples of the particle shape include spherical, powdery, fibrous, needle-like, scale-like, etc. Spherical particles are not anisotropic and are less likely to cause uneven distribution of stress, which can suppress the occurrence of distortion and contribute to suppressing warping of the film due to curing shrinkage, etc.

[0087] The average particle size of the particles is, for example, about 5 nm to 10 μm. From the viewpoint of increasing the transparency of the hard coat layer, the average particle size is preferably 1000 nm or less, more preferably 500 nm or less, even more preferably 300 nm or less, and particularly preferably 100 nm or less. The particle size can be measured using a laser diffraction / scattering particle size distribution measuring device, and the volume-based median size is taken as the average particle size.

[0088] The hard coat composition may contain surface-modified particles. Surface modification of the particles tends to improve the dispersibility of the particles in the siloxane compound. In addition, when the particle surface is modified with a polymerizable functional group that can react with an epoxy group or a (meth)acryloyl group, the functional group on the particle surface reacts with the epoxy group or the (meth)acryloyl group of the silsesquioxane compound of the present invention to form a chemical crosslink, which can be expected to improve film strength and flex resistance.

[0089] Examples of polymerizable functional groups that can react with epoxy groups include vinyl groups, (meth)acrylic groups, hydroxyl groups, phenolic hydroxyl groups, carboxyl groups, acid anhydride groups, amino groups, epoxy groups, and oxetane groups. Among these, epoxy groups are preferred. In particular, particles surface-modified with epoxy groups are preferred because they can form chemical crosslinks between the particles and the siloxane compound when the hard coat composition is cured by photocationic polymerization.

[0090] Examples of polymerizable functional groups that can react with a (meth)acryloyl group include a vinyl group, an allyl group, a (meth)acryloyl group, etc. Among these, particles surface-modified with a (meth)acryloyl group are preferred because they can form chemical crosslinks between the particles and the siloxane compound when the hard coat composition is cured by photoradical polymerization.

[0091] Examples of particles having reactive functional groups on their surfaces include surface-modified inorganic particles and core-shell polymer particles. These particles may be used alone or in combination.

[0092] <Solvent> The hard coat composition of the present invention may or may not contain a solvent. When a solvent is contained, it is preferable that the solvent does not dissolve the resin substrate. The content of the solvent is preferably 500 parts by weight or less, more preferably 300 parts by weight or less, and even more preferably 100 parts by weight or less, relative to 100 parts by weight of the silsesquioxane compound of the present invention.

[0093] <Additives> The hard coat composition of the present invention may contain additives such as inorganic pigments, organic pigments, surface conditioners, surface modifiers, plasticizers, dispersants, wetting agents, thickeners, antifoaming agents, etc. The hard coat composition may also contain a thermoplastic or thermosetting resin material other than the above-mentioned silsesquioxane compound.

[0094] <Hard Coat Film: First Hard Coat Layer> A hard coat composition is applied to a transparent resin substrate, and the solvent is removed by drying if necessary. The hard coat composition is then cured by irradiating it with active energy rays, thereby obtaining a hard coat film in which a first hard coat layer is formed on the transparent resin substrate. The first hard coat layer may be formed on only one side of the transparent resin substrate, or on both sides of the transparent resin substrate.

[0095] Before applying the hard coat layer, the surface of the resin substrate may be subjected to a surface treatment such as a corona treatment or a plasma treatment. By performing the corona treatment or the plasma treatment, the adhesion between the resin substrate and the hard coat layer is improved, and the effect of improving the flex resistance is obtained. In addition, an easy-adhesion layer (primer layer) or the like may be provided on the surface of the resin substrate. Note that the hard coat layer formed by curing the hard coat composition of the present invention exhibits high adhesion to the resin substrate, so an easy-adhesion layer or the like may not be provided. That is, in the hard coat film of the present invention, the resin substrate and the hard coat layer may be in contact with each other.

[0096] By irradiating the hard coat composition with active energy rays or by heating, an acid is generated from the photocationic polymerization initiator, and the epoxy group of the silsesquioxane compound undergoes ring-opening and cationic polymerization, thereby proceeding with curing.When the hard coat composition contains a reactive additive, in addition to the polymerization reaction between the siloxane compounds, a polymerization reaction between the epoxy group of the siloxane compound and the reactive additive also occurs.In addition, when the hard coat composition contains particles having reactive functional groups on their surfaces, the functional groups on the particle surfaces react with the epoxy group of the siloxane compound to form chemical crosslinks.

[0097] Examples of active energy rays irradiated during photocuring include visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, γ-rays, and electron beams. Ultraviolet light is preferred as the active energy ray because it has a high curing reaction rate and excellent energy efficiency. The cumulative irradiation dose of the active energy ray is, for example, 50 to 10,000 mJ / cm. 2 The curing temperature is about 150° C., and may be set depending on the type and amount of the photocationic polymerization initiator, the thickness of the hard coat layer, etc. The curing temperature is not particularly limited, but is usually 150° C. or lower.

[0098] In order to promote the photocuring reaction and obtain a hard coat film having high film strength, the curing of the hard coat composition may be carried out in an oxygen-free nitrogen atmosphere. The oxygen concentration in the curing atmosphere in the photoradical polymerization reaction is preferably 1000 ppm or less, more preferably 500 ppm or less, and even more preferably 100 ppm or less.

[0099] The thickness of the hard coat layer is preferably 0.5 μm or more, more preferably 2 μm or more, even more preferably 3 μm or more, particularly preferably 5 μm or more, and may be 10 μm or more, 20 μm or more, or 30 μm or more. The thicker the hard coat layer, the higher the surface hardness tends to be. On the other hand, from the viewpoints of transparency and flex resistance, the thickness of the hard coat layer is preferably 100 μm or less, more preferably 80 μm or less, and may be 70 μm or less.

[0100] <Transparent resin substrate (transparent film)> The transparent resin substrate is a film substrate that serves as a base for forming a hard coat layer. The total light transmittance of the transparent resin substrate is preferably 80% or more, more preferably 85% or more, and even more preferably 90% or more. The haze of the transparent resin substrate is preferably 2% or less, more preferably 1% or less.

[0101] The thickness of the transparent resin substrate is not particularly limited and is, for example, 1 to 1000 μm, preferably 5 to 500 μm, more preferably 10 to 200 μm, and even more preferably 15 to 150 μm.

[0102] The resin material constituting the transparent resin substrate is not particularly limited as long as it is a transparent resin, and examples of the transparent resin include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polycarbonate, polyamide, transparent polyimide, cyclic polyolefin, acrylic resins such as polymethyl methacrylate (PMMA), and cellulose-based resins such as triacetyl cellulose (TAC).

[0103] Among these, polyesters such as PET and transparent polyimides are preferred due to their high mechanical strength. When the hard coat film is used as a cover window for a display, the film substrate is required to have excellent heat resistance and mechanical strength, so transparent polyimides are particularly preferred as the resin material for the transparent resin substrate. While general wholly aromatic polyimides are colored yellow or brown, transparent polyimides with high visible light transmittance can be obtained by introducing an alicyclic structure, a bent structure, or a fluorine substituent.

[0104] The transparent resin substrate may be a single layer or a multilayer structure. For example, the transparent resin substrate may be a laminate in which a plurality of films are bonded together, and a functional layer such as an easy-adhesion layer, an antistatic layer, or an antireflection layer may be provided on the hard coat layer-forming surface and / or the non-hard coat layer-forming surface of the film substrate. Furthermore, the transparent resin substrate may have a hard coat layer formed of a material other than the silsesquioxane compound on one main surface.

[0105] The thickness of the resin substrate is not particularly limited and can be appropriately selected, for example, within the range of 1 to 1000 μm, preferably 5 to 500 μm, more preferably 10 to 200 μm, and even more preferably 15 to 150 μm.

[0106] <Second hard coat layer> A second hard coat layer can be provided between the first hard coat layer and the transparent resin substrate. The provision of the second hard coat layer can reduce warpage of the hard coat film.

[0107] The second hard coat layer is a cured product of a hard coat composition containing a silsesquioxane compound, which is a condensate of a silane compound including a silane compound represented by general formula (1).

[0108] When the silsesquioxane compound is obtained by condensation of a silane compound, other silane compounds may be used in addition to the silane compound (1). The other silane compounds are represented by the following general formula (5). [ka]

[0109] The weight-average molecular weight of the silsesquioxane compound is preferably 500 or more from the viewpoint of increasing the hardness of the cured product and suppressing the volatilization of the silsesquioxane compound. On the other hand, if the molecular weight is too large, cloudiness may occur due to reduced compatibility with other compositions. Therefore, the weight-average molecular weight of the silsesquioxane compound is preferably 20,000 or less.

[0110] The proportion of the silane compound represented by general formula (1) contained in the second hard coat layer is preferably greater than the proportion of the silane compound represented by general formula (1) contained in the first hard coat layer. Since the silane compound represented by general formula (1) expands upon curing, a high content of the silane compound can suppress warping of the hard coat film upon curing. The ratio of the silane compound represented by general formula (1) to the total number of Si atoms in the silsesquioxane compound contained in the second hard coat layer is preferably 0.5 or more, more preferably 0.6 or more, and even more preferably 0.8 or more, from the viewpoint of suppressing warpage, and may be 1.

[0111] The silsesquioxane compound is formed by hydrolysis and condensation of a silane compound represented by general formula (1), and contains a structural unit represented by general formula (3) or (4). The ratio [T3 isomer] / [T2 isomer] of the structural unit represented by formula (3) (a structure in which all three alkoxysilanes in a silane compound having a T unit structure where x = 3 in general formulas (1) and (2) undergo a condensation reaction to form an Si-O-Si structure; hereinafter referred to as [T3 isomer]) to the structural unit represented by formula (4) (a structure in which two of the three alkoxysilanes in a silane compound having a T unit structure where x = 3 in general formulas (1) and (2) undergo a condensation reaction to form an Si-O-Si structure; hereinafter referred to as [T2 isomer]) is preferably 0.8 or more and less than 5, more preferably 1 or more and less than 4, and even more preferably 1.5 or more and less than 3. A hard coat film having a hard coat layer made of a cured product of the silsesquioxane compound of the present invention exhibits excellent flex resistance by adjusting the ratio of the T3 isomer to the T2 isomer, [T3 isomer] / [T2 isomer], to less than 5. If the content of the T3 isomer in the condensate increases and the ratio [T3 isomer] / [T2 isomer] is 5 or more, the resulting condensate will have a dense structure and will have reduced flexibility, resulting in reduced flex resistance when formed into a hard coat film.

[0112] The hydrolysis and condensation reactions of the silsesquioxane compound are carried out in the presence of a neutral salt catalyst. By carrying out the hydrolysis and condensation reactions in the presence of a neutral salt catalyst, the silsesquioxane compound can be obtained without deactivating the epoxy groups before, after, or during storage of the silsesquioxane compound. The amount of neutral salt used is preferably 0.000001 to 0.1 mol, and particularly preferably 0.000005 to 0.01 mol, per mol of hydrolyzable silyl group in the silane compound. The amount of neutral salt remaining in the silsesquioxane compound is preferably 1 ppm to 10,000 ppm, more preferably 50 ppm to 5,000 ppm, and even more preferably 100 ppm to 1,000 ppm.

[0113] [Cationic polymerization initiator] The hard coat composition preferably contains a thermal cationic polymerization initiator or a photo-cationic polymerization initiator as a curing catalyst. The thermal cationic polymerization initiator is a compound that generates an acid upon heating (thermal acid generator), and the photo-cationic polymerization initiator is a compound that generates an acid upon irradiation with active energy rays (photo-acid generator). The acid generated by heat and the photo-acid generator promotes a ring-opening reaction and a polymerization reaction of the epoxy groups contained in the silsesquioxane compound, forming intermolecular crosslinks and curing the hard coat material.

[0114] <Hard Coat Film Having Second Hard Coat Layer and First Hard Coat Layer> A hard coat composition containing a silsesquioxane compound, which is a condensate of silane compounds including a silane compound represented by general formula (1), is applied onto a transparent resin substrate; if necessary, the solvent is dried and removed, and then the hard coat composition is cured by irradiating with active energy rays. Thereafter, a hard coat composition containing a silsesquioxane compound, which is a condensate of silane compounds including a silane compound represented by general formula (1) and a silane compound represented by general formula (2), and a hard coat composition containing a fluorine compound having a double bond, is applied; if necessary, the solvent is dried and removed, and then the hard coat composition is cured by irradiating with active energy rays, thereby obtaining a hard coat film having a second hard coat layer and a first hard coat layer.

[0115] Before applying the second hard coat layer, the surface of the resin substrate may be subjected to a surface treatment such as a corona treatment or a plasma treatment. Furthermore, before applying the first hard coat layer, the surface of the second hard coat layer may be subjected to a surface treatment such as a corona treatment or a plasma treatment. By performing the corona treatment or the plasma treatment, the adhesion between the resin substrate and the hard coat layer or between the hard coat layers is improved, and the effect of improving the flex resistance is obtained.

[0116] By irradiating the hard coat composition with active energy rays or by heating, an acid is generated from the cationic polymerization initiator, and the epoxy group of the silsesquioxane compound undergoes ring-opening and cationic polymerization, thereby proceeding with curing.When the hard coat composition contains a reactive additive, in addition to the polymerization reaction between siloxane compounds, the polymerization reaction between the epoxy group of the siloxane compound and the reactive additive also occurs.In addition, when the hard coat composition contains particles having reactive functional groups on their surfaces, the functional groups on the particle surface react with the epoxy group of the siloxane compound to form chemical crosslinks.

[0117] Examples of active energy rays irradiated during photocuring include visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, γ-rays, and electron beams. Ultraviolet light is preferred as the active energy ray because it has a high curing reaction rate and excellent energy efficiency. The cumulative irradiation dose of the active energy ray is, for example, 50 to 10,000 mJ / cm. 2 The curing temperature is about 150° C., and may be set depending on the type and amount of the photocationic polymerization initiator, the thickness of the hard coat layer, etc. The curing temperature is not particularly limited, but is usually 150° C. or lower.

[0118] The thickness of the second hard coat layer, like the first hard coat layer, is preferably 0.5 μm or more, more preferably 2 μm or more, even more preferably 3 μm or more, particularly preferably 5 μm or more, and may be 10 μm or more, 20 μm or more, or 30 μm or more. The thicker the hard coat layer, the higher the surface hardness tends to be. On the other hand, from the viewpoints of transparency and flex resistance, the thickness of the hard coat layer is preferably 100 μm or less, more preferably 80 μm or less, and may be 70 μm or less.

[0119] The total thickness of the hard coat film of the present invention can be appropriately selected from the range of 1 to 1000 μm, and is preferably 10 to 500 μm, more preferably 15 to 300 μm, and even more preferably 20 to 250 μm.

[0120] In the hard coat film of the present invention, the ratio of the thickness of the hard coat layer to the thickness of the resin substrate (thickness of hard coat layer / thickness of resin substrate) is not particularly limited and may be appropriately selected, for example, from the range of 1 / 100 to 10 / 1.

[0121] [Hard coat film characteristics] The hard coat layer formed by curing the hard coat composition of the present invention has excellent adhesion to a resin substrate. Furthermore, since the hard coat composition has a polymer matrix in which a silsesquioxane compound is crosslinked by ring-opening and polymerization of an epoxy group, it can achieve a surface hardness comparable to that of glass. The pencil hardness of the surface of the hard coat film of the present invention on which the hard coat layer of the present invention is formed is preferably HB or higher, more preferably H or higher, even more preferably 2H or higher, and particularly preferably 3H or higher.

[0122] The hard-coated film of the present invention has high surface hardness and excellent flex resistance as described above. When the hard-coated film of the present invention is subjected to a cylindrical mandrel test with the surface having the hard-coat layer of the present invention facing outward and the hard-coat layer having a thickness of 10 μm, the mandrel diameter at which cracks occur is preferably 8 mm or less, more preferably 6 mm or less, and even more preferably 4 mm or less.

[0123] The hard coat film of the present invention preferably has a water contact angle of 100° or more, more preferably 105° or more, and even more preferably 110° or more. Furthermore, even after a scratch resistance test such as a steel wool test or an eraser test, the water contact angle preferably remains 80° or more, more preferably 90° or more, and even more preferably 100° or more.

[0124] The total light transmittance of the hard coat film of the present invention is preferably 80% or more, more preferably 85% or more, and even more preferably 88% or more. The haze of the hard coat film of the present invention is preferably 1.5% or less, more preferably 0.9% or less, even more preferably 0.7% or less, and particularly preferably 0.5% or less. The YI of the hard coat film of the present invention is preferably 5 or less, more preferably 4 or less, and particularly preferably 3 or less.

[0125] As described above, during curing, an acid is generated from the cationic photopolymerization initiator (photoacid generator), and photocuring proceeds. Therefore, counter anions of the cationic photopolymerization initiator remain in the hard coat layer after curing. The hard coat layer may contain a fluorophosphate-based anion, a tetrakispentafluorophenylborate-based anion, a fluorogallium-based anion, or a salt thereof as the counter anion of the cationic photopolymerization initiator. When the hard coat composition of the present invention contains particles, the hard coat layer after photocuring also contains particles. When the hard coat composition contains particles having a polymerizable functional group capable of reacting with an epoxy group, it is preferable that the hard coat layer after photocuring has chemical crosslinks formed between the silsesquioxane compound and the particles.

[0126] [Applications of hard coated films] The hard coat film may have various functional layers on the hard coat layer or on the surface of the resin substrate where the hard coat layer is not formed. Examples of functional layers include an antireflection layer, an antiglare layer, an antistatic layer, and a transparent electrode. The hard coat film may also have a transparent pressure-sensitive adhesive layer attached thereto.

[0127] The hard coat film of the present invention has high transparency and excellent mechanical strength, so it can be suitably used for cover windows provided on the surface of image display panels, transparent substrates for displays, transparent substrates for touch panels, substrates for solar cells, and the like. In addition to transparency and mechanical strength, the hard coat film of the present invention is also excellent in bending resistance and folding resistance, and thus can be particularly suitably used as a cover window or a substrate film for a curved display, a flexible display, or the like.

Example

[0128] Hereinafter, the present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited to the following examples. The evaluation method of the condensate obtained in the following synthesis examples is as follows.

[0129] <Measurement of weight average molecular weight Mw> The weight average molecular weight was measured by GPC. GPC apparatus HLC-8220GPC manufactured by Tosoh Corporation (column: TSKgel GMH XL ×2 columns, TSKgel G3000H XL , TSKgel G2000H XL ) was used, THF was used as a solvent, and it was calculated in terms of polystyrene.

[0130] <Calculation of the ratio of T3 body to T2 body [T3 body] / [T2 body]> Using a 600 MHz-NMR manufactured by Agilent Technologies, 29 By performing Si-NMR measurement, the contents of the T3 body and the T2 body and their ratio [T3 body] / [T2 body] were calculated respectively.

[0131] <Evaluation of the residual ratio of epoxy group and acryloyl group> Using a 400 MHz-NMR manufactured by Bruker Corporation, with deuterated acetone as a solvent 1 By performing 1H-NMR measurement, the residual amounts of the epoxy group and the acryloyl group in the condensate obtained after the reaction were calculated.

[0132] [Synthesis of silsesquioxane compound] (Synthesis Example 1) A reaction vessel equipped with a thermometer, stirrer, and reflux condenser was charged with 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-303) (44.4 g; 180 mmol), 3-acryloyloxypropyltrimethoxysilane (Tokyo Chemical Industry Co., Ltd., A1597) (14.1 g; 60 mmol), propylene glycol monomethyl ether (14.7 g), and methanol (5.15 g), in that order, and stirred until homogeneous. A solution of magnesium chloride (34.3 mg; 0.36 mmol) dissolved in water (8.65 g; 480 mmol) was slowly added dropwise to this mixture and stirred until homogeneous. The mixture was then heated to 80°C and allowed to undergo polycondensation for 6 hours with stirring. After completion of the reaction, the mixture was concentrated under reduced pressure using a rotary evaporator to remove the methanol and water from the condensate, yielding silsesquioxane compound 1. Analysis of the obtained silsesquioxane compound revealed that it had a weight average molecular weight Mw of 3,200, 1 The residual rate of methoxy groups calculated by H-NMR measurement is 4.9%, the residual rate of epoxy groups is over 95%, and the residual rate of acryloyl groups is over 99%. 29 The [T3 isomer] / [T2 isomer] ratio calculated by Si-NMR measurement was 2.1. The content of magnesium chloride (neutral salt catalyst) calculated based on the above-mentioned charged weight was 807 ppm.

[0133] (Synthesis Example 2) A reaction vessel equipped with a thermometer, stirrer, and reflux condenser was charged with 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-303) (18.5 g; 75 mmol), 3-acryloyloxypropyltrimethoxysilane (Tokyo Chemical Industry Co., Ltd., A1597) (17.6 g; 75 mmol), propylene glycol monomethyl ether (9.19 g), and methanol (3.22 g) in that order and stirred until homogeneous. A solution of magnesium chloride (21.4 mg; 0.225 mmol) dissolved in water (5.41 g; 300 mmol) was slowly added dropwise to this mixture and stirred until homogeneous. The mixture was then heated to 80°C and stirred for 6 hours to carry out the polycondensation reaction. After completion of the reaction, the mixture was concentrated under reduced pressure using a rotary evaporator to remove the methanol and water from the condensate, yielding silsesquioxane compound 2. Analysis of the resulting silsesquioxane compound revealed that it had a weight average molecular weight Mw of 3,100, 1 The residual rate of methoxy groups calculated by H-NMR measurement is 4.2%, the residual rate of epoxy groups is over 95%, and the residual rate of acryloyl groups is over 99%. 29 The ratio [T3 isomer] / [T2 isomer] calculated by Si-NMR measurement was 2.1. The content of magnesium chloride (neutral salt catalyst) calculated based on the above-mentioned charged weight was 819 ppm.

[0134] (Synthesis Example 3) A reaction vessel equipped with a thermometer, stirrer, and reflux condenser was charged with 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-303) (9.24 g; 37.5 mmol), 3-acryloyloxypropyltrimethoxysilane (Tokyo Chemical Industry Co., Ltd., A1597) (26.4 g; 112.5 mmol), propylene glycol monomethyl ether (9.19 g), and methanol (3.22 g) in that order and stirred until homogeneous. A solution of magnesium chloride (21.4 mg; 0.225 mmol) dissolved in water (5.41 g; 300 mmol) was slowly added dropwise to this mixture and stirred until homogeneous. The mixture was then heated to 80°C and subjected to polycondensation for 6 hours with stirring. After the reaction was completed, the condensate was evaporated under reduced pressure and concentrated using a rotary evaporator to remove methanol and water from the condensate, thereby obtaining silsesquioxane compound 3. Analysis of the resulting silsesquioxane compound revealed that it had a weight average molecular weight Mw of 3,000 and 1 The residual rate of methoxy groups calculated by H-NMR measurement is 3.8%, the residual rate of epoxy groups is over 95%, and the residual rate of acryloyl groups is over 99%. 29 The ratio [T3 isomer] / [T2 isomer] calculated by Si-NMR measurement was 2.1. The content of magnesium chloride (neutral salt catalyst) calculated based on the above-mentioned charged weight was 835 ppm.

[0135] (Synthesis Example 4) A reaction vessel equipped with a thermometer, stirrer, and reflux condenser was charged with 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-303) (1.97 g; 8 mmol), 3-acryloyloxypropyltrimethoxysilane (Tokyo Chemical Industry Co., Ltd., A1597) (16.87 g; 72 mmol), propylene glycol monomethyl ether (4.90 g), and methanol (1.72 g), in that order, and stirred until homogeneous. A solution of magnesium chloride (11.4 mg; 0.12 mmol) dissolved in water (2.88 g; 160 mmol) was slowly added dropwise to this mixture and stirred until homogeneous. The mixture was then heated to 80°C and stirred for 6 hours to carry out the polycondensation reaction. After completion of the reaction, the mixture was concentrated under reduced pressure using a rotary evaporator to remove the methanol and water from the condensate, yielding silsesquioxane compound 4. Analysis of the resulting silsesquioxane compound revealed that it had a weight average molecular weight Mw of 3,000 and 1 The residual rate of methoxy groups calculated by H-NMR measurement is 3.6%, the residual rate of epoxy groups is over 95%, and the residual rate of acryloyl groups is over 99%. 29 The ratio [T3 isomer] / [T2 isomer] calculated by Si-NMR measurement was 2.1. The content of magnesium chloride (neutral salt catalyst) calculated based on the above-mentioned charged weight was 843 ppm.

[0136] (Synthesis Example 5) A reaction vessel equipped with a thermometer, stirrer, and reflux condenser was charged with 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane ("KBM-303" manufactured by Shin-Etsu Chemical Co., Ltd.) (61.6 g; 250 mmol) and 1-methoxy-2-propanol (PGME) (15.3 g) and stirred until homogeneous. A solution of magnesium chloride (35.7 mg; 0.375 mmol) dissolved in water (9.0 g; 499 mmol) was added dropwise to this mixture over 5 minutes and stirred until homogeneous. The mixture was then heated to 80°C and stirred for 6 hours to carry out the polycondensation reaction. After completion of the reaction, the solvent and water were removed using a rotary evaporator to obtain silsesquioxane compound 4. Analysis of the resulting silsesquioxane compound revealed that it had a weight average molecular weight Mw of 3,300 and 1 The residual rate of methoxy groups calculated by H-NMR measurement was 4.6%, and the residual rate of epoxy groups was over 95%. 29 The ratio [T3 isomer] / [T2 isomer] calculated by Si-NMR measurement was 2.3. The content of magnesium chloride (neutral salt catalyst) calculated based on the above-mentioned charged weight was 800 ppm.

[0137] (Synthesis Example 6) A reaction vessel equipped with a thermometer, stirrer, and reflux condenser was charged with 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-303) (44.4 g; 180 mmol), 3-acryloyloxypropyltrimethoxysilane (Tokyo Chemical Industry Co., Ltd., A1597) (14.1 g; 60 mmol), propylene glycol monomethyl ether (14.7 g), and methanol (5.15 g), in that order, and stirred until homogeneous. A solution of potassium carbonate (49.8 mg; 0.36 mmol) dissolved in water (8.65 g; 480 mmol) was slowly added dropwise to this mixture, and the mixture was stirred until homogeneous. The mixture was then heated to 80°C and allowed to undergo polycondensation for 6 hours with stirring. After completion of the reaction, the mixture was concentrated and devolatilized under reduced pressure using a rotary evaporator. The methanol and water in the condensate were removed, yielding silsesquioxane compound 6.

[0138] The method for preparing the hard coat composition and the method for producing the hard coat film are as follows.

[0139] [Preparation of hard coat composition and production of hard coat film] (Example 1: Preparation of hard coat film 1) Silsesquioxane compound 1 obtained in Synthesis Example 1 was diluted to 50% with propylene glycol monomethyl ether. Hard coat composition 1 was obtained by blending 2 parts by weight (solids) of a 50% propylene carbonate solution of a photocationic polymerization initiator (manufactured by San-Apro Co., Ltd.: CPI-101A), 1 part by weight (solids) of a photoradical polymerization initiator (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.: 1-hydroxycyclohexyl phenyl ketone (Irgacure 184)), and 0.5 parts by weight (solids) of a fluorine compound having a double bond (manufactured by DIC Corporation: RS-90) with 100 parts by weight of the silsesquioxane compound.

[0140] The main surface 1 of a 50 μm-thick transparent polyimide substrate was subjected to corona treatment using a corona scanner at a discharge output of 600 W·min / m2. Hard coat composition 1 was applied using a bar coater to a dry film thickness of 15 μm, and the substrate was heated at 120°C for 10 minutes. Subsequently, a high-pressure mercury lamp was used at room temperature in a nitrogen atmosphere to irradiate the substrate with an integrated light intensity of 600 mJ / cm2 at a wavelength of 365 nm. 2 The hard coat composition was cured by irradiating it with ultraviolet light so that the hard coat film 1 was obtained.

[0141] (Examples 2 to 4, Comparative Examples 1 and 2: Preparation of Hard Coat Films 2 to 6) Hard coat films 2 to 6 were obtained in the same manner as in Example 1, except that silsesquioxane compounds 2 to 6 obtained in Synthesis Examples 2 to 6 were used and the blending amounts and thicknesses were changed as shown in Table 1.

[0142] (Example 5: Preparation of hard coat film 7) Silsesquioxane compound 1 obtained in Synthesis Example 1 was diluted to 50% with propylene glycol monomethyl ether. Hard coat composition 1 was obtained by blending 2 parts by weight (solids) of a 50% propylene carbonate solution of a photocationic polymerization initiator (manufactured by San-Apro Co., Ltd.: CPI-101A), 1 part by weight (solids) of a photoradical polymerization initiator (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.: 1-hydroxycyclohexyl phenyl ketone (Irgacure 184)), and 0.5 parts by weight (solids) of a fluorine compound having a double bond (manufactured by DIC Corporation: RS-90) with 100 parts by weight of the silsesquioxane compound. Next, the silsesquioxane compound 5 obtained in Synthesis Example 5 was diluted to 50% with propylene glycol monomethyl ether. Hard coat composition 7 was obtained by blending 0.5 parts by weight (solid content) of a 50% propylene carbonate solution of a photocationic polymerization initiator (manufactured by San-Apro Co., Ltd.: CPI-101A) and 0.25 parts by weight (solid content) of a leveling agent (manufactured by BYK-Chemie KK: BYK-300) with 100 parts by weight of the silsesquioxane compound.

[0143] A corona scanner was used to apply a discharge power of 600 W·min / m to the main surface 1 of a 50 μm thick transparent polyimide substrate. 2 Hard Coat Composition 7 was applied using a bar coater to a dry film thickness of 20 μm, and heated at 120° C. for 10 minutes. Thereafter, a high-pressure mercury lamp was used to apply a 365 nm wavelength integrated light dose of 600 mJ / cm 2 . 2 UV light was irradiated so that The surface of the cured hard coat layer was scanned using a corona scanner with a discharge output of 600 W·min / m 2 After corona treatment so that the hard coat layer was coated with hard coat composition 1 using a bar coater so that the dry film thickness was 15 μm, the hard coat layer was heated at 120° C. for 10 minutes, and then heated at 120° C. for 10 minutes. After that, the hard coat composition was irradiated with a high-pressure mercury lamp at room temperature in a nitrogen atmosphere with an integrated light intensity of 600 mJ / cm at a wavelength of 365 nm. 2 The hard coat composition was cured by irradiating it with ultraviolet light so that the hard coat film 7 was obtained.

[0144] (Examples 6 to 8: Preparation of hard coat films 8 to 10) Hard coat films 8 to 10 were obtained in the same manner as in Example 5, except that hard coat compositions 2 to 4, which were prepared using silsesquioxane compounds 2 to 4 obtained in Synthesis Examples 2 to 4, were used instead of hard coat composition 1, and the blending amounts and thicknesses were changed as shown in Table 2.

[0145] The physical properties of the hard coat films obtained in the examples and comparative examples were evaluated as follows: The evaluation results of each example and comparative example are shown in Tables 1 and 2.

[0146] <Flexibility (cylindrical mandrel (diameter))> In accordance with JIS K5600-5-1:1999, a cylindrical mandrel test was performed using a Type 1 testing machine, with the hard coat layer formed on the resin substrate facing outward. Because the results of the mandrel test depend heavily on the thickness of the hard coat layer, it is preferable to compare samples with similar hard coat layer thicknesses. For the same hard coat layer thickness, a smaller mandrel diameter indicates better flex resistance. Furthermore, for the same mandrel diameter, a thicker hard coat layer indicates better flex resistance.

[0147] <Surface hardness (pencil hardness)> According to JIS K5600-5-4:1999, the pencil hardness of the surface on which the hard coat layer was formed was measured under a load of 750 g to evaluate the surface hardness.

[0148] <(Initial) contact angle> The contact angle was measured by a sessile drop method using water as a droplet, with the hard coat layer formed on the resin substrate as the upper surface.

[0149] <Scratch resistance> A friction test of the surface of the hard coat film was carried out under the following conditions using a reciprocating abrasion tester TYPE 30 manufactured by Shinto Scientific Co., Ltd., to evaluate the scratch resistance. Friction element: Steel wool #0000 made by Japan Steel Wool Co., Ltd. Friction contact area: Φ2.5cm, circular Friction distance (one way): 5cm Friction speed: 10cm / s (1 round trip / s) Load: 500g After the predetermined number of reciprocating rub tests, the surface of the hard coat film was visually observed, and the number of rubs at which scratches occurred was counted and evaluated as follows. 〇: No damage even after 1500 frictions ×: Damage occurs within 1500 frictions

[0150] <Contact angle after steel wool test> The contact angle after the steel wool test was measured by measuring the contact angle after the steel wool test. The smaller the change in contact angle before and after the steel wool test, the higher the scratch resistance and the more excellent the antifouling properties of the hard coat.

[0151] <Contact angle after steel wool test and solvent wiping> After the steel wool test, the test area was rubbed with an acetone-soaked cleaning cloth (Toray Industries, Inc.; Toraysee PW) and the water contact angle was measured. The smaller the change in contact angle before and after wiping off the solvent, the higher the scratch resistance and stain resistance of the hard coat.

[0152] <Total light transmittance and haze> Measurement was performed using a haze meter HZ-V3 manufactured by Suga Test Instruments according to the methods described in JIS K7361-1: 1999 and JIS K7136: 2000. The measurement was performed using a D65 light source, and the total light transmittance was calculated as the ratio of the total transmitted light flux (parallel light component and diffuse light component) to the parallel incident light flux on the hard-coated film.

[0153] <Total light transmittance and haze after steel wool test> After the steel wool test, the total light transmittance and haze were measured using the method described above. The change in haze before and after the steel wool test was also calculated. The smaller the change in haze before and after the steel wool test, the higher the scratch resistance and the better the stain resistance of the hard coat. [Table 1] [Table 2]

[0154] Examples 1 to 4 listed in Table 1 achieved both high surface hardness and bending resistance when the hard coat was bent outward, and also showed good values for scratch resistance.

[0155] In Comparative Example 1, which contained only a silane compound having an alicyclic epoxy group, and Comparative Example 2, which used potassium carbonate as a condensation catalyst for the silane compound, both the hard coats had poor flex resistance when bent outward.

[0156] All of Examples 5 to 8 listed in Table 2 achieved both high surface hardness and scratch resistance.

Claims

1. a silsesquioxane compound which is a condensate of a silane compound containing a silane compound represented by general formula (1) and a silane compound represented by general formula (2); A hard coat composition containing a fluorine compound having a double bond, the weight average molecular weight of the silsesquioxane compound is 500 to 20,000; The silsesquioxane compound includes a T3 structure represented by general formula (3) and a T2 structure represented by general formula (4), the ratio T3 / T2 of the content of the T3 structure to the content of the T2 structure is less than 5; a residual rate of epoxy structures in the silsesquioxane compound is 60% or more; The fluorine compound having a double bond is a fluorine-based compound represented by the following general formula (6): The composition contains 60 parts by weight or more of a silsesquioxane compound relative to 100 parts by weight of the total solid content of the composition, and 0.1 to 10% by weight of a fluorine compound having a double bond relative to 100 parts by weight of the silsesquioxane compound. Hardcoat composition. (In general formula (1), X is a monovalent organic group containing an alicyclic epoxy group, In general formula (2), Y is a monovalent organic group containing a (meth)acryloyl group, In the general formula (1) and the general formula (2), R １ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ２ is a hydrogen atom or a monovalent organic group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms; x is 2 or 3; In the general formula (3) and the general formula (4), Q is an arbitrary monovalent organic group, In general formula (4), Z is a hydrogen atom or a monovalent organic group selected from the group consisting of an alkoxy group having an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms; In the general formula (6), R f represents a (per)fluoroalkyl group or a (per)fluoropolyether group, R 3 represents a single bond or a linking group, R 4 represents a polymerizable unsaturated group, n represents an integer of 1 to 3, and m represents an integer of 1 to 3. 【Chemical 1】 【Chemistry 2】 【Chemistry 3】 【Chemistry 4】 【Chemistry 5】

2. A hard coat film comprising a transparent resin substrate and a first hard coat layer formed on at least one surface thereof, the first hard coat layer comprising a cured product containing the hard coat composition according to claim 1.

3. 3. The hard coat film according to claim 2, wherein the first hard coat layer has a thickness of 0.5 to 100 μm.

4. a second hard coat layer is further provided between the transparent resin substrate and the first hard coat layer; the second hard coat layer is a cured product of a hard coat composition containing a silsesquioxane compound, which is a condensate of a silane compound including a silane compound represented by general formula (1), the weight average molecular weight of the silsesquioxane compound is 500 to 20,000; The silsesquioxane compound includes a T3 structure represented by general formula (3) and a T2 structure represented by general formula (4), the ratio T3 / T2 of the content of the T3 structure to the content of the T2 structure is less than 5; 3. The hard coat film according to claim 2, wherein the first hard coat layer has a thickness of 0.5 to 100 μm, and the second hard coat layer has a thickness of 0.5 to 100 μm. 【Chemistry 6】 【Chemistry 7】 【Chemistry 8】

5. The hard coat film according to any one of claims 2 to 4, wherein the transparent resin substrate comprises one or more resin materials selected from the group consisting of polyester, polycarbonate, polyamide, polyimide, cyclic polyolefin, acrylic resin, and cellulose-based resin.

6. A method for producing a hard coat film, comprising applying the hard coat composition according to claim 1 onto a transparent resin substrate, and irradiating the substrate with active energy rays to cure the hard coat composition.

7. a composition containing a silane compound condensate containing a silane compound represented by general formula (1), a photocationic polymerization initiator, and 1 ppm to 10,000 ppm of a neutral salt is applied onto a transparent resin substrate, and the composition is irradiated with active energy rays to cure the hard coat composition; A method for producing a hard coat film, comprising: applying the hard coat composition according to claim 1 onto the hard coat film; and irradiating the hard coat composition with active energy rays to cure the hard coat composition. (In general formula (1), X is a monovalent organic group containing an alicyclic epoxy group, and R １ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ２ is a hydrogen atom or a monovalent organic group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 25 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms, and x is 2 or 3. 【Chemistry 9】

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