HARD COAT FILM, ARTICLE HAVING HARD COAT FILM, AND IMAGE DISPLAY DEVICE

Abstract

To provide a hard coat film which has extremely excellent repeated bending resistance, high hardness and excellent scratch resistance, an article provided with the hard coat film, and an image display device.SOLUTION: The hard coat film includes a substrate, a hard coat layer, and a scratch-resistant layer in this order. The scratch-resistant layer contains a cured product of a polyorganosilsesquioxane (c1) having a group containing a radically polymerizable double bond.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a hard coat film, an article provided with a hard coat film, and an image display device. [Background technology]

[0002] In image display devices such as display devices using cathode ray tubes (CRT), plasma displays (PDPs), electroluminescence displays (ELDs), fluorescent displays (VFDs), field emission displays (FEDs), and liquid crystal displays (LCDs), it is preferable to provide an optical film having a hard coat layer (hard coat film) on a substrate in order to prevent scratches on the display surface.

[0003] For example, Patent Document 1 describes a touch panel equipped with a multilayer film having an antifouling layer made of a cured product containing a condensate of an alkoxysilane having a perfluoropolyether structure and a compound having a trialkoxysilyl group and a polymerizable group or a derivative of the above compound. Patent Document 2 describes a transparent laminate in which a primer layer formed by curing a primer composition containing a (meth)acrylate compound is laminated on a transparent resin substrate, an intermediate layer formed by curing an intermediate layer composition containing a hydrolysis condensate of a trialkoxysilane having a (meth)acrylic group is laminated on the primer layer, and a hard coat layer formed by curing a hard coat composition containing a hydrolysis condensate of a trialkoxysilane having a (meth)acrylic group and an alkyl silicate is laminated on the intermediate layer. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2017-228238 A [Patent Document 2] JP 2017-177772 A Summary of the Invention [Problem to be solved by the invention]

[0005] In recent years, there has been an increasing need for flexible displays, for example in smartphones, etc. Accordingly, there is a demand for optical films that are resistant to breakage even when repeatedly folded (excellent resistance to repeated folding), and in particular, there is a strong demand for optical films that can balance hardness and scratch resistance with resistance to repeated folding. As a result of investigations conducted by the present inventors, it was found that the films described in Patent Documents 1 and 2 are insufficient in scratch resistance and pencil hardness, and are unable to achieve a good balance between the above-mentioned required properties. An object of the present invention is to provide a hard coat film that is extremely excellent in resistance to repeated bending, has high hardness and excellent scratch resistance, and an article and an image display device that include the hard coat film. [Means for solving the problem]

[0006] The present inventors have conducted extensive research and found that the above problems can be solved by the following means. [1] A hard coat film having a substrate, a hard coat layer, and a scratch-resistant layer in this order, The scratch-resistant layer has a thickness of 1.0 μm to 10 μm, The scratch-resistant layer contains a cured product of a polyorganosilsesquioxane compound (c1) having a group containing a radically polymerizable double bond. death , The scratch-resistant layer does not include a fine uneven structure having an uneven height of 50 to 1000 nm and an uneven period of 10 to 400 nm. Hard coat film. [ 2 ] The hard coat film according to [1], wherein the hard coat layer contains a cured product of polyorganosilsesquioxane (a1) having an epoxy group. [3] A hard coat film having a substrate, a hard coat layer, and a scratch-resistant layer in this order, The scratch-resistant layer has a thickness of 1.0 μm to 10 μm, The scratch-resistant layer contains a cured product of a polyorganosilsesquioxane compound (c1) having a group containing a radically polymerizable double bond, The hard coat film, wherein the hard coat layer contains a cured product of polyorganosilsesquioxane (a1) having an epoxy group. [4] The hard coat film according to [2] or [3], wherein the epoxy group is an alicyclic epoxy group. [ 5 ] The radically polymerizable double bond-containing group is a (meth)acryloyl group-containing group. [1] ~[4] Any one of the following 2. The hard coat film according to claim 1 . [ 6 ] The radically polymerizable double bond-containing group is an acryloyl group-containing group. [1] ~[5] Any one of the following 2. The hard coat film according to claim 1 . [ 7 ] The condensation rate of the polyorganosilsesquioxane compound (c1) having a group containing a radically polymerizable double bond is 50% or more [1] to [ 6 ] The hard coat film according to any one of the above items. [ 8 ] The scratch-resistant layer contains a cured product of a fluorine-containing compound [1] to [ 7 ] The hard coat film according to any one of the above items. [ 9 ] A mixed layer is provided between the hard coat layer and the scratch-resistant layer, The mixed layer contains a cured product of a compound (b1) having an epoxy group and a cured product of a compound (b2) having two or more (meth)acryloyl groups in one molecule [1] to [ 8 ] The hard coat film according to any one of the above items. [ 10 ] [1]~[ 9 ] An article having the hard coat film according to any one of the above items. [ 11 ] [1]~[ 9 13. An image display device comprising the hard coat film according to any one of claims 1 to 12 as a surface protective film. The present invention relates to the above-mentioned [1] to [ 11 ], other items of which are incorporated herein for reference.

[0007] <1> A hard coat film having a substrate, a hard coat layer, and a scratch-resistant layer in this order, The hard coat film, wherein the scratch-resistant layer contains a cured product of a polyorganosilsesquioxane compound (c1) having a group containing a radically polymerizable double bond. <2> The radically polymerizable double bond-containing group is a group containing a (meth)acryloyl group. <1> 2. The hard coat film according to claim 1 . <3> The radically polymerizable double bond-containing group is a group containing an acryloyl group. <1> or <2> 2. The hard coat film according to claim 1 . <4> The condensation rate of the polyorganosilsesquioxane compound (c1) having a group containing a radically polymerizable double bond is 50% or more. <1> ~ <3> 13. The hard coat film according to claim 12. <5> The scratch-resistant layer contains a cured product of a fluorine-containing compound. <1> ~ <4> 13. The hard coat film according to claim 12. <6> The hard coat layer contains a cured product of polyorganosilsesquioxane (a1) having an epoxy group. <1> ~ <5> 13. The hard coat film according to claim 12. <7> A mixed layer is provided between the hard coat layer and the scratch-resistant layer, and the mixed layer contains a cured product of a compound (b1) having an epoxy group and a cured product of a compound (b2) having two or more (meth)acryloyl groups in one molecule. <1> ~ <6> 13. The hard coat film according to claim 12. <8> <1> ~ <7> 13. An article comprising the hard coat film according to any one of claims 1 to 12. <9> <1> ~ <7> 13. An image display device comprising the hard coat film according to any one of claims 1 to 12 as a surface protective film. Effect of the Invention

[0008] According to the present invention, it is possible to provide a hard coat film that is extremely excellent in resistance to repeated bending, has high hardness and excellent scratch resistance, and an article and an image display device that include the hard coat film. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Hereinafter, the embodiments for carrying out the present invention will be described in detail, but the present invention is not limited thereto. In this specification, when a numerical value represents a physical property value, a characteristic value, etc., the description "(Numerical value 1) to (Numerical value 2)" means "(Numerical value 1) or more and (Numerical value 2) or less." In addition, in this specification, the description "(meth)acrylate" means "at least one of acrylate and methacrylate." The same applies to "(meth)acrylic acid," "(meth)acryloyl," etc.

[0010] [Hard coat film] The hard coat film of the present invention is A hard coat film having a substrate, a hard coat layer, and a scratch-resistant layer in this order, The scratch-resistant layer is a hard coat film containing a cured product of polyorganosilsesquioxane (c1) having a group containing a radically polymerizable double bond.

[0011] In developing a hard coat film with excellent repeated bending resistance, the present inventors first inferred that the repeated bending resistance of the hard coat film can be improved by reducing the compressive stress applied to the scratch-resistant layer in the hard coat film during a bending test using a folding resistance tester, and as a result of further investigation, it was confirmed that the reduction in the elastic modulus of the scratch-resistant layer is effective in reducing the compressive stress. That is, it was inferred that the repeated bending resistance of the hard coat film can be improved by reducing the elastic modulus of the scratch-resistant layer. On the other hand, the scratch resistance of the hard coat film is thought to be correlated with the crosslink density of the polymerizable compound, which is the matrix forming component of the scratch-resistant layer. In order to reduce the elastic modulus of the scratch-resistant layer, it is generally necessary to increase the crosslinking group equivalent in the polymerizable compound (e.g., a multifunctional (meth)acrylate compound), which is the matrix forming component of the scratch-resistant layer, or to reduce the crosslinking group reaction rate, which is thought to reduce the crosslink density and the scratch resistance. Furthermore, there is a concern that the reduction in the elastic modulus of the scratch-resistant layer will cause a reduction in pencil hardness. Therefore, in order to realize a scratch-resistant layer that reduces the elastic modulus of the scratch-resistant layer while not causing a decrease in scratch resistance and pencil hardness, the inventors conducted extensive research and found that it is effective to use a polyorganosilsesquioxane having a group containing a radically polymerizable double bond as a matrix-forming component in the scratch-resistant layer, which led to the present invention.

[0012] The mechanism by which the hard coat film of the present invention has excellent resistance to repeated bending, high hardness, and excellent scratch resistance is not clear, but the present inventors speculate as follows. The cured product of the polyorganosilsesquioxane having a radically polymerizable double bond-containing group has a crosslinked structure formed by siloxane bonds (Si-O-Si) in addition to the crosslinked structure obtained by polymerization of the radically polymerizable double bonds. Since the crosslinked structure formed by siloxane bonds is flexible compared to the crosslinked structure obtained by polymerization of the radically polymerizable double bonds, it is presumed that it is possible to reduce the elastic modulus of the scratch-resistant layer while exhibiting the scratch resistance due to the high crosslinking density brought about by the above two types of crosslinked structures. Furthermore, it is presumed that the crosslinked structure formed by siloxane bonds exhibits a high deformation recovery rate, so that the pencil hardness can be maintained at a good level even if the elastic modulus of the scratch-resistant layer is reduced. Each layer of the hard coat film of the present invention will now be described.

[0013] <Base material> The substrate of the hard coat film of the present invention will be described. The substrate preferably has a transmittance in the visible light region of 70% or more, more preferably 80% or more, and even more preferably 90% or more.The substrate preferably contains a polymer.

[0014] (polymer) As the polymer, a polymer excellent in optical transparency, mechanical strength, thermal stability, and the like is preferable.

[0015] Examples of the polymer include polycarbonate-based polymers, polyester-based polymers such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), styrene-based polymers such as polystyrene and acrylonitrile-styrene copolymers (AS resins), etc. In addition, examples include polyolefins such as polyethylene and polypropylene, polyolefin-based polymers such as norbornene-based resins and ethylene-propylene copolymers, (meth)acrylic polymers such as polymethyl methacrylate, vinyl chloride-based polymers, amide-based polymers such as nylon and aromatic polyamide, imide-based polymers, sulfone-based polymers, polyethersulfone-based polymers, polyetheretherketone-based polymers, polyphenylene sulfide-based polymers, vinylidene chloride-based polymers, vinyl alcohol-based polymers, vinyl butyral-based polymers, arylate-based polymers, polyoxymethylene-based polymers, epoxy-based polymers, cellulose-based polymers such as triacetyl cellulose, copolymers of the above polymers, and polymers in which the above polymers are mixed.

[0016] In particular, amide-based polymers such as aromatic polyamides and imide-based polymers are preferably used as the substrate because they have a large number of bending cycles to break measured by an MIT testing machine according to JIS (Japanese Industrial Standards) P8115 (2001) and a relatively high hardness. For example, aromatic polyamides as described in Example 1 of Japanese Patent No. 5699454 and polyimides described in Japanese Translation of PCT International Publication No. 2015-508345 and Japanese Translation of PCT International Publication No. 2016-521216 can be preferably used as the substrate.

[0017] The base material can also be formed as a cured layer of ultraviolet-curable or thermosetting resin, such as acrylic, urethane, acrylic urethane, epoxy, or silicone.

[0018] (Softening material) The substrate may contain a material that further softens the above-mentioned polymer. The softening material refers to a compound that increases the number of times the polymer can be bent to break. Examples of the softening material that can be used include rubber-like elastomers, brittleness improvers, plasticizers, and slide-ring polymers. Specifically, the softening material is described in paragraph number 2 of JP 2016-167043 A. <0051> ~ <0114> The softening material described in the above can be suitably used.

[0019] The softening material may be mixed with the polymer alone, or a combination of multiple softening materials may be appropriately mixed. Alternatively, the softening material alone or a combination of multiple softening materials may be used as the base material without being mixed with the polymer.

[0020] There is no particular restriction on the amount of these softening materials to be mixed in. A polymer that has a sufficient number of folds to break on its own may be used as the base material of the film alone, a softening material may be mixed in, or the entire film may be made of softening materials (100%) to provide a sufficient number of folds to break.

[0021] (Other additives) Various additives (e.g., ultraviolet absorbers, matting agents, antioxidants, peel promoters, retardation (optical anisotropy) regulators, etc.) can be added to the substrate depending on the application. They may be solid or oily. In other words, there is no particular limitation on their melting point or boiling point. The additives may be added at any time during the process of preparing the substrate, or a process of adding and preparing the additives may be added to the material preparation process. Furthermore, the amount of each material added is not particularly limited as long as the function is expressed. Other additives include those listed in paragraph number JP2016-167043A. <0117> ~ <0122> The additives described in the above can be suitably used.

[0022] The above additives may be used alone or in combination of two or more.

[0023] (UV absorber) Examples of the ultraviolet absorber include benzotriazole compounds, triazine compounds, and benzoxazine compounds. The benzotriazole compounds are compounds having a benzotriazole ring, and specific examples thereof include various benzotriazole-based ultraviolet absorbers described in, for example, JP-A-2013-111835, paragraph 0033. The triazine compounds are compounds having a triazine ring, and specific examples thereof include various triazine-based ultraviolet absorbers described in, for example, JP-A-2013-111835, paragraph 0033. The benzoxazine compounds may be those described in, for example, JP-A-2014-209162, paragraph 0031. The content of the ultraviolet absorber in the substrate is, for example, about 0.1 to 10 parts by mass relative to 100 parts by mass of the polymer contained in the substrate, but is not particularly limited. For the ultraviolet absorber, reference may also be made to JP-A-2013-111835, paragraph 0032. In the present invention, ultraviolet absorbers having high heat resistance and low volatility are preferred. Examples of such ultraviolet absorbents include UVSORB101 (manufactured by FUJIFILM Finechemicals Co., Ltd.), TINUVIN 360, TINUVIN 460, TINUVIN 1577 (manufactured by BASF), LA-F70, LA-31, LA-46 (manufactured by ADEKA Corporation), and the like.

[0024] From the viewpoint of transparency, it is preferable that the difference in refractive index between the flexible material and various additives used in the substrate and the polymer is small.

[0025] (Substrate containing imide-based polymer) A substrate containing an imide-based polymer can be preferably used as the substrate. In this specification, the imide-based polymer means a polymer containing at least one of the repeating structural units represented by formula (PI), formula (a), formula (a') and formula (b). In particular, the repeating structural unit represented by formula (PI) is preferred as the main structural unit of the imide-based polymer from the viewpoint of film strength and transparency. The repeating structural unit represented by formula (PI) is preferably 40 mol% or more, more preferably 50 mol% or more, even more preferably 70 mol% or more, particularly preferably 90 mol% or more, and even more preferably 98 mol% or more, based on the total repeating structural units of the imide-based polymer.

[0026] [ka]

[0027] In formula (PI), G represents a tetravalent organic group, and A represents a divalent organic group. 2 represents a trivalent organic group, A 2 represents a divalent organic group. 3 represents a tetravalent organic group, A 3 represents a divalent organic group. 4 and A 4 Each of represents a divalent organic group.

[0028] In formula (PI), the organic group of the tetravalent organic group represented by G (hereinafter, sometimes referred to as the organic group of G) may be a group selected from the group consisting of acyclic aliphatic groups, cyclic aliphatic groups, and aromatic groups. From the viewpoint of transparency and flexibility of the substrate containing an imide-based polymer, the organic group of G is preferably a tetravalent cyclic aliphatic group or a tetravalent aromatic group. Examples of the aromatic group include a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group having two or more aromatic rings and connected to each other directly or via a bonding group. From the viewpoint of transparency of the resin film and suppression of coloration, the organic group of G is preferably a cyclic aliphatic group, a cyclic aliphatic group having a fluorine-based substituent, a monocyclic aromatic group having a fluorine-based substituent, a condensed polycyclic aromatic group having a fluorine-based substituent, or a non-condensed polycyclic aromatic group having a fluorine-based substituent. In this specification, the fluorine-based substituent means a group containing a fluorine atom. The fluorine-based substituent is preferably a fluoro group (fluorine atom, -F) or a perfluoroalkyl group, more preferably a fluoro group or a trifluoromethyl group.

[0029] More specifically, the organic group of G is selected from, for example, a saturated or unsaturated cycloalkyl group, a saturated or unsaturated heterocycloalkyl group, an aryl group, a heteroaryl group, an arylalkyl group, an alkylaryl group, a heteroalkylaryl group, and a group having any two of these groups (which may be the same) and which are linked to each other directly or via a bonding group. Examples of the bonding group include -O-, an alkylene group having 1 to 10 carbon atoms, -SO 2 Examples thereof include -, -CO-, and -CO-NR- (R represents an alkyl group having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, or a propyl group, or a hydrogen atom).

[0030] The number of carbon atoms in the tetravalent organic group represented by G is usually 2 to 32, preferably 4 to 15, more preferably 5 to 10, and further preferably 6 to 8. When the organic group of G is a cyclic aliphatic group or an aromatic group, at least one of the carbon atoms constituting these groups may be replaced with a heteroatom. Examples of the heteroatom include O, N, and S.

[0031] Specific examples of G include groups represented by the following formula (20), formula (21), formula (22), formula (23), formula (24), formula (25) or formula (26). In the formula, * represents a bond. In formula (26), Z represents a single bond, -O-, -CH 2 -, -C(CH 3 ) 2 -, -Ar-O-Ar-, -Ar-CH 2 -Ar-, -Ar-C(CH 3 ) 2 -Ar- or -Ar-SO 2 It represents -Ar-. Ar represents an aryl group having 6 to 20 carbon atoms, and may be, for example, a phenylene group. At least one of the hydrogen atoms of these groups may be substituted with a fluorine-based substituent.

[0032] [ka]

[0033] In formula (PI), the organic group of the divalent organic group represented by A (hereinafter, sometimes referred to as the organic group of A) may be a group selected from the group consisting of acyclic aliphatic groups, cyclic aliphatic groups, and aromatic groups. The divalent organic group represented by A is preferably selected from divalent cyclic aliphatic groups and divalent aromatic groups. Examples of the aromatic group include monocyclic aromatic groups, condensed polycyclic aromatic groups, and non-condensed polycyclic aromatic groups having two or more aromatic rings and connected to each other directly or via a bonding group. From the viewpoint of transparency of the resin film and suppression of coloration, it is preferable that a fluorine-based substituent is introduced into the organic group of A.

[0034] More specifically, the organic group of A is selected from, for example, a saturated or unsaturated cycloalkyl group, a saturated or unsaturated heterocycloalkyl group, an aryl group, a heteroaryl group, an arylalkyl group, an alkylaryl group, a heteroalkylaryl group, and a group having any two of these groups (which may be the same) and linked to each other directly or via a bonding group. Examples of the heteroatom include O, N, and S, and examples of the bonding group include -O-, an alkylene group having 1 to 10 carbon atoms, -SO2 -CO- or -CO-NR- (where R represents an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group or a hydrogen atom) can be mentioned.

[0035] The number of carbon atoms of the divalent organic group represented by A is usually 2 to 40, preferably 5 to 32, more preferably 12 to 28, and still more preferably 24 to 27.

[0036] Specific examples of A include groups represented by the following formula (30), formula (31), formula (32), formula (33) or formula (34). * in the formula indicates a bond. Z 1 ~Z 3 each independently represents a single bond, -O-, -CH 2 -, -C(CH 3 ) 2 -, -SO 2 -, -CO- or -CO-NR- (where R represents an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group or a hydrogen atom). In the following groups, Z 1 and Z 2 , and Z 2 and Z 3 are each preferably in the meta or para position with respect to each ring. Also, Z 1 and the terminal single bond, Z 2 and the terminal single bond, and Z 3 and the terminal single bond are each preferably in the meta or para position. In one example of A, Z 1 and Z 3 are -O-, and Z 2 is -CH 2 -, -C(CH 3 ) 2 - or -SO 2 -. One or more of the hydrogen atoms of these groups may be substituted with a fluorine-based substituent.

[0037]

Chemical formula

[0038] At least one of the hydrogen atoms constituting at least one of A and G may be substituted with at least one functional group selected from the group consisting of a fluorine-based substituent, a hydroxyl group, a sulfone group, and an alkyl group having 1 to 10 carbon atoms. When the organic group of A and the organic group of G are each a cyclic aliphatic group or an aromatic group, it is preferable that at least one of A and G has a fluorine-based substituent, and it is more preferable that both A and G have a fluorine-based substituent.

[0039] G in formula (a) 2 is a trivalent organic group. This organic group can be selected from the same groups as the organic group of G in formula (PI), except that it is a trivalent group. G 2 Examples of the group include those in which one of the four bonds of the groups represented by formulae (20) to (26) given as specific examples of G is replaced with a hydrogen atom. A2 in formula (a) can be selected from the same groups as A in formula (PI).

[0040] G in formula (a') 3 can be selected from the same groups as G in formula (PI). 3 can be selected from the same groups as A in formula (PI).

[0041] G in formula (b) 4 is a divalent organic group. This organic group can be selected from the same groups as the organic group of G in formula (PI), except that it is a divalent group. G 4 Examples of the group represented by formula (20) to formula (26) given as specific examples of G include groups in which any two of the four bonds are replaced with hydrogen atoms. 4 can be selected from the same groups as A in formula (PI).

[0042] The imide-based polymer contained in the substrate containing an imide-based polymer may be a condensation polymer obtained by polycondensing diamines and at least one of tetracarboxylic acid compounds (including tetracarboxylic acid compound analogues such as acid chloride compounds and tetracarboxylic dianhydrides) or tricarboxylic acid compounds (including tricarboxylic acid compound analogues such as acid chloride compounds and tricarboxylic anhydrides). Furthermore, dicarboxylic acid compounds (including analogues such as acid chloride compounds) may be polycondensed. The repeating structural unit represented by formula (PI) or formula (a') is usually derived from diamines and tetracarboxylic acid compounds. The repeating structural unit represented by formula (a) is usually derived from diamines and tricarboxylic acid compounds. The repeating structural unit represented by formula (b) is usually derived from diamines and dicarboxylic acid compounds.

[0043] The tetracarboxylic acid compound may be an aromatic tetracarboxylic acid compound, an alicyclic tetracarboxylic acid compound, or an acyclic aliphatic tetracarboxylic acid compound. These may be used in combination of two or more. The tetracarboxylic acid compound is preferably a tetracarboxylic acid dianhydride. The tetracarboxylic acid dianhydride may be an aromatic tetracarboxylic acid dianhydride, an alicyclic tetracarboxylic acid dianhydride, or an acyclic aliphatic tetracarboxylic acid dianhydride.

[0044] From the viewpoints of solubility of the imide polymer in a solvent and transparency and flexibility when a substrate is formed, the tetracarboxylic acid compound is preferably an alicyclic tetracarboxylic acid compound or an aromatic tetracarboxylic acid compound, etc. From the viewpoints of transparency and suppression of coloration of the substrate containing the imide polymer, the tetracarboxylic acid compound is preferably selected from an alicyclic tetracarboxylic acid compound having a fluorine-based substituent and an aromatic tetracarboxylic acid compound having a fluorine-based substituent, and is more preferably an alicyclic tetracarboxylic acid compound having a fluorine-based substituent.

[0045] Examples of the tricarboxylic acid compound include aromatic tricarboxylic acid, alicyclic tricarboxylic acid, acyclic aliphatic tricarboxylic acid, and their related acid chloride compounds, acid anhydrides, etc. The tricarboxylic acid compound is preferably selected from aromatic tricarboxylic acid, alicyclic tricarboxylic acid, acyclic aliphatic tricarboxylic acid, and their related acid chloride compounds. Two or more types of tricarboxylic acid compounds may be used in combination.

[0046] From the viewpoints of solubility of the imide polymer in a solvent and transparency and flexibility when a substrate containing the imide polymer is formed, the tricarboxylic acid compound is preferably an alicyclic tricarboxylic acid compound or an aromatic tricarboxylic acid compound. From the viewpoints of transparency and suppression of coloration of the substrate containing the imide polymer, the tricarboxylic acid compound is more preferably an alicyclic tricarboxylic acid compound having a fluorine-based substituent or an aromatic tricarboxylic acid compound having a fluorine-based substituent.

[0047] Examples of the dicarboxylic acid compound include aromatic dicarboxylic acids, alicyclic dicarboxylic acids, acyclic aliphatic dicarboxylic acids, and their related acid chloride compounds, acid anhydrides, etc. The dicarboxylic acid compound is preferably selected from aromatic dicarboxylic acids, alicyclic dicarboxylic acids, acyclic aliphatic dicarboxylic acids, and their related acid chloride compounds. Two or more dicarboxylic acid compounds may be used in combination.

[0048] From the viewpoints of solubility of the imide polymer in a solvent and transparency and flexibility when a substrate containing the imide polymer is formed, the dicarboxylic acid compound is preferably an alicyclic dicarboxylic acid compound or an aromatic dicarboxylic acid compound. From the viewpoints of transparency and suppression of coloration of the substrate containing the imide polymer, the dicarboxylic acid compound is more preferably an alicyclic dicarboxylic acid compound having a fluorine-based substituent or an aromatic dicarboxylic acid compound having a fluorine-based substituent.

[0049] Examples of the diamines include aromatic diamines, alicyclic diamines, and aliphatic diamines, and two or more of these may be used in combination. From the viewpoints of the solubility of the imide-based polymer in a solvent and the transparency and flexibility of a substrate containing the imide-based polymer, the diamines are preferably selected from alicyclic diamines and aromatic diamines having a fluorine-based substituent.

[0050] By using such an imide-based polymer, it is easy to obtain a resin film having particularly excellent flexibility, high light transmittance (for example, 85% or more, preferably 88% or more for light of 550 nm), low yellowness (YI value, 5 or less, preferably 3 or less), and low haze (1.5% or less, preferably 1.0% or less).

[0051] The imide-based polymer may be a copolymer containing a plurality of different types of the above repeating structural units. The weight-average molecular weight of the polyimide-based polymer is usually 10,000 to 500,000. The weight-average molecular weight of the imide-based polymer is preferably 50,000 to 500,000, more preferably 70,000 to 400,000. The weight-average molecular weight is a standard polystyrene-equivalent molecular weight measured by gel permeation chromatography (GPC). When the weight-average molecular weight of the imide-based polymer is large, it tends to be easy to obtain high flexibility, but when the weight-average molecular weight of the imide-based polymer is too large, the viscosity of the varnish tends to increase and the processability tends to decrease.

[0052] The imide-based polymer may contain halogen atoms such as fluorine atoms that can be introduced by the above-mentioned fluorine-based substituents, etc. When the polyimide-based polymer contains halogen atoms, the elastic modulus of the substrate containing the imide-based polymer can be improved and the yellowness can be reduced. This can suppress scratches and wrinkles that occur in the resin film and improve the transparency of the substrate containing the imide-based polymer. The halogen atom is preferably a fluorine atom. The content of halogen atoms in the polyimide-based polymer is preferably 1 to 40 mass %, more preferably 1 to 30 mass %, based on the mass of the polyimide-based polymer.

[0053] The substrate containing the imide-based polymer may contain one or more ultraviolet absorbents. The ultraviolet absorbent may be appropriately selected from those commonly used as ultraviolet absorbents in the field of resin materials. The ultraviolet absorbent may contain a compound that absorbs light with a wavelength of 400 nm or less. Examples of the ultraviolet absorbent that can be appropriately combined with the imide-based polymer include at least one compound selected from the group consisting of benzophenone-based compounds, salicylate-based compounds, benzotriazole-based compounds, and triazine-based compounds. In this specification, the term "based compound" refers to a derivative of a compound to which the term "based compound" is attached. For example, a "benzophenone-based compound" refers to a compound having benzophenone as a parent skeleton and a substituent bonded to the benzophenone.

[0054] The content of the ultraviolet absorbing agent is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and usually 10% by mass or less, preferably 8% by mass or less, more preferably 6% by mass or less, based on the total mass of the resin film. By including the ultraviolet absorbing agent in these amounts, the weather resistance of the resin film 10 can be improved.

[0055] The substrate containing the imide-based polymer may further contain an inorganic material such as inorganic particles. The inorganic material is preferably a silicon material containing silicon atoms. By containing an inorganic material such as a silicon material in the substrate containing the imide-based polymer, the tensile modulus of the substrate containing the imide-based polymer can be easily set to 4.0 GPa or more. However, the method of controlling the tensile modulus of the substrate containing the imide-based polymer is not limited to the blending of an inorganic material.

[0056] Examples of silicon materials containing silicon atoms include silica particles, quaternary alkoxysilanes such as tetraethyl orthosilicate (TEOS), and silicon compounds such as silsesquioxane derivatives. Among these silicon materials, silica particles are preferred from the viewpoints of transparency and flexibility of the substrate containing the imide polymer.

[0057] The average primary particle size of the silica particles is usually 100 nm or less. When the average primary particle size of the silica particles is 100 nm or less, the transparency tends to be improved.

[0058] The average primary particle diameter of the silica particles in the substrate containing the imide-based polymer can be determined by observation with a transmission electron microscope (TEM). The primary particle diameter of the silica particles can be a unidirectional diameter measured with a transmission electron microscope (TEM). The average primary particle diameter can be determined by measuring the primary particle diameter at 10 points by TEM observation and averaging the results. The particle distribution of the silica particles before forming the substrate containing the imide-based polymer can be determined by a commercially available laser diffraction particle size distribution analyzer.

[0059] In the substrate containing an imide-based polymer, the blending ratio of the imide-based polymer to the inorganic material is preferably 1:9 to 10:0, more preferably 3:7 to 10:0, even more preferably 3:7 to 8:2, and even more preferably 3:7 to 7:3, in terms of mass ratio, assuming that the total of the two is 10. The ratio of the inorganic material to the total mass of the imide-based polymer and the inorganic material is usually 20 mass% or more, preferably 30 mass% or more, and usually 90 mass% or less, preferably 70 mass% or less. When the blending ratio of the imide-based polymer to the inorganic material (silicon material) is within the above range, the transparency and mechanical strength of the substrate containing an imide-based polymer tend to be improved. In addition, the tensile modulus of the substrate containing an imide-based polymer can be easily set to 4.0 GPa or more.

[0060] The substrate containing the imide-based polymer may further contain components other than the imide-based polymer and inorganic materials, as long as the transparency and flexibility are not significantly impaired. Examples of the components other than the imide-based polymer and inorganic materials include antioxidants, release agents, stabilizers, colorants such as bluing agents, flame retardants, lubricants, thickeners, and leveling agents. The ratio of the components other than the imide-based polymer and inorganic materials is preferably more than 0% and 20% by mass or less, more preferably more than 0% and 10% by mass or less, based on the mass of the resin film 10.

[0061] When the imide-based polymer-containing substrate contains an imide-based polymer and a silicon material, it is preferable that the atomic ratio Si / N of silicon atoms to nitrogen atoms on at least one of the main surfaces 10a is equal to or greater than 8. This atomic ratio Si / N is a value calculated from the abundance of silicon atoms and the abundance of nitrogen atoms obtained by evaluating the composition of the imide-based polymer-containing substrate by X-ray photoelectron spectroscopy (XPS).

[0062] By setting the Si / N ratio on the main surface 10a of the substrate containing an imide-based polymer to 8 or more, sufficient adhesion with the functional layer 20 described below can be obtained. From the viewpoint of adhesion, the Si / N ratio is more preferably 9 or more, and even more preferably 10 or more, and is preferably 50 or less, and more preferably 40 or less.

[0063] (Thickness of substrate) The thickness of the substrate is preferably 100 μm or less, more preferably 80 μm or less, and most preferably 50 μm or less. If the thickness of the substrate is thin, the difference in curvature between the front and back sides when folded is small, so that cracks are less likely to occur, and the substrate does not break even when folded multiple times. On the other hand, from the viewpoint of ease of handling the substrate, the thickness of the substrate is preferably 3 μm or more, more preferably 5 μm or more, and most preferably 15 μm or more.

[0064] (Method of preparing the substrate) The substrate may be formed into a film by thermally melting a thermoplastic polymer, or may be formed into a film by solution film-forming (solvent casting method) from a solution in which the polymer is uniformly dissolved. In the case of thermal melt film-forming, the above-mentioned softening material and various additives can be added at the time of thermal melting. On the other hand, in the case of preparing the substrate by a solution film-forming method, the above-mentioned softening material and various additives can be added to the polymer solution (hereinafter also referred to as dope) in each preparation step. The addition may be made at any time during the dope preparation step, or a step of adding the additives to prepare the dope may be added to the last preparation step of the dope preparation step.

[0065] A protective film may be attached to one or both sides of the substrate to protect the surface or maintain the smoothness of the substrate. As the protective film, a protective film in which an adhesive containing an antistatic agent is laminated on one side of the support is preferable. By using such a protective film, it is possible to prevent dust from adhering when the protective film is peeled off and the hard coat layer is formed.

[0066] <Hard coat layer> The hard coat layer of the hard coat film of the present invention will be described. The hard coat layer in the present invention preferably contains a cured product of a polymerizable compound. The hard coat layer in the present invention more preferably contains at least one selected from a cured product of polyorganosilsesquioxane (A) having a polymerizable group, a cured product of compound (a2) having two or more (meth)acryloyl groups in one molecule, a cured product of compound (a3) ​​having a polymerizable functional group, and inorganic fine particles, and from the viewpoints of pencil hardness and repeated bending resistance, it is particularly preferable to have a cured product of polyorganosilsesquioxane (A) having a polymerizable group.

[0067] (Polyorganosilsesquioxane (A) Having Polymerizable Groups) The polymerizable group in the polyorganosilsesquioxane (A) having a polymerizable group is not particularly limited, but is preferably a radically polymerizable or cationic polymerizable group. The radically polymerizable group may be a generally known radically polymerizable group, and a suitable example thereof may be a (meth)acryloyl group. The cationic polymerizable group may be a generally known cationic polymerizable group, and specifically, may be an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro orthoester group, a vinyloxy group, etc. Among them, an alicyclic ether group and a vinyloxy group are preferred, an epoxy group, an oxetanyl group, and a vinyloxy group are particularly preferred, and an epoxy group is most preferred.

[0068] The polyorganosilsesquioxane (A) having a polymerizable group is preferably a polyorganosilsesquioxane (a1) having an epoxy group. The cured product of the polyorganosilsesquioxane (a1) having an epoxy group is preferably obtained by curing a curable composition containing the polyorganosilsesquioxane (a1) having an epoxy group by heating and / or exposure to ionizing radiation.

[0069] (Polyorganosilsesquioxane (a1) having epoxy groups) The polyorganosilsesquioxane (a1) having an epoxy group (also referred to as "polyorganosilsesquioxane (a1)") has at least a siloxane constituent unit containing an epoxy group, and is preferably a polyorganosilsesquioxane represented by the following general formula (1).

[0070] [ka]

[0071] In the general formula (1), Rb represents a group containing an epoxy group, and Rc represents a monovalent group. q and r represent the ratio of Rb and Rc in the general formula (1), where q+r=100, q is greater than 0, and r is 0 or greater. When there are multiple Rb and Rc in the general formula (1), the multiple Rb and Rc may be the same or different. When there are multiple Rc in the general formula (1), the multiple Rc may form a bond with each other.

[0072] In the general formula (1), [SiO 1.5 represents a structural portion constituted by a siloxane bond (Si-O-Si) in the polyorganosilsesquioxane. Polyorganosilsesquioxane is a network-type polymer or polyhedral cluster having siloxane building blocks derived from a hydrolyzable trifunctional silane compound, and can form a random structure, a ladder structure, a cage structure, or the like through siloxane bonds. 1.5 The structural portion represented by "]" may be any of the above structures, but preferably contains a large amount of ladder structures. By forming the ladder structure, the deformation recovery property of the hard coat film can be maintained well. The formation of the ladder structure is observed when the FT-IR (Fourier Transform Infrared Spectroscopy) is measured at 1020-1050 cm -1 This can be qualitatively confirmed by the presence or absence of absorption due to the Si-O-Si stretching characteristic of the ladder structure that appears in the vicinity.

[0073] In general formula (1), Rb represents a group containing an epoxy group. Examples of the group containing an epoxy group include known groups having an oxirane ring. Rb is preferably a group represented by the following formulas (1b) to (4b).

[0074] [ka]

[0075] In the above formulas (1b) to (4b), ** represents a linking portion with Si in general formula (1), and R 1b , R 2b , R 3b and R 4b represents a substituted or unsubstituted alkylene group. R 1b , R 2b , R 3b and R 4b The alkylene group represented by is preferably a linear or branched alkylene group having 1 to 10 carbon atoms, and examples thereof include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, an i-propylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, and an n-decylene group. R 1b , R 2b , R 3b and R 4b When the alkylene group represented by the formula (I) has a substituent, examples of the substituent include a hydroxyl group, a carboxyl group, an alkoxy group, an aryl group, a heteroaryl group, a halogen atom, a nitro group, a cyano group, and a silyl group. R 1b , R 2b , R 3b and R 4b is preferably an unsubstituted linear alkylene group having 1 to 4 carbon atoms or an unsubstituted branched alkylene group having 3 or 4 carbon atoms, more preferably an ethylene group, an n-propylene group, or an i-propylene group, and even more preferably an ethylene group or an n-propylene group.

[0076] The polyorganosilsesquioxane (a1) preferably has an alicyclic epoxy group (a group having a condensed ring structure of an epoxy group and an alicyclic group). Rb in the general formula (1) is preferably an alicyclic epoxy group, more preferably a group having an epoxycyclohexyl group, and further preferably a group represented by the above formula (1b).

[0077] In addition, Rb in the general formula (1) is derived from a group bonded to a silicon atom in a hydrolyzable trifunctional silane compound used as a raw material for polyorganosilsesquioxane (a group other than an alkoxy group and a halogen atom; for example, Rb in a hydrolyzable silane compound represented by the following formula (B)).

[0078] Specific examples of Rb are shown below, but the present invention is not limited thereto. In the following specific examples, ** represents the linking portion with Si in the general formula (1).

[0079]

Chemical formula

[0080] In the general formula (1), Rc represents a monovalent group. Examples of the monovalent group represented by Rc include a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group.

[0081] Examples of the alkyl group represented by Rc include alkyl groups having 1 to 10 carbon atoms, such as linear or branched alkyl groups such as methyl group, ethyl group, propyl group, n-butyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, and isopentyl group. Examples of the cycloalkyl group represented by Rc include cycloalkyl groups having 3 to 15 carbon atoms, such as cyclobutyl group, cyclopentyl group, and cyclohexyl group. Examples of the alkenyl group represented by Rc include alkenyl groups having 2 to 10 carbon atoms, such as linear or branched alkenyl groups such as vinyl group, allyl group, and isopropenyl group. Examples of the aryl group represented by Rc include aryl groups having 6 to 15 carbon atoms, such as phenyl group, tolyl group, and naphthyl group. The aralkyl group represented by Rc includes aralkyl groups having 7 to 20 carbon atoms, such as a benzyl group and a phenethyl group.

[0082] Examples of the above-mentioned substituted alkyl group, substituted cycloalkyl group, substituted alkenyl group, substituted aryl group and substituted aralkyl group include groups in which a hydrogen atom or a part or all of the main chain skeleton of the above-mentioned alkyl group, cycloalkyl group, alkenyl group, aryl group and aralkyl group is substituted with at least one selected from the group consisting of an ether group, an ester group, a carbonyl group, a halogen atom (such as a fluorine atom), an acryl group, a methacryl group, a mercapto group and a hydroxyl group.

[0083] Rc is preferably a substituted or unsubstituted alkyl group, and more preferably an unsubstituted alkyl group having 1 to 10 carbon atoms.

[0084] When there are multiple Rc's in general formula (1), the multiple Rc's may form a bond with each other. It is preferable that two or three Rc's form a bond with each other, and it is more preferable that two Rc's form a bond with each other.

[0085] A group formed by combining two Rc's together (Rc 2 ) is preferably an alkylene group formed by bonding with the substituted or unsubstituted alkyl groups represented by the above Rc.

[0086] Rc 2 Examples of the alkylene group represented by include linear or branched alkylene groups such as methylene, ethylene, propylene, isopropylene, n-butylene, isobutylene, s-butylene, t-butylene, n-pentylene, isopentylene, s-pentylene, t-pentylene, n-hexylene, isohexylene, s-hexylene, t-hexylene, n-heptylene, isoheptylene, s-heptylene, t-heptylene, n-octylene, isooctylene, s-octylene, and t-octylene.

[0087] Rc 2 The alkylene group represented by is preferably an unsubstituted alkylene group having 2 to 20 carbon atoms, more preferably an unsubstituted alkylene group having 2 to 20 carbon atoms, still more preferably an unsubstituted alkylene group having 2 to 8 carbon atoms, and particularly preferably an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, or an n-octylene group.

[0088] A group formed by combining three Rc together (Rc 3 ) is the above-mentioned Rc 2 In the alkylene group represented by the formula (I), it is preferable that the alkylene group is a trivalent group in which one arbitrary hydrogen atom is removed from the alkylene group.

[0089] In addition, Rc in the general formula (1) is a group bonded to a silicon atom in the hydrolyzable silane compound used as a raw material for the polyorganosilsesquioxane (a group other than an alkoxy group and a halogen atom; for example, Rc in the hydrolyzable silane compounds represented by the formulas (C1) to (C3) described later). 1 ~Rc 3 etc.)

[0090] In general formula (1), q is greater than 0 and r is 0 or greater. The ratio q / (q+r) is preferably 0.5 to 1.0. By making the number of groups represented by Rb equal to or more than half of the total number of groups represented by Rb or Rc contained in the polyorganosilsesquioxane (a1), a network formed by organic crosslinking groups is sufficiently formed, so that each performance such as hardness and repeated bending resistance can be maintained at a good level. The ratio q / (q+r) is more preferably from 0.7 to 1.0, further preferably from 0.9 to 1.0, and particularly preferably from 0.95 to 1.0.

[0091] In the general formula (1), it is also preferable that there are multiple Rc's and the multiple Rc's form bonds with each other. In this case, it is preferable that r / (q+r) is 0.005 to 0.20. The ratio r / (q+r) is more preferably from 0.005 to 0.10, further preferably from 0.005 to 0.05, and particularly preferably from 0.005 to 0.025.

[0092] The number average molecular weight (Mn) of the polyorganosilsesquioxane (a1) in terms of standard polystyrene measured by gel permeation chromatography (GPC) is preferably 500 to 6,000, more preferably 1,000 to 4,500, and even more preferably 1,500 to 3,000.

[0093] The polyorganosilsesquioxane (a1) has a molecular weight dispersity (Mw / Mn) calculated based on standard polystyrene by GPC of, for example, 1.0 to 4.0, preferably 1.1 to 3.7, more preferably 1.2 to 3.0, and further preferably 1.3 to 2.5, where Mn represents the number average molecular weight.

[0094] The weight average molecular weight and molecular weight dispersity of the polyorganosilsesquioxane (a1) were measured using the following device and under the following conditions. Measuring device: Product name "LC-20AD" (manufactured by Shimadzu Corporation) Column: Shodex KF-801 x 2, KF-802, and KF-803 (Showa Denko K.K.) Measurement temperature: 40℃ Eluent: tetrahydrofuran (THF), sample concentration 0.1 to 0.2% by mass Flow rate: 1mL / min Detector: UV-VIS detector (product name "SPD-20A", manufactured by Shimadzu Corporation) Molecular weight: Standard polystyrene equivalent

[0095] <Method for producing polyorganosilsesquioxane (a1)> The polyorganosilsesquioxane (a1) can be produced by a known production method, and is not particularly limited, but can be produced by a method of hydrolyzing and condensing one or more hydrolyzable silane compounds. As the hydrolyzable silane compound, it is preferable to use a hydrolyzable trifunctional silane compound (a compound represented by the following formula (B)) for forming a siloxane structural unit containing an epoxy group as the hydrolyzable silane compound. When r in the general formula (1) is greater than 0, it is preferable to use a compound represented by the following formula (C1), (C2) or (C3) in combination as the hydrolyzable silane compound.

[0096] [ka]

[0097] Rb in formula (B) has the same meaning as Rb in general formula (1) above, and preferred examples are also the same.

[0098] X in formula (B) 2 represents an alkoxy group or a halogen atom. X 2 Examples of the alkoxy group in include alkoxy groups having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, and an isobutyloxy group. X 2 Examples of the halogen atom in include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. X 2 As the X, an alkoxy group is preferable, and a methoxy group or an ethoxy group is more preferable. 2 may be the same or different.

[0099] The compound represented by the above formula (B) is a compound that forms a siloxane constitutional unit having Rb.

[0100] [ka]

[0101] [ka]

[0102] [ka]

[0103] Rc in formula (C1) 1 has the same meaning as Rc in the above general formula (1), and preferred examples are also the same. Rc in formula (C2) 2 represents a group formed by bonding two Rc's together in the above general formula (1) (Rc 2 ) and preferred examples are also the same. Rc in formula (C3) 3 represents a group formed by bonding together three Rc's in the above general formula (1) (Rc 3 ) and preferred examples are also the same.

[0104] X in the above formulas (C1) to (C3) 3 is X in the above formula (B) 2 The same applies to preferred examples. 3 may be the same or different.

[0105] The hydrolyzable silane compound may be used in combination with a hydrolyzable silane compound other than the compounds represented by the above formulas (B), (C1) to (C3). For example, hydrolyzable trifunctional silane compounds, hydrolyzable monofunctional silane compounds, hydrolyzable difunctional silane compounds, etc., other than the compounds represented by the above formulas (B), (C1) to (C3) may be used.

[0106] Rc in the hydrolyzable silane compounds represented by the above formulas (C1) to (C3) 1 ~Rc 3In the case where the compound is derived from the above, q / (q+r) in the general formula (1) can be adjusted by adjusting the compounding ratio (molar ratio) of the compounds represented by the above formulas (B) and (C1) to (C3). Specifically, for example, in order to adjust q / (q+r) to 0.5 to 1.0, the value represented by the following (Z2) may be adjusted to 0.5 to 1.0, and these compounds may be produced by a method of hydrolyzing and condensing them. (Z2) = Compound represented by formula (B) (molar amount) / {Compound represented by formula (B) (molar amount) + Compound represented by formula (C1) (molar amount) + Compound represented by formula (C2) (molar amount) × 2 + Compound represented by formula (C3) (molar amount) × 3}

[0107] The amount and composition of the hydrolyzable silane compound used can be appropriately adjusted depending on the desired structure of the polyorganosilsesquioxane (a1).

[0108] The hydrolysis and condensation reactions of the hydrolyzable silane compound can be carried out simultaneously or successively. When the reactions are carried out successively, the order of the reactions is not particularly limited.

[0109] The hydrolysis and condensation reaction of the hydrolyzable silane compound can be carried out in the presence or absence of a solvent, and is preferably carried out in the presence of a solvent. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran, and dioxane; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, isopropyl acetate, and butyl acetate; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; nitriles such as acetonitrile, propionitrile, and benzonitrile; and alcohols such as methanol, ethanol, isopropyl alcohol, and butanol. The solvent is preferably a ketone or an ether, and the solvent may be used alone or in combination of two or more.

[0110] The amount of the solvent used is not particularly limited, and can be appropriately adjusted in the range of 0 to 2000 parts by mass relative to 100 parts by mass of the total amount of the hydrolyzable silane compounds, depending on the desired reaction time, etc.

[0111] The hydrolysis and condensation reaction of the hydrolyzable silane compound is preferably carried out in the presence of a catalyst and water. The catalyst may be an acid catalyst or an alkali catalyst. Examples of the acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid; phosphate esters; carboxylic acids such as acetic acid, formic acid, and trifluoroacetic acid; sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid; solid acids such as activated clay; and Lewis acids such as iron chloride. Examples of the alkali catalyst include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; hydroxides of alkaline earth metals such as magnesium hydroxide, calcium hydroxide, and barium hydroxide; carbonates of alkali metals such as lithium carbonate, sodium carbonate, potassium carbonate, and cesium carbonate; carbonates of alkaline earth metals such as magnesium carbonate; hydrogen carbonates of alkali metals such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and cesium hydrogen carbonate; organic acid salts of alkali metals such as lithium acetate, sodium acetate, potassium acetate, and cesium acetate (e.g., acetates); magnesium acetate, alkali metal alkoxides such as lithium methoxide, sodium methoxide, sodium ethoxide, sodium isopropoxide, potassium ethoxide, potassium t-butoxide, etc.; alkali metal phenoxides such as sodium phenoxide, etc.; amines (tertiary amines, etc.) such as triethylamine, N-methylpiperidine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, etc.; and nitrogen-containing aromatic heterocyclic compounds such as pyridine, 2,2'-bipyridyl, 1,10-phenanthroline, etc. The catalyst may be used alone or in combination of two or more kinds. The catalyst may be used in a state of being dissolved or dispersed in water or a solvent. The catalyst is preferably a base catalyst. By using a base catalyst, the condensation rate of the polyorganosilsesquioxane can be increased, and the deformation recovery rate when cured can be maintained at a good level.

[0112] The amount of the catalyst used is not particularly limited, and can be appropriately adjusted within the range of 0.002 to 0.200 mol per mol of the total amount of the hydrolyzable silane compounds.

[0113] The amount of water used in the above hydrolysis and condensation reactions is not particularly limited, and can be appropriately adjusted within the range of 0.5 to 20 moles per mole of the total amount of the hydrolyzable silane compounds.

[0114] The method of adding water is not particularly limited, and the total amount of water used (total amount used) may be added all at once or gradually. When the water is added gradually, it may be added continuously or intermittently.

[0115] As the reaction conditions when carrying out the hydrolysis and condensation reaction of the hydrolyzable silane compound, it is particularly important to select reaction conditions such that the condensation rate of the polyorganosilsesquioxane (a1) is 80% or more. The reaction temperature of the hydrolysis and condensation reaction is, for example, 40 to 100°C, preferably 45 to 80°C. By controlling the reaction temperature within the above range, the condensation rate tends to be controlled to 80% or more. The reaction time of the hydrolysis and condensation reaction is, for example, 0.1 to 10 hours, preferably 1.5 to 8 hours. The hydrolysis and condensation reaction can be carried out under normal pressure, or under pressure or reduced pressure. The atmosphere when carrying out the hydrolysis and condensation reaction may be, for example, a nitrogen atmosphere, an inert gas atmosphere such as an argon atmosphere, or in the presence of oxygen such as air, but an inert gas atmosphere is preferred.

[0116] The hydrolysis and condensation reaction of the hydrolyzable silane compound produces polyorganosilsesquioxane (a1). After the completion of the hydrolysis and condensation reaction, it is preferable to neutralize the catalyst in order to suppress the ring-opening of the epoxy group. In addition, the polyorganosilsesquioxane (a1) may be separated and purified by, for example, washing with water, washing with an acid, washing with an alkali, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination of these separation means.

[0117] In the hard coat layer of the hard coat film of the present invention, the condensation rate of the polyorganosilsesquioxane (a1) is preferably 80% or more from the viewpoint of the hardness of the film, more preferably 90% or more, and even more preferably 95% or more. The above condensation ratio was measured for a hard coat film sample having a hard coat layer containing a cured product of polyorganosilsesquioxane (a1). 29 It is possible to perform Si NMR (nuclear magnetic resonance) spectrum measurement and use the measurement results to perform the calculation.

[0118] In the cured product of the polyorganosilsesquioxane (a1) having an epoxy group, the epoxy group is preferably ring-opened by a polymerization reaction. In the hard coat layer of the hard coat film of the present invention, the ring-opening rate of the epoxy group of the cured product of the polyorganosilsesquioxane (a1) is preferably 40% or more from the viewpoint of the hardness of the film, more preferably 50% or more, and even more preferably 60% or more. The ring-opening ratio can be calculated from the change in peak height derived from the epoxy group by performing FT-IR (Fourier Transform Infrared Spectroscopy) single reflection ATR (Attenuated Total Reflection) measurement on a sample of a hard coat layer-forming composition containing the polyorganosilsesquioxane (a1) before and after complete curing and heat treatment.

[0119] The polyorganosilsesquioxane (a1) may be used alone or in combination of two or more kinds having different structures.

[0120] When the hard coat layer in the present invention contains a cured product of polyorganosilsesquioxane (A) having a polymerizable group as a cured product of a polymerizable compound, the content of the cured product of polyorganosilsesquioxane (A) having a polymerizable group is preferably 50 mass% or more and 100 mass% or less, more preferably 70 mass% or more and 100 mass% or less, and even more preferably 80 mass% or more and 100 mass% or less, based on the total mass of the hard coat layer.

[0121] When the hard coat layer in the present invention contains a cured product of a polyorganosilsesquioxane (A) having a polymerizable group as a cured product of a polymerizable compound, it may further contain a dispersant, an antifouling agent, an antistatic agent, an ultraviolet absorber, an antioxidant, etc. The type of the antistatic agent is not particularly limited, and an ion-conductive or electron-conductive antistatic agent can be preferably used. As a specific example of an electron-conductive antistatic agent, Sepulgida (manufactured by Shin-Etsu Polymer Co., Ltd.) using a polythiophene conductive polymer can be preferably used.

[0122] The hard coat layer in the present invention may contain a cured product of a compound (a2) having two or more (meth)acryloyl groups in one molecule.

[0123] (Compound (a2) having a (meth)acryloyl group in one molecule) The cured product of the compound (a2) having two or more (meth)acryloyl groups in one molecule is preferably obtained by curing a curable composition containing a compound having two or more (meth)acryloyl groups in one molecule by heating and / or irradiating with ionizing radiation. The compound (a2) having two or more (meth)acryloyl groups in one molecule (also referred to as "polyfunctional (meth)acrylate compound (a2)") is preferably a compound having three or more (meth)acryloyl groups in one molecule. The polyfunctional (meth)acrylate compound (a2) may be a crosslinkable monomer, a crosslinkable oligomer, or a crosslinkable polymer.

[0124] The polyfunctional (meth)acrylate compound (a2) has the same meaning as the polyfunctional (meth)acrylate compound (b2) described below, and the preferred range is also the same.

[0125] The polyfunctional (meth)acrylate compound (a2) may be used alone or in combination of two or more compounds having different structures.

[0126] When the hard coat layer in the present invention contains a cured product of a polyfunctional (meth)acrylate compound (a2) as a cured product of a polymerizable compound, the content of the cured product of the polyfunctional (meth)acrylate compound (a2) is preferably from 50% by mass to 100% by mass, more preferably from 70% by mass to 100% by mass, and even more preferably from 80% by mass to 100% by mass, based on the total mass of the hard coat layer.

[0127] The hard coat layer in the present invention may contain a cured product of the compound (a3) ​​having a polymerizable functional group and inorganic fine particles. In the case where the hard coat layer in the present invention contains a cured product of the compound (a3) ​​having a polymerizable functional group and inorganic fine particles, it is preferable that the inorganic fine particles are contained in a matrix (a3) ​​containing the cured product of the compound (a3) ​​having a polymerizable functional group.

[0128] (Matrix (a3)) From the viewpoint of repeated bending resistance, the matrix (a3) ​​has an indentation modulus E M The indentation elastic modulus E of the matrix (a3) ​​is preferably 1.5 GPa or less, more preferably 1.0 GPa or less, and even more preferably 0.5 GPa or less. MThis is the indentation elastic modulus when a diamond knoop indenter is used to apply a load perpendicularly to a layer formed by hardening the composition for forming the matrix (a3) ​​described below, and the indentation elastic modulus is determined by indenting the matrix layer by 2% relative to its thickness in an indentation test.

[0129] The matrix (a3) ​​is preferably a polymer (cured product) obtained by polymerizing a composition for forming the matrix (a3) ​​containing a compound (a3) ​​having a polymerizable functional group by irradiation with ionizing radiation or heating. M In order to make the polymerizable functional group equivalent in the composition for forming the matrix (a3) ​​fall within the above range, it is preferable that the polymerizable functional group equivalent in the composition for forming the matrix (a3) ​​is not less than 250. If the polymerizable functional group equivalent in the composition for forming the matrix (a3) ​​is too large, the chemical bonds with the functional groups modified on the surfaces of the inorganic fine particles described below may decrease, resulting in a deterioration in hardness and resistance to repeated bending, but this can be compensated for by appropriate selection of the average primary particle diameter of the inorganic fine particles and the surface modifier.

[0130] The polymerizable functional group equivalent e in the composition for forming the matrix (a3) ​​is calculated from the following formula (4): In the formula, the mass ratios of the components 1, 2, ..., n contained in the composition for forming the matrix (a3) ​​are R 1 , R 2 , …R n , and the weight average molecular weight of each component is M 1 , M 2 , …, M N , the number of polymerizable functional groups in one molecule of each component is C 1 , C 2 , … , C n This is expressed as:

[0131]

number

[0132] (Compound (a3) ​​Having a Polymerizable Functional Group) As the compound (a3) ​​having a polymerizable functional group, various monomers, oligomers and polymers can be used. As the polymerizable functional group (polymerizable group), those which are polymerizable by light, electron beam or radiation are preferred, and among these, photopolymerizable functional groups are preferred.

[0133] Examples of the photopolymerizable functional group include polymerizable unsaturated groups (carbon-carbon unsaturated double bond groups) such as a (meth)acryloyl group, a vinyl group, a styryl group, and an allyl group, and ring-opening polymerizable groups such as an epoxy group and an oxetanyl group. Among these, a (meth)acryloyl group is preferred.

[0134] Specific examples of the compound having a (meth)acryloyl group include (meth)acrylic acid diesters of alkylene glycols, such as neopentyl glycol acrylate, 1,6-hexanediol (meth)acrylate, and propylene glycol di(meth)acrylate; (meth)acrylic acid diesters of polyoxyalkylene glycols, such as triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate; (Meth)acrylic acid diesters of polyhydric alcohols such as pentaerythritol di(meth)acrylate; Examples of the photopolymerizable monomer include (meth)acrylic acid diesters of ethylene oxide or propylene oxide adducts such as 2,2-bis{4-(acryloxy-diethoxy)phenyl}propane and 2-2-bis{4-(acryloxy-polypropoxy)phenyl}propane. Furthermore, epoxy (meth)acrylates, urethane (meth)acrylates, and polyester (meth)acrylates are also preferably used as the photopolymerizable monomer.

[0135] In order to make the polymerizable functional group equivalent in the composition for forming the matrix (a3) ​​250 or more, the compound having a polymerizable functional group is preferably a compound having a polymerizable functional group equivalent of 250 or more. Two or more types of compounds having a polymerizable functional group may be used in combination, and in this case, the polymerizable functional group equivalent in the composition for forming the matrix (a3) ​​may be adjusted to 250 or more by using a compound having a polymerizable functional group equivalent of 250 or more in combination with a compound having a polymerizable functional group equivalent of 250 or less.

[0136] When the compound (a3) ​​having a polymerizable functional group is a monomer, the compound preferably has 1 to 6 polymerizable functional groups in one molecule, more preferably has 1 to 3 polymerizable functional groups, and particularly preferably has 2 polymerizable functional groups. When the compound (a3) ​​having a polymerizable functional group is an oligomer or polymer, the polymerizable functional group may be present at the main chain terminal or in a side chain.

[0137] Specific examples of compounds with a polymerizable functional group equivalent of 250 or more include DPCA-120 (molecular weight 1947, number of polymerizable functional groups 6, polymerizable functional group equivalent 325) manufactured by Nippon Kayaku Co., Ltd., Shikoh UV-3000B (molecular weight 18000, number of functional groups 2, functional group equivalent 9000), UV-3200B (molecular weight 10000, number of functional groups 2, functional group equivalent 5000), and UV-3210EA (molecular weight 9000, number of functional groups 2, functional group equivalent 5000) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. Number of groups 2, functional group equivalent 4500), UV-3310B (molecular weight 5000, number of functional groups 2, functional group equivalent 2500), UV-3700B (molecular weight 38000, number of functional groups 2, functional group equivalent 19000), U V-6640B (molecular weight 5000, number of functional groups 2, functional group equivalent weight 2500), UV-2000B (molecular weight 13000, number of functional groups 2, functional group equivalent weight 6500), UV-2750B (molecular weight 3000, functional group equivalent weight 6500) number 2, functional group equivalent 1500), ATM-35E (molecular weight 1892, number of functional groups 4, functional group equivalent 473) manufactured by Shin Nakamura Chemical Co., Ltd. A-GLY-9E (molecular weight 811, number of functional groups 3, functional group equivalent 270), A-GLY-20E (molecular weight 1295, number of functional groups 3, functional group equivalent weight 432), A-400 (molecular weight 508, number of functional groups 2, functional group equivalent weight 254), A-600 (molecular weight 708, number of functional groups 2, functional group equivalent weight 3) 54), UA-1000 (molecular weight 1108, number of functional groups 2, functional group equivalent 554), UA-160TM (molecular weight 2700, number of functional groups 2, functional group equivalent 1350), UA-290TM (molecular weight 2900, number of functional groups 2, functional group equivalent 1450), UA-4200 (molecular weight 1000, number of functional groups 2, functional group equivalent 500), and UA-4400 (molecular weight 1400, number of functional groups 2, functional group equivalent 700).

[0138] (Polymerization initiator) The composition for forming the matrix (a3) ​​may contain a polymerization initiator.

[0139] When the compound (a3) ​​having a polymerizable functional group is a photopolymerizable compound, it preferably contains a photopolymerization initiator. Examples of the photopolymerization initiator include acetophenones, benzoins, benzophenones, phosphine oxides, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkyldione compounds, disulfide compounds, fluoroamine compounds, aromatic sulfonium compounds, lophine dimers, onium salts, borate salts, active esters, active halogens, inorganic complexes, coumarins, etc. Specific examples of the photopolymerization initiator, preferred embodiments, and commercially available products are described in paragraph 1 of JP-A-2009-098658. <0133> ~ <0151> and can be suitably used in the present invention as well. Various examples are described in "Latest UV Curing Technology" {Technical Information Association, Inc.} (1991), p. 159, and "Ultraviolet Curing System" by Kato Kiyomi (published by the General Technology Center in 1989), pp. 65-148, which are useful for the present invention. The content of the polymerization initiator in the composition for forming the matrix (a3) ​​is preferably from 0.5 to 8 mass %, more preferably from 1 to 5 mass %, based on the total solid content in the composition for forming the matrix (a3).

[0140] (Other additives) The composition for forming the matrix (a3) ​​may contain components other than those mentioned above, such as a dispersant, a leveling agent, an antifouling agent, an antistatic agent, an ultraviolet absorber, an antioxidant, etc. The type of antistatic agent is not particularly limited, and an ionically conductive or electronically conductive antistatic agent can be preferably used. As a specific example of an electronically conductive antistatic agent, Sepulgida (manufactured by Shin-Etsu Polymer Co., Ltd.) using a polythiophene conductive polymer can be preferably used.

[0141] (Inorganic fine particles) Hardness can be increased by adding inorganic fine particles to the hard coat layer. Examples of inorganic fine particles include silica particles, titanium dioxide particles, zirconia particles, aluminum oxide particles, diamond powder, sapphire particles, boron carbide particles, silicon carbide particles, and antimony pentoxide particles. Among them, silica particles and zirconia particles are preferred from the viewpoint of ease of modification.

[0142] The surface of the inorganic fine particles is preferably treated with a surface modifier containing an organic segment. The surface modifier preferably has a functional group capable of forming a bond with the inorganic fine particles or adsorbing to the inorganic particles, and a functional group having high affinity with the organic component in the same molecule. As the surface modifier having a functional group capable of bonding or adsorbing to the inorganic fine particles, a metal alkoxide surface modifier such as silane, aluminum, titanium, zirconium, etc., or a surface modifier having an anionic group such as a phosphoric acid group, a sulfuric acid group, a sulfonic acid group, or a carboxylic acid group is preferable, and among them, a silane alkoxide surface modifier (silane coupling agent) is preferable from the viewpoint of ease of modification. Furthermore, as a functional group having high affinity with the organic component, a functional group capable of chemically bonding with the matrix component may be used which is simply a combination of hydrophilicity and hydrophobicity with the matrix component, but a functional group capable of chemically bonding with the matrix component is preferable, and an ethylenically unsaturated double bond group or a ring-opening polymerizable group is particularly preferable. In the present invention, a preferred inorganic fine particle surface modifier is a curable resin having a metal alkoxide or an anionic group and an ethylenically unsaturated double bond group or a ring-opening polymerizable group in the same molecule. The number of ethylenically unsaturated double bond groups or ring-opening polymerizable groups in one molecule is preferably from 1.0 to 5.0, and more preferably from 1.1 to 3.0. By setting the number of ethylenically unsaturated double bond groups or ring-opening polymerizable groups in one molecule within the above range, the bond between the matrix component and the inorganic fine particles can be strengthened.

[0143] Specific examples of the silane coupling agent include, for example, silane coupling agents having an ethylenically unsaturated double bond group such as 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropyldimethylmethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, 2-(meth)acryloxyethyltrimethoxysilane, 2-(meth)acryloxyethyltriethoxysilane, 4-(meth)acryloxybutyltrimethoxysilane, 4-(meth)acryloxybutyltriethoxysilane, etc., and silane coupling agents having a ring-opening polymerizable group such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane. More specifically, KBM-303, KBM-403, KBM-503, KBM-5103 (all manufactured by Shin-Etsu Chemical Co., Ltd.), and silane coupling agents C-1, C-2, etc. represented by the following structural formula can be mentioned.

[0144]

Chemical formula

[0145]

Chemical formula

[0146] For the inorganic fine particles, it is preferable that 0.2 to 4.0 surface modifiers are bonded or adsorbed per 1 nm 2 of the surface area of the inorganic fine particles, more preferably 0.5 to 3.0 per 1 nm 2 of the surface area of the inorganic fine particles, and even more preferably 0.8 to 2.0 per 1 nm 2 of the surface area of the inorganic fine particles.

[0147] The surface modification of these inorganic fine particles is preferably carried out in a solution. After the inorganic fine particles are synthesized in a solution, a surface modifier is added and stirred, or the inorganic fine particles are mechanically finely dispersed together with the surface modifier, or the inorganic fine particles are finely dispersed and then the surface modifier is added and stirred, or the inorganic fine particles may be surface-modified before being finely dispersed (if necessary, heated or dried, then heated or pH changed), and then finely dispersed. As the solution for dissolving the surface modifier, an organic solvent with high polarity is preferred. Specific examples include known solvents such as alcohols, ketones, and esters.

[0148] The inorganic fine particles have an average primary particle size of 3 to 100 nm, preferably 4 to 50 nm, and more preferably 5 to 20 nm. By setting the average primary particle size within the above range, the bond between the matrix component and the inorganic fine particles can be strengthened. The average primary particle size of inorganic particles in a hard coat film is obtained by observing the cross section of a thin-section sample obtained by slicing the hard coat film with a transmission electron microscope (TEM) at an appropriate magnification (approximately 400,000 times), measuring the diameter of each of 100 primary particles, calculating their volume, and determining the cumulative 50% particle size as the average primary particle size. If the particles are not spherical, the average value of the major and minor diameters is considered to be the diameter of the primary particles. Thin-section samples can be prepared by a microtome method using a cross-section cutting device called an ultramicrotome, or a thin-section processing method using a focused ion beam (FIB) device. When measuring powder particles or particles in a particle dispersion, the powder particles or particle dispersion are observed with a TEM in the same manner as above, and the average primary particle size is calculated.

[0149] The inorganic fine particles may be used alone or in combination of two or more kinds. When using two or more kinds, it is preferable to use particles having different particle diameters from the viewpoint of increasing the volume filling rate of the particles in the hard coat layer.

[0150] In the present invention, when the hard coat layer contains, as the cured product of the polymerizable compound, a cured product of the compound (a3) ​​having a polymerizable functional group and inorganic fine particles, the volume ratio of the inorganic fine particles in the hard coat layer is preferably 50 volume % or more.

[0151] The inorganic fine particles are preferably solid particles from the viewpoint of particle strength. The shape of the inorganic fine particles is most preferably spherical, but may be non-spherical, such as amorphous.

[0152] In the case where the hard coat layer in the present invention contains, as the cured product of the polymerizable compound, a cured product of the compound (a3) ​​having a polymerizable functional group and inorganic fine particles, the content of the cured product of the compound (a3) ​​having a polymerizable functional group and the inorganic fine particles is preferably from 50% by mass to 100% by mass, more preferably from 70% by mass to 100% by mass, and further preferably from 80% by mass to 100% by mass, based on the total mass of the hard coat layer.

[0153] (Other additives) The hard coat layer may contain components other than those mentioned above, such as a dispersant, a leveling agent, an antifouling agent, an antistatic agent, an ultraviolet absorber, an antioxidant, etc. The type of antistatic agent is not particularly limited, and an ionically conductive or electronically conductive antistatic agent can be preferably used. As a specific example of an electronically conductive antistatic agent, Sepulgida (manufactured by Shin-Etsu Polymer Co., Ltd.) using a polythiophene conductive polymer can be preferably used.

[0154] The leveling agent is not particularly limited, but a polymer obtained by polymerizing a monomer having two or more groups with a radically polymerizable double bond, having a weight average molecular weight of 1000 to 50000, and having at least one selected from a fluorine atom, a silicon atom, and a linear or branched alkyl group having 3 or more carbon atoms can be preferably used. Hereinafter, a monomer having two or more groups having a radically polymerizable double bond is also referred to as "monomer (K1)". In addition, a polymer obtained by polymerizing a monomer (K1) having two or more groups having a radically polymerizable double bond, having a weight average molecular weight of 1000 to 50000, and having at least one selected from a fluorine atom, a silicon atom, and a linear or branched alkyl group having 3 or more carbon atoms is also referred to as a "polymer (X)".

[0155] <Monomer (K1)> -Group having a radically polymerizable double bond- The monomer (K1) contains two or more groups having a radical polymerizable double bond. When the monomer (K1) contains two or more groups having a radical polymerizable double bond, the polymer (X) has a branched structure, and the compatibility with the curable component (polyorganosilsesquioxane having a polymerizable group) and the like contained in the composition containing the polymer (X) is improved.

[0156] The group having a radical polymerizable double bond contained in the monomer (K1) is not particularly limited, and the two or more groups having a radical polymerizable double bond contained in the monomer (K1) may be the same or different.

[0157] The number of groups having radical polymerizable double bonds in the monomer (K1) is preferably 3 or more, more preferably 3 to 9, and even more preferably 3 to 6. By making the number of groups having radical polymerizable double bonds 3 or more, the branched structure of the polymer (X) becomes a highly branched structure, the entanglement between the molecular chains of the polymer (X) is reduced, the compatibility with the curable component and the solubility in various organic solvents are improved, and the uniform coatability of the composition and the surface condition of the resulting coating film are improved. In addition, by making the number of groups having radical polymerizable double bonds 9 or less, the molecular weight is prevented from becoming too high, and the solubility in the solvent can be maintained.

[0158] The group having a radically polymerizable double bond is preferably any of the groups represented by the following general formulas (Z1) to (Z6). The multiple groups having radically polymerizable double bonds contained in the monomer (K1) may be the same or different.

[0159] [ka]

[0160] R in general formula (Z3) m1 and R in general formula (Z4) m2 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

[0161] R in general formula (Z3) m1 and R in general formula (Z4) m2 is preferably a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably a hydrogen atom, a methyl group, or an ethyl group.

[0162] The group having a radically polymerizable double bond is preferably a group represented by general formula (Z1), (Z2), (Z3) or (Z4), and more preferably a group represented by general formula (Z1) or (Z2).

[0163] The group represented by the above general formula (Z3) or (Z4) is a group that contains a radically polymerizable double bond and also contains a nitrogen atom.

[0164] -Nitrogen atom-

[0165] The monomer (K1) preferably contains at least one nitrogen atom. When the monomer (K1) contains a nitrogen atom, the polymer (X) also contains a nitrogen atom, and the compatibility of the polymer (X) with the curable component and the like contained in the composition containing the polymer (X) is improved. In particular, when the polymer (X) contains a nitrogen atom, the compatibility of the polymer (X) with the polyorganosilsesquioxane (A) having a polymerizable group is improved.

[0166] The nitrogen atom is preferably contained in the polymer (X) as at least one structure selected from an isocyanuric ring, a urethane bond, an amide bond, and a urea bond, more preferably contained in the polymer (X) as an isocyanuric ring, a urethane bond, or an amide bond, and further preferably contained in the polymer (X) as an isocyanuric ring. That is, the polymer (X) preferably has at least one selected from an isocyanuric ring, a urethane bond, an amide bond, and a urea bond, more preferably has an isocyanuric ring, a urethane bond, or an amide bond, and further preferably has an isocyanuric ring.

[0167] The number of nitrogen atoms contained in the monomer (K1) is preferably 2 or more, and more preferably 3 or more, from the viewpoint of improving compatibility with the curable component and the like.

[0168] The monomer (K1) is preferably a compound represented by any one of the following general formulas (NI) to (NV).

[0169] [ka]

[0170] In the general formula (NI), L 11 , L 12 and L 13 each independently represents a divalent or trivalent linking group; R 11 , R 12 and R 13 each independently represents a hydrogen atom or a methyl group, and n11 to n13 each independently represent 1 or 2. When n11 represents 2, two R 11 may be the same or different. When n12 represents 2, two R 12 may be the same or different. When n13 represents 2, two R 13 may be the same or different.

[0171] [ka]

[0172] In general formula (NII), R 21 and R 22 each independently represent a hydrogen atom or a methyl group. L 21 represents a linking group having a valence of 2 to 6. n21 represents an integer of 1 to 5. When n21 represents an integer of 2 or more, a plurality of R 22 may be the same or different from each other.

[0173]

Chemical formula

[0174] In general formula (NIII), L 31 and L 32 each independently represent a linking group having a valence of 2 to 4, L 33 represents a divalent linking group, R 31 and R 32 each independently represent a hydrogen atom or a methyl group, and n31 and n32 each independently represent an integer of 1 to 3. When n31 represents an integer of 2 or more, a plurality of R 31 may be the same or different from each other. When n32 represents an integer of 2 or more, a plurality of R 32 may be the same or different from each other.

[0175]

Chemical formula

[0176] In general formula (NIV), Y 41 represents a linking group having a valence of 2 to 6, R 41 represents a hydrogen atom or a methyl group, R 42 and R 43 each independently represent a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 10 carbon atoms. n41 represents an integer of 2 to 6. When n41 represents an integer of 2 or more, a plurality of R 41 may be the same or different from each other, and a plurality of R 42may be the same or different, and multiple R 43 may be the same or different.

[0177] [ka]

[0178] In the general formula (NV), Y 51 represents a divalent to hexavalent linking group; R 51 represents a hydrogen atom or a methyl group, R 52 , R 53 and R 54 each independently represents a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 10 carbon atoms. n51 represents an integer of 2 to 6. When n51 represents an integer of 2 or more, a plurality of R 51 may be the same or different, and multiple R 52 may be the same or different, and multiple R 53 may be the same or different, and multiple R 54 may be the same or different.

[0179] In the general formula (NI), L 11 , L 12 and L 13 each independently represents a divalent or trivalent linking group. L 11 , L 12 and L 13 Examples of the divalent linking group represented by include an alkylene group, a cycloalkylene group, an arylene group, -O-, -S-, -CO-, -COO-, -NH-, -NHCO-, -NHCOO-, and a divalent linking group formed by combining these groups. The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and examples thereof include an ethylene group, an n-propylene group, an i-propylene group, an n-butylene group, an n-hexylene group, etc. The alkylene group may be linear or branched. The cycloalkylene group is preferably a cycloalkylene group having 6 to 20 carbon atoms, more preferably a cycloalkylene group having 6 to 10 carbon atoms, and examples thereof include a cyclohexylene group and a cycloheptylene group. The arylene group is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 10 carbon atoms, and examples thereof include a phenylene group and a naphthylene group. The alkylene group, cycloalkylene group, or arylene group may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, an amino group, a cyano group, a nitro group, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, and an acyl group.

[0180] L 11 , L 12 and L 13 The divalent linking group represented by is preferably an alkylene group or a divalent linking group formed by combining an alkylene group with at least one group selected from -O-, -S-, -CO-, -COO-, -NH-, -NHCO-, and -NHCOO-, and is more preferably an alkylene group.

[0181] L 11 , L 12 and L 13 The trivalent linking group represented by the above-mentioned L 11 , L 12 and L 13 Examples of such linking groups include those obtained by removing any one hydrogen atom from the divalent linking group represented by the following formula:

[0182] In the general formula (NI), R 11 , R 12 and R 13 each independently represents a hydrogen atom or a methyl group, and preferably represents a hydrogen atom.

[0183] In formula (NI), n11 to n13 each independently represent 1 or 2. It is preferable that n11 to n13 each represent 1.

[0184] The compound represented by the general formula (NI) can be synthesized according to the method described in JP-A-2004-141732.

[0185] Next, the compound represented by the above general formula (NII) will be described.

[0186] In the general formula (NII), R 21 and R 22 each independently represents a hydrogen atom or a methyl group, and preferably represents a hydrogen atom. L 21 represents a divalent to hexavalent linking group, and the divalent linking group is the same as the above-mentioned L 11 , L 12 and L 13 The divalent linking group represented by L is the same as that represented by L. 21 When represents a trivalent to hexavalent linking group, each of the above L 11 , L 12 and L 13 Examples of linking groups include those obtained by removing any one to four hydrogen atoms from a divalent linking group represented by the following formula: n21 represents an integer of 1 to 5, and preferably an integer of 1 to 3.

[0187] The compound represented by the above general formula (II) can be synthesized according to the method described in JP-A-2012-206992.

[0188] Next, the compound represented by the above general formula (NIII) will be described.

[0189] In general formula (NIII), R 31 and R 32 each independently represents a hydrogen atom or a methyl group, and preferably represents a hydrogen atom. L 31 and L 32 Each independently represents a divalent to tetravalent linking group, and the divalent linking group is the same as the above-mentioned L 11 , L 12 and L 13 The divalent linking group represented by L is the same as that represented by L. 31 and L 32 When represents a trivalent or tetravalent linking group, the above-mentioned L11 , L 12 and L 13 Examples of linking groups include those obtained by removing any one or two hydrogen atoms from a divalent linking group represented by the following formula: L 33 represents a divalent linking group, and the above-mentioned L 11 , L 12 and L 13 The divalent linking group is the same as that represented by the formula (I). n31 and n32 each independently represent an integer of 1 to 3, and preferably represent 1 or 2.

[0190] The compound represented by the above general formula (NIII) can be synthesized according to the method described in JP-A-2016-65199.

[0191] [ka]

[0192] In the general formula (NIV), Y 41 represents a divalent to hexavalent linking group; R 41 represents a hydrogen atom or a methyl group, R 42 and R 43 each independently represents a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 10 carbon atoms. n41 represents an integer of 1 to 6. When n41 represents an integer of 2 or more, a plurality of R 41 may be the same or different, and multiple R 42 may be the same or different, and multiple R 43 may be the same or different.

[0193] Y 41 Examples of the divalent linking group represented by include an alkylene group, a cycloalkylene group, an arylene group, -CO-, or a divalent linking group formed by combining these groups.

[0194] The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and examples thereof include an ethylene group, an n-propylene group, an i-propylene group, an n-butylene group, an n-hexylene group, etc. The alkylene group may be linear or branched. The cycloalkylene group is preferably a cycloalkylene group having 6 to 20 carbon atoms, more preferably a cycloalkylene group having 6 to 10 carbon atoms, and examples thereof include a cyclohexylene group and a cycloheptylene group. The arylene group is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 10 carbon atoms, and examples thereof include a phenylene group and a naphthylene group.

[0195] The alkylene group, cycloalkylene group, or arylene group may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, an amino group, a cyano group, a nitro group, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, and an acyl group.

[0196] Y 41 The divalent linking group represented by is preferably an alkylene group.

[0197] Also, Y 41 When represents a trivalent to hexavalent linking group, each of the above Y 41 Examples of linking groups include those obtained by removing any one to four hydrogen atoms from a divalent linking group represented by the following formula:

[0198] R 41 R represents a hydrogen atom or a methyl group. 41 is preferably a hydrogen atom.

[0199] R 42 and R 43 each independently represents a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 10 carbon atoms. As the alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable. R42 and R 43 preferably represents a hydrogen atom.

[0200] n41 represents an integer of 1 to 6. n41 is preferably an integer of 1 to 4.

[0201] The monomer represented by the general formula (NIV) can be synthesized according to the method described in International Publication No. 2016 / 92844.

[0202] [Chemical formula]

[0203] In the general formula (NV), Y 51 represents a divalent to hexavalent linking group, and R 51 represents a hydrogen atom or a methyl group, and R 52 , R 53 and R 54 each independently represents a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 10 carbon atoms. n51 represents an integer of 1 to 6. When n51 represents an integer of 2 or more, a plurality of R 51 may be the same or different from each other, a plurality of R 52 may be the same or different from each other, a plurality of R 53 may be the same or different from each other, a plurality of R 54 may be the same or different from each other.

[0204] Y 51 Examples of the divalent linking group represented by Y include an alkylene group, a cycloalkylene group, an arylene group, -CO-, or a divalent linking group formed by combining these groups.

[0205] As the alkylene group, an alkylene group having 1 to 20 carbon atoms is preferable, and an alkylene group having 1 to 10 carbon atoms is more preferable. Examples thereof include an ethylene group, an n-propylene group, an i-propylene group, an n-butylene group, an n-hexylene group, and the like. The alkylene group may be linear or branched. The cycloalkylene group is preferably a cycloalkylene group having 6 to 20 carbon atoms, more preferably a cycloalkylene group having 6 to 10 carbon atoms, and examples thereof include a cyclohexylene group and a cycloheptylene group. The arylene group is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 10 carbon atoms, and examples thereof include a phenylene group and a naphthylene group.

[0206] The alkylene group, cycloalkylene group, or arylene group may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, an amino group, a cyano group, a nitro group, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, and an acyl group.

[0207] Y 51 The divalent linking group represented by is preferably an alkylene group.

[0208] Also, Y 51 When represents a trivalent to hexavalent linking group, each of the above Y 51 Examples of linking groups include those obtained by removing any one to four hydrogen atoms from a divalent linking group represented by the following formula:

[0209] R 51 R represents a hydrogen atom or a methyl group. 51 is preferably a hydrogen atom.

[0210] R 52 , R 53 and R 54 each independently represents a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 10 carbon atoms. As the alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 6 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable. R 52 , R 53 and R 54 is preferably a hydrogen atom.

[0211] n51 represents an integer of 1 to 6. n51 is preferably an integer of 1 to 4.

[0212] The monomer represented by the above general formula (NV) can be synthesized according to the method described in WO 2016 / 92844.

[0213] The monomer (K1) is more preferably a monomer represented by the general formula (NI) above.

[0214] As the monomer (K1), a commercially available product may be used. For example, examples of the monomer (K1) containing a nitrogen atom as a urethane bond include UA-306H, UA-306I, UA-306T, UA-510H, UF-8001G, UA-101I, UA-101T, AT-600, AH-600, and AI-600 manufactured by Kyoeisha Chemical Co., Ltd.; U-4HA, U-6HA, U-6LPA, UA-32P, U-15HA, UA-1100H, A-9300, A-9200, A-9300-1CL, and A-9300-3CL manufactured by Shin-Nakamura Chemical Co., Ltd.; and Shikoh UV-1400B, UV-1700B, and UV-6 manufactured by Nippon Synthetic Chemical Industry Co., Ltd. 300B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV-7640B, UV-6630B, UV-7000B, UV-7510B, UV-7461TE, UV-3000B, UV-3200B, UV-3210EA, UV-3310EA, UV-3310B, UV-3500BA, UV-3520TL, UV-3700B, UV-6100B, UV-6640B, UV-2000B, UV-2010B, and UV-2250EA. Further examples include Shikoh UV-2750B manufactured by Nippon Synthetic Chemical Industry Co., Ltd., UL-503LN manufactured by Kyoeisha Chemical Co., Ltd., Unidic 17-806, 17-813, V-4030, and V-4000BA manufactured by Dainippon Ink and Chemicals, Inc., EB-1290K manufactured by Daicel UCB Ltd., and Hi-Cop AU-2010 and AU-2020 manufactured by Tokushiki Co., Ltd.

[0215] Specific examples of the monomer (K1) are shown below, but the present invention is not limited to these.

[0216]

change

[0217]

change

[0218]

change

[0219]

change

[0220]

change

[0221]

change

[0222]

change

[0223]

change

[0224]

change

[0225]

change

[0226] The polymer (X) has at least one selected from a fluorine atom, a silicon atom, and a linear or branched alkyl group having 3 or more carbon atoms. By containing a fluorine atom, a silicon atom, or a linear or branched alkyl group having 3 or more carbon atoms in the polymer (X), the surface tension of the coating film when the composition containing the polymer (X) is applied is further reduced, and the uniform coating property is further improved. In addition, the migration of the polymer (X) to the coating surface is further improved, and the surface condition of the coating surface is also improved.

[0227] As the linear or branched alkyl group having 3 or more carbon atoms, a linear or branched alkyl group having 3 to 30 carbon atoms is preferable, and a linear or branched alkyl group having 4 to 20 carbon atoms is more preferable.

[0228] The polymer (X) more preferably contains a fluorine atom.

[0229] To introduce at least one selected from a fluorine atom, a silicon atom, and a linear or branched alkyl group having 3 or more carbon atoms into the polymer (X), at least one selected from a fluorine atom, a silicon atom, and a linear or branched alkyl group having 3 or more carbon atoms may be introduced into the above-mentioned monomer (K1) and polymerized with the monomer (K1). Alternatively, at least one selected from a fluorine atom, a silicon atom, and a linear or branched alkyl group having 3 or more carbon atoms may be introduced into a raw material monomer other than the monomer (K1) (referred to as monomer (K2)), and at least one selected from a fluorine atom, a silicon atom, and a linear or branched alkyl group having 3 or more carbon atoms may be copolymerized with the monomer (K1) to introduce at least one selected from a fluorine atom, a silicon atom, and a linear or branched alkyl group having 3 or more carbon atoms into the polymer (X). From the viewpoint of improving the surface condition of the coating film, it is preferable to introduce at least one selected from a fluorine atom, a silicon atom, and a linear or branched alkyl group having 3 or more carbon atoms into the polymer (X) by copolymerizing the monomer (K1) and the monomer (K2).

[0230] <Monomer (K2)> The monomer (K2) preferably has at least one selected from a fluorine atom, a silicon atom, and a linear or branched alkyl group having 3 or more carbon atoms. The fluorine atom is preferably contained in the monomer (K2) in the form of an alkyl group having 1 to 20 carbon atoms and at least one fluorine atom, or an alkenyl group having 2 to 20 carbon atoms and at least one fluorine atom. The silicon atom is preferably contained in the monomer (K2) as a siloxane bond, and more preferably contained in the monomer (K2) as a polysiloxane structure.

[0231] The monomer (K2) is preferably a compound having a (meth)acryloyl group, and more preferably any of the compounds represented by the following general formulas (s1) to (s3).

[0232] [ka]

[0233] In general formula (s1), R 1s represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; R 2s represents an alkyl group having 1 to 20 carbon atoms and at least one fluorine atom, or an alkenyl group having 2 to 20 carbon atoms and at least one fluorine atom.

[0234] R 1s preferably represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, still more preferably represents a hydrogen atom, a methyl group, an ethyl group, or an n-propyl group, and particularly preferably represents a hydrogen atom or a methyl group.

[0235] R 2a The alkyl group or alkenyl group represented by the formula (I) preferably has 1 to 15 carbon atoms, and more preferably has 1 to 10 carbon atoms. R 2a The alkyl or alkenyl group represented by the formula (I) preferably has 1 to 20 fluorine atoms, and more preferably has 3 to 17 fluorine atoms.

[0236] From the viewpoints of reducing the surface energy of the composition containing the polymer (X), enhancing uniform coating properties, and improving the surface condition, R 2s is preferably an alkyl group having 1 to 10 carbon atoms and having at least one fluorine atom, or an alkenyl group having 2 to 10 carbon atoms and having at least one fluorine atom, more preferably an alkyl group having 1 to 10 carbon atoms and having at least one fluorine atom; R 2s It is particularly preferable that half or more of the carbon atoms contained in the above formula have a fluorine atom as a substituent.

[0237] The compound represented by general formula (s1) is more preferably a compound represented by the following general formula (s11).

[0238] [ka]

[0239] In general formula (s11), R 1s represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, ma and na each independently represent an integer of 0 or more, X 1 represents a hydrogen atom or a fluorine atom.

[0240] R in general formula (s11) 1s R in general formula (s1) 1s The same applies to preferred examples. ma and na each independently represent an integer of 0 or more. ma is preferably an integer of 1-10, and more preferably an integer of 1-5. Preferably, na is an integer of 4-12, and more preferably an integer of 4-10. X represents a hydrogen atom or a fluorine atom, and is preferably a fluorine atom.

[0241] Examples of the monomer represented by the general formula (s1) include 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3,3-pentafluoropropyl (meth)acrylate, 2-(perfluorobutyl)ethyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate, 2-(perfluorooctyl)ethyl (meth)acrylate, 2-(perfluorodecyl)ethyl (meth)acrylate, 2-(perfluoro-3-methylbutyl)ethyl (meth)acrylate, 2-(perfluoro-5-methylhexyl)ethyl (meth)acrylate, 2-(perfluoro-7-methyloctyl)ethyl (meth)acrylate, 1H,1H,3H-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, 1H,1H, 7H-dodecafluoroheptyl (meth)acrylate, 1H,1H,9H-hexadecafluorononyl (meth)acrylate, 1H-1-(trifluoromethyl)trifluoroethyl (meth)acrylate, 1H,1H,3H-hexafluorobutyl (meth)acrylate, 3-perfluorobutyl-2-hydroxypropyl (meth)acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth)acrylate, 3-perfluorooctyl-2-hydroxypropyl (meth)acrylate, 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl (meth)acrylate, 3-(perfluoro-5-methylhexyl)-2-hydroxypropyl (meth)acrylate, 3-(perfluoro-7-methyloctyl)-2-hydroxypropyl (meth)acrylate, and the like.

[0242] [ka]

[0243] In general formula (s2), R 1s represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; R 3s , R 4s , R 6s and R 7seach independently represents an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; R 5s represents an alkyl group having 1 to 20 carbon atoms, mm represents an integer of 1 to 10, and nn represents an integer of 1 or more. 3s and R 4s may be the same or different.

[0244] R in general formula (s2) 1s R in general formula (s1) 1s The same applies to preferred examples. R 3s , R 4s , R 6s and R 7s Examples of the alkyl group having 1 to 20 carbon atoms represented by R include a methyl group, an ethyl group, and a hexyl group. 3s , R 4s , R 6s and R 7s The alkyl group represented by is preferably an alkyl group having 1 to 10 carbon atoms. R 3s , R 4s , R 6s and R 7s Examples of the haloalkyl group having 1 to 20 carbon atoms represented by R include a trifluoromethyl group and a pentafluoroethyl group. 3s , R 4s , R 6s and R 7s The haloalkyl group represented by is preferably a fluorinated alkyl group having 1 to 10 carbon atoms. R 3s , R 4s , R 6s and R 7s Examples of the aryl group having 6 to 20 carbon atoms represented by R include a phenyl group and a naphthyl group. 3s , R 4s , R 6s and R 7s The aryl group represented by is preferably an aryl group having 6 to 20 carbon atoms. R 3s , R 4s , R 6s and R7s is preferably a methyl group, a trifluoromethyl group, or a phenyl group, and more preferably a methyl group. R 5s Examples of the alkyl group having 1 to 20 carbon atoms represented by R include a methyl group, an ethyl group, and a hexyl group. 5s The alkyl group represented by is preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms.

[0245] mm represents an integer of 1 to 10. mm is preferably an integer of 1 to 6. nn is preferably an integer of 1 to 1000, more preferably an integer of 20 to 500, and further preferably an integer of 30 to 200.

[0246] As the monomer represented by general formula (s2), commercially available products may be used, and examples thereof include polysiloxane macromers containing one terminal (meth)acryloyl group (for example, Silaplane FM-0721, Silaplane 0725, Silaplane 0711 (all trade names, manufactured by JNC Corporation), AK-5, AK-30, AK-32 (all trade names, manufactured by Toagosei Co., Ltd.), KF-100T, X-22-169AS, KF-102, X-22-3701IE, X-22-164B, X-22-164C, X-22-5002, X-22-173B, X-22-174D, X-22-167B, X-22-161AS (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0247] [ka]

[0248] In general formula (s3), R 1s represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; R 8s represents a linear or branched alkyl group having 3 or more carbon atoms.

[0249] R in general formula (s3) 1s R in general formula (s1) 1s The same applies to preferred examples. R8s The linear or branched alkyl group having 3 or more carbon atoms represented by is preferably a linear or branched alkyl group having 3 to 30 carbon atoms, and more preferably a linear or branched alkyl group having 6 to 20 carbon atoms.

[0250] The monomer (K2) is preferably a monomer represented by the above general formula (s1). That is, the polymer (X) preferably has a structure represented by the following general formula (s).

[0251] [ka]

[0252] In general formula (s), R 1s represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; R 2s represents an alkyl group having 1 to 20 carbon atoms and at least one fluorine atom, or an alkenyl group having 1 to 20 carbon atoms and at least one fluorine atom. * represents a bond.

[0253] In general formula (s), R 1s and R 2s is R in the above general formula (s1). 1s and R 2s The same applies to preferred examples. * represents a bond.

[0254] The content of the structure selected from fluorine atoms, silicon atoms, and linear or branched alkyl groups having 3 or more carbon atoms in the polymer (X) can be appropriately adjusted depending on the structure used, but is preferably 1 to 99 mol %, more preferably 10 to 90 mol %.

[0255] As described above, the polymer (X) may be a homopolymer of the monomer (K1) or a copolymer of the monomer (K1) and the monomer (K2). When the polymer (X) is a copolymer of the monomer (K1) and the monomer (K2), the ratio of the two can be appropriately adjusted depending on the type of monomer used, but from the viewpoint of improving the surface condition and solvent extractability, the content of the monomer (K2) relative to the total monomer amount is preferably 20 to 90 mol%, more preferably 40 to 80 mol%. By making it 20 mol% or more, it is possible to maintain good surface condition, and by making it 90 mol% or less, it is possible to maintain good solvent extractability. By making it 40 to 80 mol%, it is possible to maintain a good balance between improving the surface condition of the polymer (X) and solvent extractability.

[0256] The polymer (X) may be a polymer obtained by polymerizing raw material monomers other than the monomer (K1) and the monomer (K2) in combination.

[0257] <Weight average molecular weight (Mw)> The weight-average molecular weight of the polymer (X) is 1000 to 50000. By making the weight-average molecular weight 50000 or less, the polymer (X) becomes soluble in a general-purpose organic solvent, so that a composition for forming a hard coat layer can be prepared as a solution in which the polymer (X) is dissolved in an organic solvent, and it becomes possible to coat various general-purpose substrates such as triacetyl cellulose (TAC), polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate resin (PMMA) with a uniform coating surface state. In addition, by making the Mw 1000 or more, the effect of improving the surface state is increased. In the present invention, the polymer (X) being soluble in an organic solvent means that the turbidity of the solution after mixing the polymer (X) / organic solvent (25°C) at a mass ratio of 1 / 4 and leaving the mixture for 5 minutes is 1.0 ppm (parts per million) or less.

[0258] The weight average molecular weight of the polymer (X) is more preferably from 1,000 to 30,000, further preferably from 1,000 to 8,000, and particularly preferably from 1,000 to 5,000.

[0259] The molecular weight distribution (Mw / Mn) of the polymer (X) is preferably from 1.00 to 5.00, and more preferably from 1.00 to 3.00.

[0260] The weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution of the polymer (X) are values ​​measured by gel permeation chromatography (GPC) under the following conditions. [Eluent]: Tetrahydrofuran (THF) [Device name]: Ecosec HLC-8220GPC (Tosoh Corporation) [Column]: TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZM200 (manufactured by Tosoh Corporation) [Column temperature]: 40℃ [Flow rate]:50ml / min [Molecular weight]: Standard polystyrene equivalent

[0261] The content of hydroxyl groups in the polymer (X) is preferably 0% by mass to 10% by mass, as calculated from the following formula, relative to the amount of polyorganosilsesquioxane (A) having a polymerizable group added in the composition (also referred to as the OH content).

[0262] (Amount of polymer (X) added / Amount of polyorganosilsesquioxane having polymerizable group added)×(OH content in polymer (X))×100 (%)

[0263] For example, when the polymer (X) is obtained by polymerizing the monomer (K1) and the monomer (K2), and the monomer (K1) contains a hydroxyl group, the OH content in the polymer (X) is calculated by the following formula.

[0264] [Content (g) of polymer (X) / Content (g) of polyorganosilsesquioxane having a polymerizable group] × (Content (mass ratio) of monomer (K1) in polymer (X)) × [(Molecular weight of OH) × (Number of OH groups in monomer (K1)) / (Molecular weight of monomer (K1))]

[0265] The OH content calculated from the above formula is preferably 0 to 0.006% by mass, more preferably 0 to 0.002% by mass, and even more preferably 0 to 0.0001% by mass. A small OH content reduces the interaction with the OH group in the polyorganosilsesquioxane (A) having a polymerizable group, and the solvent extractability of the polymer (X) is improved.

[0266] <Synthesis method> As a synthesis method for the polymer (X), radical polymerization such as solution, suspension and emulsion polymerization is preferred from the viewpoint of controlling the molecular weight, and solution polymerization is particularly preferred.

[0267] Regarding the polymerization solvent used in the reaction, various organic solvents can be suitably used. Examples of such organic solvents include dibutyl ether, dimethoxyethane, diethoxyethane, propylene oxide, 1,4-dioxane, 1,3-dioxolane, 1,3,5-trioxane, tetrahydrofuran, anisole, phenetole, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, acetone, methyl ethyl ketone (MEK), diethyl ketone, dipropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone, 2-methoxyacetate, 2-ethoxyacetate, 2-ethoxyethyl acetate, 2-ethoxypropionate, 2-methoxyethanol, 2-propoxyethanol, 2-butoxyethane, ethyl ketone ... Examples of the solvent include ethanol, 1,2-diacetoxyacetone, acetylacetone, diacetone alcohol, methyl acetoacetate, ethyl acetoacetate, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, t-amyl alcohol, cyclohexyl alcohol, isobutyl acetate, methyl isobutyl ketone (MIBK), 2-octanone, 2-pentanone, 2-hexanone, ethylene glycol ethyl ether, ethylene glycol isopropyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, ethyl carbitol, butyl carbitol, hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane, benzene, toluene, and xylene. These can be used alone or in combination of two or more.

[0268] As the radical polymerization initiator, any known radical polymerization initiator can be used without any limitation.

[0269] Here, in the radical solution polymerization, the number average molecular weight (Mn) of the polymer (X) obtained is represented by the following formula (1).

[0270]

number

[0271] The parameters in the above formula (1) are as follows: [I], [M], and [S] are the concentrations (mol / L) of the initiator, monomer, and solvent, respectively. k d : initiator decomposition rate constant, k t : termination reaction rate constant, k p : growth reaction rate constant, Cs(=k trs / k p ): Chain transfer constant of the solvent (k trs : chain transfer reaction rate constant to the solvent), C M (=k trM / k p ): Chain transfer constant of monomer (k trM : chain transfer reaction rate constant to monomer), f: initiator efficiency, M I : Molecular weight of monomer

[0272] Factors that affect the molecular weight of the polymer (X) synthesized by solution radical polymerization include the monomer / initiator concentration ratio [M] / [I] and the monomer / solvent concentration ratio [M] / [S]. In other words, the molecular weight of the polymer (X) can be controlled by lowering the monomer concentration and / or adjusting the initiator concentration.

[0273] The polymer (X) can be solubilized in a general-purpose organic solvent (eg, MEK) by adjusting the concentration of the compound (M) and / or the concentration of the initiator in the polymerization reaction.

[0274] The radical polymerization concentration (monomer concentration relative to the solvent during radical solution polymerization) is preferably from 3 to 40% by mass, and more preferably from 5 to 35% by mass.

[0275] From the viewpoint of solubility in organic solvents, the amount of the radical polymerization initiator is preferably 250 mol % or more relative to the di(poly)functional monomer.

[0276] Specific examples of the polymer (X) are shown below, but the present invention is not limited to these.

[0277] [ka]

[0278] [ka]

[0279] [ka]

[0280] The content of the polymer (X) in the composition for forming a hard coat layer can be appropriately adjusted depending on the coating amount and the effect of improving the surface condition of the polymer (X), but is preferably 0.001% by mass to 20% by mass, more preferably 0.005% by mass to 10% by mass, and even more preferably 0.01% by mass to 1% by mass, based on the total solid content. The solid content refers to components other than the solvent.

[0281] In addition, when the hard coat layer has a cured product of polyorganosilsesquioxane (a1) having an epoxy group, the hard coat layer may or may not contain a cured product of a compound having a (meth)acryloyl group. The content of the cured product of the compound having a (meth)acryloyl group is preferably less than 10 mass% with respect to the total amount of the polyorganosilsesquioxane (a1) and the cured product of the (meth)acrylate compound. By making the content of the cured product of the (meth)acrylate compound in the hard coat layer less than 10 mass%, the deformation recovery of the hard coat film is improved, and as a result, the hardness is increased.

[0282] (Film thickness) The thickness of the hard coat layer is not particularly limited, but is preferably from 1 to 100 μm, more preferably from 5 to 50 μm, and further preferably from 10 to 20 μm. The thickness of the hard coat layer is calculated by observing the cross section of the hard coat film under an optical microscope. Cross-sectional samples can be prepared by a microtome method using a cross-section cutting device called an ultramicrotome, or a cross-section processing method using a focused ion beam (FIB) device.

[0283] <Mixed layer> The hard coat film of the present invention may have a mixed layer between the hard coat layer and the scratch-resistant layer. When the hard coat layer contains a cured product of the polyorganosilsesquioxane (a1) having an epoxy group, it is preferable to have a mixed layer containing a cured product of the compound (b1) having an epoxy group and a cured product of the compound (b2) having two or more (meth)acryloyl groups in one molecule. The cured product of the compound (b1) having an epoxy group and the cured product of the compound (b2) having two or more (meth)acryloyl groups in one molecule are preferably obtained by curing a curable composition containing the compound (b1) having an epoxy group and the compound (b2) having two or more (meth)acryloyl groups in one molecule by heating and / or irradiating with ionizing radiation.

[0284] (Compound (b1) having an epoxy group) As the compound (b1) having an epoxy group (also referred to as "epoxy compound (b1)"), a compound having one or more epoxy groups (oxirane rings) in the molecule can be used, and examples thereof include, but are not limited to, epoxy compounds containing an alicyclic ring, aromatic epoxy compounds, aliphatic epoxy compounds, polyorganosilsesquioxane (a1) having an epoxy group used in forming the above-mentioned hard coat layer, and the like.

[0285] Examples of the epoxy compound containing an alicyclic ring include known compounds having one or more alicyclic rings and one or more epoxy groups in the molecule, and are not particularly limited. (1) Compounds having an alicyclic epoxy group; (2) Compounds in which an epoxy group is directly bonded to an alicyclic ring via a single bond; (3) Compounds having an alicyclic ring and a glycidyl ether group in the molecule (glycidyl ether type epoxy compounds).

[0286] The above (1) compound having an alicyclic epoxy group includes a compound represented by the following formula (i).

[0287] [ka]

[0288] In the above formula (i), Y represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include a divalent hydrocarbon group, an alkenylene group in which a part or all of the carbon-carbon double bonds are epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and a group in which a plurality of these are linked together.

[0289] Examples of the divalent hydrocarbon group include a substituted or unsubstituted linear or branched alkylene group having 1 to 18 carbon atoms, and a divalent substituted or unsubstituted alicyclic hydrocarbon group. Examples of the alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, an i-propylene group, and an n-propylene group. Examples of the divalent alicyclic hydrocarbon group include a divalent cycloalkylene group (including a cycloalkylidene group) such as a 1,2-cyclopentylene group, a 1,3-cyclopentylene group, a cyclopentylidene group, a 1,2-cyclohexylene group, a 1,3-cyclohexylene group, a 1,4-cyclohexylene group, and a cyclohexylidene group.

[0290] Examples of the alkenylene group in the alkenylene group in which some or all of the carbon-carbon double bonds have been epoxidized (sometimes referred to as "epoxidized alkenylene group") include linear or branched alkenylene groups having 2 to 8 carbon atoms, such as vinylene group, propenylene group, 1-butenylene group, 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group, and octenylene group. In particular, the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds have been epoxidized, and more preferably an alkenylene group in which all of the carbon-carbon double bonds have been epoxidized and have 2 to 4 carbon atoms.

[0291] Representative examples of the alicyclic epoxy compound represented by the above formula (i) include 3,4,3',4'-diepoxybicyclohexane and compounds represented by the following formulas (i-1) to (i-10). In the following formulas (i-5) and (i-7), l and m each represent an integer of 1 to 30. In the following formula (i-5), R' is an alkylene group having 1 to 8 carbon atoms, and among these, a linear or branched alkylene group having 1 to 3 carbon atoms, such as a methylene group, an ethylene group, an n-propylene group, or an i-propylene group, is preferred. In the following formulas (i-9) and (i-10), n1 to n6 each represent an integer of 1 to 30. Other examples of the alicyclic epoxy compound represented by the above formula (i) include 2,2-bis(3,4-epoxycyclohexyl)propane, 1,2-bis(3,4-epoxycyclohexyl)ethane, 2,3-bis(3,4-epoxycyclohexyl)oxirane, and bis(3,4-epoxycyclohexylmethyl)ether.

[0292] [ka]

[0293] [ka]

[0294] Examples of the compound (2) in which an epoxy group is directly bonded to an alicyclic ring via a single bond include a compound represented by the following formula (ii).

[0295] [ka]

[0296] In formula (ii), R" is a group (p-valent organic group) obtained by removing p hydroxyl groups (-OH) from the structural formula of p-valent alcohol, and p and n each represent a natural number. Examples of p-valent alcohols [R"(OH)p] include polyhydric alcohols (alcohols having 1 to 15 carbon atoms, etc.) such as 2,2-bis(hydroxymethyl)-1-butanol. p is preferably 1 to 6, and n is preferably 1 to 30. When p is 2 or more, n in the groups in ( ) (in the outer parentheses) may be the same or different. Specific examples of the compound represented by formula (ii) include 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol [for example, trade name "EHPE3150" (manufactured by Daicel Corporation)], etc.

[0297] Examples of the above-mentioned (3) compound having an alicyclic ring and a glycidyl ether group in the molecule include, for example, glycidyl ethers of alicyclic alcohols (particularly, alicyclic polyhydric alcohols). More specifically, for example, compounds obtained by hydrogenating 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 Examples of such epoxy compounds include hydrogenated compounds of bisphenol F type epoxy compounds such as [3-(2,3-epoxypropoxy)cyclohexyl]methane (hydrogenated bisphenol F type epoxy compounds); hydrogenated biphenol type epoxy compounds; hydrogenated phenol novolac type epoxy compounds; hydrogenated cresol novolac type epoxy compounds; hydrogenated cresol novolac type epoxy compounds of bisphenol A; hydrogenated naphthalene type epoxy compounds; hydrogenated epoxy compounds of epoxy compounds obtained from trisphenolmethane; and hydrogenated epoxy compounds of the aromatic epoxy compounds listed below.

[0298] Examples of the aromatic epoxy compounds include epi-bis-type glycidyl ether epoxy resins obtained by a condensation reaction between bisphenols [e.g., bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, etc.] and epihalohydrin; high molecular weight epi-bis-type glycidyl ether epoxy resins obtained by further addition reaction of these epi-bis-type glycidyl ether epoxy resins with the above-mentioned bisphenols; phenols [e.g., phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol Novolak alkyl type glycidyl ether epoxy resins obtained by condensing polyhydric alcohols obtained by the condensation reaction of polyphenols (e.g., phenolic acid, phenol F, bisphenol S, etc.) with aldehydes (e.g., formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, salicylaldehyde, etc.) with epihalohydrin; epoxy compounds in which two phenol 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 the phenol skeletons, either directly or via an alkyleneoxy group.

[0299] Examples of the aliphatic epoxy compound include glycidyl ethers of s-valent alcohols (where s is a natural number) that do not have a cyclic structure; glycidyl esters of monovalent or polyvalent carboxylic acids (e.g., acetic acid, propionic acid, butyric acid, stearic acid, adipic acid, sebacic acid, maleic acid, itaconic acid, etc.); epoxidized products of oils and fats having double bonds, such as epoxidized linseed oil, epoxidized soybean oil, and epoxidized castor oil; and epoxidized products of polyolefins (including polyalkadienes), such as epoxidized polybutadiene. Examples of the s-valent alcohols not having a cyclic structure include monohydric alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, and 1-butanol; dihydric alcohols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol; and trihydric or higher polyhydric alcohols such as glycerin, diglycerin, erythritol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and sorbitol. The s-valent alcohol may be polyether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol, and the like.

[0300] The epoxy compound (b1) is preferably a polyorganosilsesquioxane having an epoxy group, and the preferred range is the same as that of the polyorganosilsesquioxane (a1) having an epoxy group of the hard coat layer described above.

[0301] The epoxy compound (b1) may be used alone or in combination of two or more kinds having different structures.

[0302] The content of the cured epoxy compound (b1) is preferably from 10 to 90% by mass, more preferably from 20 to 80% by mass, and even more preferably from 25 to 75% by mass, based on the total mass of the mixed layer.

[0303] (Compound (b2) having two or more (meth)acryloyl groups in one molecule) The compound (b2) having two or more (meth)acryloyl groups in one molecule (also referred to as "polyfunctional (meth)acrylate compound (b2)") is preferably a compound having three or more (meth)acryloyl groups in one molecule. The polyfunctional (meth)acrylate compound (b2) may be a crosslinkable monomer, a crosslinkable oligomer, or a crosslinkable polymer. Examples of the crosslinkable oligomer or crosslinkable polymer include polyorganosilsesquioxane (c1) having a radically polymerizable double bond-containing group, which will be described later.

[0304] The polyfunctional (meth)acrylate compound (b2) may be an ester of polyhydric alcohol and (meth)acrylic acid.Specific examples include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol hexa(meth)acrylate, etc., but in terms of high crosslinking, pentaerythritol triacrylate, pentaerythritol tetraacrylate, or dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, or a mixture thereof are preferred. As the polyfunctional (meth)acrylate compound (b2), a compound having two or more (meth)acryloyl groups and a urethane bond in one molecule (urethane (meth)acrylate) is also preferred.

[0305] The polyfunctional (meth)acrylate compound (b2) may be used alone or in combination of two or more compounds having different structures.

[0306] The content of the cured product of the polyfunctional (meth)acrylate compound (b2) in the mixed layer is preferably 10% by mass or more based on the total amount of the cured product of the epoxy compound (b1) and the cured product of the polyfunctional (meth)acrylate compound (b2). By setting the content of the cured product of the polyfunctional (meth)acrylate compound (b2) in the mixed layer within the above range, the scratch resistance of the hard coat film can be improved. The content of the cured product of the polyfunctional (meth)acrylate compound (b2) in the mixed layer is preferably 10% by mass to 90% by mass, and more preferably 20% by mass to 80% by mass, based on the total amount of the cured product of the epoxy compound (b1) and the cured product of the polyfunctional (meth)acrylate compound (b2).

[0307] (Other additives) The mixed layer may contain components other than those described above, such as a dispersant, a leveling agent, an antifouling agent, an antistatic agent, an ultraviolet absorber, an antioxidant, and a cured product of another polymerizable compound. The type of antistatic agent is not particularly limited, and an ion-conductive or electron-conductive antistatic agent can be preferably used. A specific example of an electron-conductive antistatic agent that can be preferably used is Sepulgida (manufactured by Shin-Etsu Polymer Co., Ltd.), which uses a polythiophene conductive polymer. Examples of the cured product of other polymerizable compounds include cured products of compounds having an epoxy group and a (meth)acryloyl group in one molecule. Specific examples of the compounds include cured products of Cyclomer M100 manufactured by Daicel, Light Ester G (trade name) manufactured by Kyoeisha Chemical Co., Ltd., 4HBAGE manufactured by Nippon Kasei Co., Ltd., SP series (trade name) manufactured by Showa Polymer Co., Ltd., such as SP-1506, 500, SP-1507, 480, VR series (trade name) manufactured by Showa Polymer Co., Ltd., EA-1010 / ECA, EA-11020, EA-1025, EA-6310 / ECA (trade name) manufactured by Shin-Nakamura Chemical Co., Ltd.

[0308] (Film thickness) When the hard coat film of the present invention has a mixed layer, the thickness of the mixed layer is preferably 0.05 μm to 10 μm. By making it 0.05 μm or more, the scratch resistance of the film is improved, and by making it 10 μm or less, the hardness and repeated bending resistance are improved. The thickness of the mixed layer is more preferably 0.1 μm to 5 μm, and further preferably 0.1 μm to 3 μm.

[0309] In the hard coat film of the present invention, the hard coat layer and the mixed layer are preferably bonded by a covalent bond. The epoxy group of the polyorganosilsesquioxane (a1) in the hard coat layer and the epoxy group of the epoxy compound (b1) in the mixed layer form a bond at the interface between the two layers, resulting in a highly adhesive laminate structure, which is particularly preferred in that it is possible to exhibit higher scratch resistance.

[0310] <Abrasion resistant layer> The hard coat film of the present invention has a scratch-resistant layer.

[0311] The scratch-resistant layer contains a cured product of polyorganosilsesquioxane (c1) having a group containing a radically polymerizable double bond (also referred to as "polyorganosilsesquioxane (c1)"). The cured product of the polyorganosilsesquioxane (c1) is preferably obtained by curing a curable composition containing the polyorganosilsesquioxane (c1) by heating and / or irradiation with ionizing radiation.

[0312] Examples of the group containing a radically polymerizable double bond contained in the polyorganosilsesquioxane (c1) include groups containing a (meth)acryloyl group, a vinyl group, a styryl group, an allyl group, etc., and among these, a group containing a (meth)acryloyl group is preferred, and a group containing an acryloyl group is more preferred.

[0313] The polyorganosilsesquioxane (c1) having a group containing a radically polymerizable double bond has at least a siloxane constituent unit containing a group containing a (meth)acryloyl group, and is preferably a polyorganosilsesquioxane represented by the following general formula (2).

[0314] [ka]

[0315] In the general formula (2), Ra represents a group containing a (meth)acryloyl group, and Rc represents a monovalent substituent. t and u represent the ratio of Ra and Rc in the general formula (2), where t+u=100, t is greater than 0, and u is 0 or greater. When there are multiple Ra and Rc in the general formula (2), the multiple Ra and Rc may be the same or different. When there are multiple Rc in the general formula (2), the multiple Rc may form a bond with each other.

[0316] In the general formula (2), [SiO 1.5 represents a structural portion constituted by a siloxane bond (Si-O-Si) in the polyorganosilsesquioxane. In the general formula (2), [SiO 1.5 The structural portion represented by the formula "1" may be any of a random structure, a ladder structure, a cage structure, and the like, and is not particularly limited. From the viewpoint of pencil hardness, it is preferable that the ladder structure is contained in a large amount. By forming the ladder structure, the deformation recovery property of the hard coat film can be maintained well. The formation of the ladder structure is observed when the 1020-1050 cm -1 This can be qualitatively confirmed by the presence or absence of absorption due to the Si-O-Si stretching characteristic of the ladder structure that appears in the vicinity.

[0317] In formula (2), Ra represents a group containing a (meth)acryloyl group. Examples of the group containing a (meth)acryloyl group include known groups having a (meth)acryloyl group. Ra is preferably a group represented by the following general formula (1a).

[0318] *-R 11a -OCO-CR 12a =CH 2 (1a)

[0319] In general formula (1a), * represents a linking portion to Si in general formula (2), and R 11a represents a substituted or unsubstituted alkylene group or a substituted or unsubstituted phenylene group; R 12a represents a hydrogen atom or a substituted or unsubstituted alkyl group.

[0320] R 11a represents a substituted or unsubstituted alkylene group, or a substituted or unsubstituted phenylene group. R 11a The substituted or unsubstituted alkylene group represented by the formula (I) includes a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms. Examples of the alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a propylene group, an isopropylene group, an n-butylene group, an isobutylene group, an s-butylene group, a t-butylene group, an n-pentylene group, an isopentylene group, an s-pentylene group, a t-pentylene group, an n-hexylene group, an isohexylene group, an s-hexylene group, and a t-hexylene group. When the alkylene group has a substituent, examples of the substituent include a hydroxyl group, a carboxyl group, an alkoxy group, an aryl group, a heteroaryl group, a halogen atom, a nitro group, a cyano group, and a silyl group.

[0321] R 11a When the phenylene group represented by the formula (I) has a substituent, examples of the substituent include a hydroxyl group, a carboxyl group, an alkoxy group, an alkyl group, and a halogen atom.

[0322] R 11ais preferably an unsubstituted linear alkylene group having 1 to 3 carbon atoms, and more preferably a propylene group.

[0323] R 12a represents a hydrogen atom or a substituted or unsubstituted alkyl group. R 12a The substituted or unsubstituted alkyl group represented by the formula (I) includes a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms. When the alkyl group has a substituent, examples of the substituent include a hydroxyl group, a carboxyl group, an alkoxy group, an aryl group, a heteroaryl group, a halogen atom, a nitro group, a cyano group, and a silyl group. R 12a is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

[0324] Ra is also preferably a group containing a plurality of (meth)acryloyl groups, and is, for example, preferably a group represented by the following general formula (2a).

[0325] [ka]

[0326] In general formula (2a), * represents a linking portion to Si in general formula (2), L 2a represents a single bond or a divalent linking group, R 22a represents a hydrogen atom or a substituted or unsubstituted alkyl group; L 3a represents a linking group having a valence of na+1, and na represents an integer of 2 or greater.

[0327] L 2a Examples of the divalent linking group represented by the formula (I) include a substituted or unsubstituted alkylene group (preferably having 1 to 10 carbon atoms), -O-, -CO-, -COO-, -S-, -NH-, and divalent linking groups obtained by combinations of these. The substituted or unsubstituted alkylene group is R 11a Examples of the substituted or unsubstituted alkylene groups include those represented by the following formula:

[0328] L 2a is preferably a group in which two adjacent carbon atoms in a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms are bonded via at least one bond selected from -O-, -CO-, -COO-, -S-, and -NH-.

[0329] R 22a R in general formula (1a) 12a The same applies to preferred examples. Preferably, na represents an integer of 2 to 4, and more preferably 2 or 3.

[0330] L 3a represents a linking group having a valence of n+1, and preferably represents a hydrocarbon group having a valence of n+1. L 3a When represents a hydrocarbon group with a valence of (na+1), it may further have a substituent (e.g., a hydroxyl group, a carboxyl group, an alkoxy group, an aryl group, or a halogen atom), and may contain a heteroatom (e.g., an oxygen atom, a sulfur atom, or a nitrogen atom) in the hydrocarbon chain.

[0331] In addition, Ra in the general formula (2) is derived from a group (a group other than an alkoxy group and a halogen atom; for example, Ra in the hydrolyzable silane compound represented by the formula (A) described later) bonded to a silicon atom in the hydrolyzable trifunctional silane compound used as a raw material for the polyorganosilsesquioxane.

[0332] Specific examples of Ra are shown below, but the present invention is not limited to these. In the following specific examples, * represents the linking portion to Si in general formula (2).

[0333] [ka]

[0334] In formula (2), Rc represents a monovalent group. The monovalent group represented by Rc in the general formula (2) has the same meaning as Rc in the general formula (1), and the preferred groups are also the same. However, in order to maintain a good deformation recovery rate, it is preferable that the monovalent group represented by Rc in the general formula (2) does not contain a perfluoropolyether group.

[0335] When there are multiple Rc's in general formula (2), the multiple Rc's may form a bond with each other. It is preferable that two or three Rc's form a bond with each other, and it is more preferable that two Rc's form a bond with each other.

[0336] The group formed by combining two Rc's in the general formula (2) (Rc 2 ), a group formed by combining three Rc together (Rc 3 ) is a group formed by combining two Rc's in the above general formula (1) together (Rc 2 ), a group formed by combining three Rc together (Rc 3 ) and the preferred groups are also the same.

[0337] In addition, Rc in the general formula (2) is a group bonded to a silicon atom in the hydrolyzable silane compound used as a raw material for polyorganosilsesquioxane (a group other than an alkoxy group and a halogen atom; for example, Rc in the hydrolyzable silane compound represented by the above formulas (C1) to (C3) 1 ~Rc 3 etc.)

[0338] In general formula (2), t is greater than 0, and u is 0 or greater. The ratio t / (t+u) is preferably 0.5 to 1.0. By making the number of groups represented by Ra equal to or greater than half of the total number of groups represented by Ra or Rc contained in the polyorganosilsesquioxane (c1), crosslinks between the polyorganosilsesquioxane molecules are sufficiently formed, so that good scratch resistance can be maintained. t / (t+u) is more preferably from 0.7 to 1.0, further preferably from 0.9 to 1.0, and particularly preferably from 0.95 to 1.0.

[0339] In the general formula (2), it is also preferable that there are multiple Rc's and the multiple Rc's form bonds with each other. In this case, it is preferable that u / (t+u) is 0.00 to 0.20. The value of u / (t+u) is more preferably from 0.00 to 0.10, further preferably from 0.00 to 0.05, and particularly preferably from 0.00 to 0.025.

[0340] The number average molecular weight (Mn) of the polyorganosilsesquioxane (c1) in terms of standard polystyrene measured by gel permeation chromatography (GPC) is preferably 500 to 6,000, more preferably 1,000 to 4,500, and even more preferably 1,500 to 3,000.

[0341] The polyorganosilsesquioxane (c1) has a molecular weight dispersity (Mw / Mn) calculated based on standard polystyrene by GPC of, for example, 1.0 to 4.0, preferably 1.1 to 3.7, more preferably 1.1 to 3.0, and further preferably 1.1 to 2.5, where Mn represents the number average molecular weight.

[0342] The weight average molecular weight and the molecular weight dispersity of the polyorganosilsesquioxane (c1) were measured in the same manner as for the polyorganosilsesquioxane (a1).

[0343] <Method for producing polyorganosilsesquioxane (c1)> The polyorganosilsesquioxane (c1) can be produced by a known production method, and is not particularly limited, but can be produced by a method of hydrolyzing and condensing one or more hydrolyzable silane compounds. As the hydrolyzable silane compound, it is preferable to use a hydrolyzable trifunctional silane compound (a compound represented by the following formula (A)) for forming a siloxane constitutional unit containing a (meth)acryloyl group as the hydrolyzable silane compound. When u in the general formula (2) is greater than 0, it is preferable to use a compound represented by the above formula (C1), (C2) or (C3) in combination as the hydrolyzable silane compound.

[0344] [ka]

[0345] Ra in formula (A) has the same meaning as Ra in general formula (2) above, and preferred examples are also the same.

[0346] X in formula (A) 1 represents an alkoxy group or a halogen atom. X 1 Examples of the alkoxy group in include alkoxy groups having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, and an isobutyloxy group. X 1 Examples of the halogen atom in include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. X 1 As the X, an alkoxy group is preferable, and a methoxy group or an ethoxy group is more preferable. 1 may be the same or different.

[0347] The compound represented by the above formula (A) is a compound that forms a siloxane constitutional unit having Ra.

[0348] The hydrolyzable silane compound may be used in combination with a hydrolyzable silane compound other than the compounds represented by the above formulas (A) and (C1) to (C3). For example, hydrolyzable trifunctional silane compounds, hydrolyzable monofunctional silane compounds, hydrolyzable difunctional silane compounds, hydrolyzable tetrafunctional silane compounds, etc., other than the compounds represented by the above formulas (A) and (C1) to (C3) may be used. Specific examples include tetraalkoxysilanes, dialkoxysilanes, and monoalkoxysilanes.

[0349] Rc in the hydrolyzable silane compounds represented by the above formulas (C1) to (C3) 1 ~Rc 3When the compound is derived from the above, t / (t+u) in the general formula (2) can be adjusted by adjusting the compounding ratio (molar ratio) of the compounds represented by the above formulas (A) and (C1) to (C3). Specifically, for example, in order to adjust t / (t+u) to 0.5 to 1.0, the value represented by the following (Z3) may be adjusted to 0.5 to 1.0, and these compounds may be produced by a method of hydrolyzing and condensing them. (Z3) = Compound represented by formula (A) (molar amount) / {Compound represented by formula (A) (molar amount) + Compound represented by formula (C1) (molar amount) + Compound represented by formula (C2) (molar amount) × 2 + Compound represented by formula (C3) (molar amount) × 3}

[0350] The amount and composition of the hydrolyzable silane compound used can be appropriately adjusted depending on the desired structure of the polyorganosilsesquioxane (c1). In the polyorganosilsesquioxane (c1), the component derived from the compound represented by formula (A) is preferably contained in an amount of 70 mol% to 100 mol%, more preferably 75 mol% to 100 mol%. By making the component derived from the compound represented by formula (A) 70 mol% or more, it is possible to maintain a good pencil hardness due to a sufficient deformation recovery rate while ensuring sufficient scratch resistance.

[0351] The hydrolysis and condensation reaction of the hydrolyzable silane compound can be carried out in the same manner as the hydrolysis and condensation reaction of the hydrolyzable silane compound in the above-mentioned method for producing polyorganosilsesquioxane (a1).

[0352] The hydrolysis and condensation reaction of the hydrolyzable silane compound produces polyorganosilsesquioxane (c1). After the completion of the hydrolysis and condensation reaction, it is preferable to neutralize the catalyst in order to suppress the polymerization of the (meth)acryloyl group. In addition, the polyorganosilsesquioxane (c1) may be separated and purified by, for example, washing with water, washing with an acid, washing with an alkali, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination of these separation means.

[0353] The polyorganosilsesquioxane (c1) may be used alone or in combination of two or more kinds having different structures.

[0354] The content of the cured product of polyorganosilsesquioxane (c1) can be appropriately adjusted from the viewpoint of film thickness and performance, but is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 75% by mass or more, based on the total mass of the scratch-resistant layer. By making the content of the cured product of polyorganosilsesquioxane (c1) 50% or more, it is preferable because the deformation recovery property of the hard coat film can be maintained well.

[0355] In the scratch-resistant layer of the hard coat film of the present invention, the condensation rate of the polyorganosilsesquioxane (c1) is preferably 50% or more from the viewpoint of the hardness of the film, more preferably 80% or more, and even more preferably 90% or more. The condensation rate is the ratio of the polyorganosilsesquioxane (c1) before curing. 29 It is possible to perform Si NMR (nuclear magnetic resonance) spectrum measurement and use the measurement results to perform the calculation. 29 In a Si NMR spectrum, each silicon atom shows a signal (peak) at a different position (chemical shift) depending on the bonding state of the silicon atom, so the condensation rate can be calculated by assigning each signal and calculating the integral ratio.

[0356] (Other additives) The scratch-resistant layer may contain components other than those mentioned above, such as inorganic particles, hollow particles, a leveling agent, an antifouling agent, an antistatic agent, and a slipping agent. The hollow particles are components used to lower the refractive index of the scratch-resistant layer and impart an anti-reflection function. The amount of hollow particles added when using the hollow particles can be appropriately changed depending on the type of hollow particles used, but is preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 80% by mass or less. In particular, it is preferable to contain the following fluorine-containing compound or a cured product of a fluorine-containing compound as a slipping agent. The following fluorine-containing compound and the cured product of a fluorine-containing compound are components different from the polyorganosilsesquioxane (c1) and the cured product thereof.

[0357] [Fluorine-containing compounds, cured products of fluorine-containing compounds] The fluorine-containing compound may be any of a monomer, an oligomer, and a polymer. The fluorine-containing compound preferably has a substituent that contributes to bond formation or compatibility with the polyorganosilsesquioxane (c1) in the scratch-resistant layer. The substituent may be the same or different, and it is preferable that there are a plurality of substituents. The substituent is preferably a polymerizable group, and may be any polymerizable reactive group exhibiting any one of radical polymerization, cationic polymerization, anionic polymerization, condensation polymerization, and addition polymerization, and preferred examples of the substituent include an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, a cinnamoyl group, an epoxy group, an oxetanyl group, a hydroxyl group, a polyoxyalkylene group, a carboxyl group, and an amino group. Among these, a radical polymerizable group is preferred, and an acryloyl group and a methacryloyl group are particularly preferred. The fluorine-containing compound may be a polymer or oligomer with a compound not containing a fluorine atom.

[0358] The above-mentioned fluorine-containing compound is preferably a fluorine-based compound represented by the following general formula (F). General formula (F): (R f )-[(W)-(R A ) nf ] mf (In the formula, R f is a (per)fluoroalkyl group or a (per)fluoropolyether group, W is a single bond or a linking group, R A represents a polymerizable unsaturated group. nf represents an integer of 1 to 3. mf represents an integer of 1 to 3.

[0359] In general formula (F), R Arepresents a polymerizable unsaturated group. The polymerizable unsaturated 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. A (meth)acryloyl group, a (meth)acryloyloxy group, and groups in which any hydrogen atom in these groups is substituted with a fluorine atom are preferably used.

[0360] In general formula (F), R f represents 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. f The higher the fluorine content in the polymer, the more preferable.

[0361] The (per)fluoroalkyl group is preferably a group having 1 to 20 carbon atoms, and more preferably a group having 1 to 10 carbon atoms. (Per)fluoroalkyl groups have a straight chain structure (e.g., -CF 2 CF 3 , -CH 2 (CF 2 ) 4 H, -CH 2 (CF 2 ) 8 CF 3 , -CH 2 CH 2 (CF 2 ) 4 Even if the fluorine-containing compound has a branched structure (e.g. -CH(CF 3 ) 2 , -CH 2 CF(CF 3 ) 2 , -CH(CH 3 )CF 2 CF 3 , -CH(CH 3 )(CF 2 )5 CF 2 H) or an alicyclic structure (preferably a 5- or 6-membered ring, such as a perfluorocyclohexyl group and a perfluorocyclopentyl group, and alkyl groups substituted with these groups).

[0362] 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 -CH 2 OCH 2 CF 2 CF 3 , -CH 2 CH 2 OCH 2 C 4 F 8 H, -CH 2 CH 2 OCH 2 CH 2 C 8 F 17 , -CH 2 CH 2 OCF 2 CF 2 OCF 2 CF 2 H, a fluorocycloalkyl group having 4 to 20 carbon atoms and 4 or more fluorine atoms, etc. Examples of the perfluoropolyether group include -(CF 2 O) pf -(CF 2 CF 2 O) qf -,-[CF(CF 3 )CF 2 O] pf - [CF(CF 3 )] qf -, -(CF 2 CF 2 CF 2 O) pf -, -(CF 2 CF 2 O) pf - etc. The above pf and qf each independently represent an integer of 0 to 20, with the proviso that pf+qf is an integer of 1 or more. The total of pf and qf is preferably from 1 to 83, more preferably from 1 to 43, and even more preferably from 5 to 23. From the viewpoint of excellent scratch resistance, the above fluorine-containing compound is - (CF 2 O) pf - (CF 2 CF 2 O) qf - and particularly preferably has a perfluoropolyether group represented by.

[0363] In the present invention, the fluorine-containing compound preferably has a perfluoropolyether group and a plurality of polymerizable unsaturated groups in one molecule.

[0364] In the general formula (F), W represents a linking group. Examples of W include an alkylene group, an arylene group, and a heteroalkylene group, and a linking group formed by combining these groups. These linking groups may further have a functional group such as an oxy group, a carbonyl group, a carbonyloxy group, a carbonylimino group, and a sulfonamide group, and a functional group formed by combining these groups. As W, preferably, an ethylene group, more preferably, an ethylene group bonded to a carbonylimino group.

[0365] Although there is no particular limitation on the fluorine atom content of the fluorine-containing compound, 20% by mass or more is preferable, 30 to 70% by mass is more preferable, and 40 to 70% by mass is even more preferable.

[0366] Examples of preferable fluorine-containing compounds include R-2020, M-2020, R-3833, M-3833, and Optool DAC (the above trade names) manufactured by Daikin Chemical Industry Co., Ltd., Megafac F-171, F-172, F-179A, RS-78, RS-90, Defender MCF-300, and MCF-323 (the above trade names) manufactured by DIC Corporation, but are not limited thereto.

[0367] From the viewpoint of scratch resistance, in the general formula (F), the product (nf × mf) of nf and mf is preferably 2 or more, and more preferably 4 or more.

[0368] (Molecular weight of fluorine-containing compound) The weight average molecular weight (Mw) of the fluorine-containing compound having a polymerizable unsaturated group can be measured using molecular exclusion chromatography, for example, gel permeation chromatography (GPC). The Mw of the fluorine-containing compound 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 still more preferably 400 or more and less than 25,000.

[0369] (Amount of fluorine-containing compound added) The amount of the fluorine-containing compound added is preferably 0.01 to 5% by mass, more preferably 0.1 to 5% by mass, still more preferably 0.5 to 5% by mass, and particularly preferably 0.5 to 2% by mass based on the total mass of the scratch-resistant layer.

[0370] The film thickness of the scratch-resistant layer is preferably 0.1 μm to 10 μm, more preferably 0.1 μm to 6 μm, and particularly preferably 0.1 μm to 4 μm.

[0371] (Other layers) In addition to the hard coat layer, the scratch-resistant layer and the mixed layer, the hard coat film of the present invention may further have other layers. For example, preferred embodiments include those having a hard coat layer on both sides of the substrate, those having an easy adhesion layer for improving adhesion between the substrate and the hard coat layer, and those having an antistatic layer for imparting antistatic properties, and a plurality of these may be provided.

[0372] [Manufacturing method of hard coat film] The manufacturing method of the hard coat film of the present invention is not particularly limited, but as one of the preferred embodiments, a method (Embodiment A) is to apply and semi-cure a composition for forming a hard coat layer on a substrate, apply a composition for forming a scratch-resistant layer on the semi-cured hard coat layer, and then fully cure each layer. In Embodiment A, when the hard coat film of the present invention further has a mixed layer, it is preferable to apply a composition for forming a mixed layer on the semi-cured hard coat layer, semi-cure it, apply a composition for forming a scratch-resistant layer on the semi-cured mixed layer, and then fully cure each layer. Another preferred embodiment is a method of forming a mixed layer in a hard coat film by laminating an uncured hard coat layer and an abrasion-resistant layer on a substrate, forming a mixed layer by interfacial mixing at the interface between the two layers, and then fully curing each layer. For example, a method (embodiment B) is included in which an uncured hard coat layer is formed on a substrate, and a laminate in which an uncured abrasion-resistant layer is formed on a temporary support is separately prepared, and the laminate is laminated so that the abrasion-resistant layer side contacts the hard coat layer, forming a mixed layer by interfacial mixing at the laminated surface, and then fully curing each layer and then removing the temporary support. In addition, a method (embodiment C) is also included in which a composition for forming a hard coat and a composition for forming an abrasion-resistant layer are multi-layer coated on a substrate, forming a mixed layer at the interface between the two layers, and then fully curing each layer.

[0373] The above-mentioned embodiment A will be described in detail below by taking as an example a case where the hard coat layer contains a cured product of polyorganosilsesquioxane (a1) having an epoxy group, and the mixed layer contains a cured product of compound (b1) having an epoxy group and a cured product of compound (b2) having two or more (meth)acryloyl groups in one molecule. Specifically, embodiment A is a production method including the following steps (I) to (VI). (I) A step of applying a composition for forming a hard coat layer containing the polyorganosilsesquioxane (a1) having an epoxy group onto a substrate to form a coating film (i). (II) A step of semi-curing the coating film (i) (III) A step of applying a mixed layer-forming composition containing the epoxy compound (b1) and the polyfunctional (meth)acrylate compound (b2) onto the semi-cured coating film (i) to form a coating film (ii). (IV) A step of semi-curing the coating film (ii) formed in the above step (III) (V) A step of applying a composition for forming an abrasion-resistant layer containing a polyorganosilsesquioxane (c1) having a group containing a radically polymerizable double bond onto the semi-cured coating film (ii) to form a coating film (iii). (VI) A step of subjecting the coating film (i), the coating film (ii), and the coating film (iii) to a total curing treatment.

[0374] <Process (I)> Step (I) is a step of applying a composition for forming a hard coat layer, which contains the above-mentioned polyorganosilsesquioxane (a1) having an epoxy group, onto a substrate to provide a coating film. The substrate is as described above. The composition for forming a hard coat layer is a composition for forming the above-mentioned hard coat layer. The composition for forming a hard coat layer is usually in the form of a liquid. The composition for forming a hard coat layer is preferably prepared by dissolving or dispersing the polyorganosilsesquioxane (a1) and, if necessary, various additives and a polymerization initiator in a suitable solvent. In this case, the concentration of the solid content is generally about 10 to 90 mass%, preferably about 20 to 80 mass%, and particularly preferably about 40 to 70 mass%.

[0375] <Polymerization initiator> The polyorganosilsesquioxane (a1) contains a cationic polymerizable group (epoxy group). The composition for forming a hard coat layer preferably contains a cationic photopolymerization initiator in order to initiate and advance the polymerization reaction of the polyorganosilsesquioxane (a1) by light irradiation. Only one type of cationic photopolymerization initiator may be used, or two or more types having different structures may be used in combination. The cationic photopolymerization initiator will be described below.

[0376] (Cationic photopolymerization initiator) The cationic photopolymerization initiator may be any one that can generate cations as active species by irradiation with light, and known cationic photopolymerization initiators can be used without any restrictions. Specific examples include known sulfonium salts, ammonium salts, iodonium salts (e.g., diaryliodonium salts), triarylsulfonium salts, diazonium salts, and iminium salts. More specifically, examples include cationic photopolymerization initiators represented by formulas (25) to (28) shown in paragraphs 0050 to 0053 of JP-A-8-143806, and those exemplified as cationic polymerization catalysts in paragraph 0020 of JP-A-8-283320. In addition, the cationic photopolymerization initiator can be synthesized by a known method and is also available as a commercial product. Examples of commercially available products include CI-1370, CI-2064, CI-2397, CI-2624, CI-2639, CI-2734, CI-2758, CI-2823, CI-2855, and CI-5102 manufactured by Nippon Soda Co., Ltd., PHOTOINITIATOR 2047 manufactured by Rhodia, UVI-6974 and UVI-6990 manufactured by Union Carbide Corporation, and CPI-10P manufactured by San-Apro Ltd.

[0377] As the cationic photopolymerization initiator, diazonium salts, iodonium salts, sulfonium salts, and iminium salts are preferred from the viewpoints of the sensitivity of the photopolymerization initiator to light, the stability of the compound, etc. Also, from the viewpoint of weather resistance, iodonium salts are most preferred.

[0378] Specific examples of commercially available iodonium salt-based cationic photopolymerization initiators include B2380 manufactured by Tokyo Chemical Industry Co., Ltd., BBI-102 manufactured by Midori Chemical Industry Co., Ltd., WPI-113 manufactured by Wako Pure Chemical Industries, Ltd., WPI-124 manufactured by Wako Pure Chemical Industries, Ltd., WPI-169 manufactured by Wako Pure Chemical Industries, Ltd., WPI-170 manufactured by Wako Pure Chemical Industries, Ltd., and DTBPI-PFBS manufactured by Toyo Gosei Chemical Co., Ltd.

[0379] Specific examples of iodonium salt compounds that can be used as cationic photopolymerization initiators include the following compounds FK-1 and FK-2.

[0380] [Chemical formula]

[0381] [Chemical formula]

[0382] The content of the polymerization initiator in the composition for forming the hard coat layer may be appropriately adjusted within a range that allows the polymerization reaction (cationic polymerization) of the above polyorganosilsesquioxane (a1) to proceed well, and is not particularly limited. For example, it is in the range of 0.1 to 200 parts by mass, preferably 1 to 20 parts by mass, and more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the above polyorganosilsesquioxane (a1).

[0383] [Optional component] The composition for forming the hard coat layer may further contain one or more optional components in addition to the above polyorganosilsesquioxane (a1) and the polymerization initiator. Specific examples of the optional components include solvents and various additives.

[0384] (Solvent) As the solvent that may be included as an optional component, an organic solvent is preferable, and one or more organic solvents may be mixed in any ratio and used. Specific examples of the organic solvent include alcohols such as methanol, ethanol, propanol, n-butanol, and i-butanol; ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, and cyclohexanone; cellosolves such as ethyl cellosolve; aromatics such as toluene and xylene; glycol ethers such as propylene glycol monomethyl ether; acetates such as methyl acetate, ethyl acetate, and butyl acetate; and diacetone alcohol. The amount of the solvent in the composition can be appropriately adjusted within a range that ensures the coating suitability of the composition. For example, the amount can be 50 to 500 parts by mass, preferably 80 to 200 parts by mass, relative to 100 parts by mass of the total amount of the polyorganosilsesquioxane (a1) and the polymerization initiator.

[0385] (Additives) The composition may further contain one or more known additives as necessary. Examples of such additives include dispersants, leveling agents, antifouling agents, antistatic agents, ultraviolet absorbers, and antioxidants. For details, see, for example, paragraphs 0032 to 0034 of JP 2012-229412 A. However, the present invention is not limited to these additives, and various additives that can be generally used in polymerizable compositions can be used. The type of antistatic agent is not particularly limited, and ion-conductive or electron-conductive antistatic agents can be preferably used. As a specific example of an electron-conductive antistatic agent, Sepulgida (manufactured by Shin-Etsu Polymer Co., Ltd.) using polythiophene conductive polymers can be preferably used. Furthermore, the amount of additives added to the composition may be appropriately adjusted, and is not particularly limited.

[0386] <Method of preparing the composition> The composition for forming a hard coat layer used in the present invention can be prepared by mixing the various components described above simultaneously or sequentially in any order. The preparation method is not particularly limited, and a known mixer or the like can be used for preparation.

[0387] The method for applying the composition for forming a hard coat layer is not particularly limited, and any known method can be used, such as dip coating, air knife coating, curtain coating, roller coating, wire bar coating, gravure coating, and die coating.

[0388] <Process (II)> Step (II) is a step of semi-curing the coating film (i). The type of ionizing radiation is not particularly limited, and examples include X-rays, electron beams, ultraviolet rays, visible light, and infrared rays. However, ultraviolet rays are preferably used. For example, if the coating film is ultraviolet-curable, 2 mJ / cm ionizing radiation is applied by an ultraviolet lamp. 2 ~1000mJ / cm 2 It is preferable to cure the curable compound by irradiating the curable compound with ultraviolet light having an irradiation amount of 2 mJ / cm. 2 ~100mJ / cm 2 More preferably, 5 mJ / cm 2 ~50mJ / cm 2 As the type of ultraviolet lamp, a metal halide lamp, a high pressure mercury lamp, or the like is preferably used.

[0389] The oxygen concentration during curing is not particularly limited, but when a component susceptible to curing inhibition (a compound having a (meth)acryloyl group) is contained, it is preferable to adjust the oxygen concentration to 0.1 to 2.0% by volume, since this allows a semi-cured state in which surface functionality remains. When a component susceptible to curing inhibition (a compound having a (meth)acryloyl group) is not contained, it is preferable to replace the atmosphere during curing with dry nitrogen, since this allows the effect of the epoxy group reacting with water vapor in the air to be eliminated.

[0390] After step (I) or before step (II), or after step (II) or before step (III), or both, a drying treatment may be performed as necessary. The drying treatment may be performed by blowing hot air, placing in a heating furnace, transporting in a heating furnace, or the like. The heating temperature is not particularly limited as long as it is set to a temperature at which the solvent can be dried and removed. Here, the heating temperature refers to the temperature of the hot air or the atmospheric temperature in the heating furnace.

[0391] By semi-curing the coating film (i) in step (II), the unreacted epoxy groups in the polyorganosilsesquioxane (a1) contained in the composition for forming a hard coat layer and the epoxy compound contained in the composition for forming a mixed layer form bonds in steps (IV) and (VI) described below. The formation of the bonds allows the hard coat film of the present invention to have a highly adhesive laminate structure and exhibit higher scratch resistance.

[0392] <Process (III)> Step (III) is a step of applying a mixed layer-forming composition containing the epoxy compound (b1) and the polyfunctional (meth)acrylate compound (b2) onto the semi-cured coating film (i) to form a coating film (ii). The mixed layer-forming composition is a composition for forming the above-mentioned mixed layer. The mixed layer forming composition is usually in the form of a liquid. The mixed layer forming composition is preferably prepared by dissolving or dispersing the epoxy compound (b1) and the polyfunctional (meth)acrylate compound (b2), and, if necessary, various additives and a polymerization initiator in a suitable solvent. In this case, the solid content concentration is generally about 2 to 90 mass%, preferably about 2 to 80 mass%, and particularly preferably about 2 to 70 mass%.

[0393] (Polymerization initiator) The mixed layer forming composition contains an epoxy compound (b1) (cationically polymerizable compound) and a polyfunctional (meth)acrylate compound (b2) (radical polymerizable compound). In order to initiate and progress the polymerization reactions of these polymerizable compounds, which have different polymerization modes, by light irradiation, the mixed layer forming composition preferably contains a radical photopolymerization initiator and a cationic photopolymerization initiator. Only one type of radical photopolymerization initiator may be used, or two or more types having different structures may be used in combination. This also applies to the cationic photopolymerization initiator. Hereinafter, each photopolymerization initiator will be described in order.

[0394] (Radical photopolymerization initiator) The radical photopolymerization initiator may be any one that can generate radicals as active species by irradiation with light, and any known radical photopolymerization initiator may be used without any restrictions.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- Acetophenones such as [4-(1-methylvinyl)phenyl]propanone oligomer and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one; oxime esters such as 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) Benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, o-benzoyl methyl benzoate, 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) benzophenones such as (4-benzoylbenzyl)trimethylammonium chloride, (4-benzoylbenzyl)trimethylammonium bromide, etc.; thioxanthones such as 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H-thioxanthone-9-one mesochloride, etc.;Examples of the acylphosphine oxides include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. In addition, triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler's ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, (n-butoxy)ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone may be used in combination as an auxiliary for the radical photopolymerization initiator. The above radical photopolymerization initiators and assistants can be synthesized by known methods, and are also available as commercial products.

[0395] The content of the radical photopolymerization initiator in the mixed layer forming composition is not particularly limited, and may be appropriately adjusted within a range in which the polymerization reaction (radical polymerization) of the radical polymerizable compound proceeds well. For example, the content is in the range of 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, and more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the radical polymerizable compound contained in the composition.

[0396] The cationic photopolymerization initiator may be the cationic photopolymerization initiator that can be contained in the composition for forming a hard coat layer described above. The content of the cationic photopolymerization initiator in the mixed layer-forming composition is not particularly limited and may be appropriately adjusted within a range in which the polymerization reaction (cationic polymerization) of the cationic polymerizable compound proceeds well. For example, the content is in the range of 0.1 to 200 parts by mass, preferably 1 to 150 parts by mass, and more preferably 1 to 100 parts by mass, relative to 100 parts by mass of the cationic polymerizable compound.

[0397] <Optional ingredients> In addition to the above epoxy compound, polyfunctional (meth)acrylate compound (b2), and polymerization initiator, the composition for forming the mixed layer may further contain one or more optional components. Specific examples of the optional components include solvents and various additives that can be used in the composition for forming the hard coat layer.

[0398] <Method for Preparing the Composition> The composition for forming the mixed layer used in the present invention can be prepared by simultaneously mixing the various components described above or sequentially mixing them in any order. The preparation method is not particularly limited, and known stirrers and the like can be used for the preparation.

[0399] As the method for applying the composition for forming the mixed layer, there is no particular limitation, and known methods can be used.

[0400] <Step (IV)> Step (IV) is a step of semi-curing the coating film (ii) formed in the above step (III).

[0401] It is preferable to cure the coating film by irradiating it with ionizing radiation from the coating film side.

[0402] Regarding the type and irradiation dose of the ionizing radiation, in the above step (II), the ionizing radiation and irradiation dose for semi-curing the coating film (i) can be preferably used.

[0403] After step (III), before step (IV), or after step (IV), before step (V), or both, a drying treatment may be performed as necessary.

[0404] By semi-curing the curing of the coating film (ii) in step (IV), the unreacted (meth)acryloyl groups in the polyfunctional (meth)acrylate compound (b2) contained in the composition for forming the mixed layer and the groups containing radical-polymerizable double bonds in the polyorganosilsesquioxane (c1) containing radical-polymerizable double bonds contained in the composition for forming the scratch-resistant layer form a bond in step (VI) described later. Also, the epoxy compound (b1) contained in the composition for forming the mixed layer and the unreacted epoxy groups in the polyorganosilsesquioxane (c1) contained in the composition for forming the scratch-resistant layer form a bond in step (VI) described later. By forming the above bonds, the hard coat film of the present invention has a laminated structure with high adhesion and can exhibit higher scratch resistance. The oxygen concentration during curing is not particularly limited, but it is preferably adjusted to 0.1 to 2.0% by volume. By setting the oxygen concentration within the above range, the above semi-curing can be adjusted.

[0405] <Step (V)> Step (V) is a step of applying a composition for forming a scratch-resistant layer containing the polyorganosilsesquioxane (c1) having a group containing a radical-polymerizable double bond onto the semi-cured coating film (ii) to form a coating film (iii). The composition for forming the scratch-resistant layer is the composition for forming the aforementioned scratch-resistant layer. The composition for forming the scratch-resistant layer usually takes the form of a liquid. Also, the composition for forming the scratch-resistant layer is preferably prepared by dissolving or dispersing the above polyorganosilsesquioxane (c1), various additives and a polymerization initiator as required in a suitable solvent. At this time, the concentration of the solid content is generally about 2 to 90% by mass, preferably 2 to 80% by mass, and particularly preferably about 2 to 70% by mass.

[0406] (Polymerization initiator) The composition for forming an abrasion-resistant layer contains polyorganosilsesquioxane (c1) having a group containing a radically polymerizable double bond. In order to initiate and progress the polymerization reaction of polyorganosilsesquioxane (c1) by light irradiation, the composition for forming an abrasion-resistant layer preferably contains a radical photopolymerization initiator. Only one type of radical photopolymerization initiator may be used, or two or more types having different structures may be used in combination. Examples of the radical photopolymerization initiator include the radical photopolymerization initiators that can be contained in the composition for forming a mixed layer described above.

[0407] The content of the radical photopolymerization initiator in the composition for forming the scratch-resistant layer is not particularly limited, and may be appropriately adjusted within a range in which the polymerization reaction (radical polymerization) of the radical polymerizable compound proceeds well. For example, the content is in the range of 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, and more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the radical polymerizable compound contained in the composition.

[0408] <Optional ingredients> The mixed layer forming composition may further contain one or more optional components in addition to the polyorganosilsesquioxane (c1) and the polymerization initiator.Specific examples of the optional components include the fluorine-containing compound, as well as the solvent and various additives that can be used in the hard coat layer forming composition.

[0409] <Method of preparing the composition> The composition for forming the scratch-resistant layer used in the present invention can be prepared by mixing the various components described above simultaneously or sequentially in any order. The preparation method is not particularly limited, and a known mixer or the like can be used for preparation.

[0410] The method for applying the composition for forming the scratch-resistant layer is not particularly limited, and any known method can be used.

[0411] <Process (VI)> Step (VI) is a step of subjecting the coating film (i), the coating film (ii), and the coating film (iii) to a total curing treatment.

[0412] The coating is preferably cured by irradiating the coating with ionizing radiation from the coating side.

[0413] Regarding the type and dose of ionizing radiation, the ionizing radiation and dose for curing the coating film (i) and the coating film (ii) in the above step (IV) can be suitably used.

[0414] After step (V), before step (VI), or after step (VI), or both, a drying treatment may be carried out as necessary.

[0415] The present invention also relates to an article having the above-mentioned hard coat film of the present invention, and an image display device having the above-mentioned hard coat film of the present invention as a surface protective film. The hard coat film of the present invention is particularly preferably applied to flexible displays in smartphones and the like. EXAMPLES

[0416] The present invention will be described in more detail below with reference to examples, but the scope of the present invention should not be construed as being limited thereto.

[0417] <Preparation of substrate> (Production of polyimide powder) In a 1L reactor equipped with a stirrer, nitrogen injector, dropping funnel, temperature controller and cooler, 832g of N,N-dimethylacetamide (DMAc) was added under nitrogen flow, and the temperature of the reactor was set to 25°C. 64.046g (0.2mol) of bistrifluoromethylbenzidine (TFDB) was added and dissolved therein. While maintaining the obtained solution at 25°C, 31.09g (0.07mol) of 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) and 8.83g (0.03mol) of biphenyltetracarboxylic dianhydride (BPDA) were added and reacted for a certain period of time by stirring. Then, 20.302g (0.1mol) of terephthaloyl chloride (TPC) was added to obtain a polyamic acid solution with a solid content concentration of 13% by mass. Next, 25.6g of pyridine and 33.1g of acetic anhydride were added to the polyamic acid solution and stirred for 30 minutes, then stirred for another hour at 70°C, and cooled to room temperature. 20L of methanol was added to the solution, and the precipitated solid was filtered and pulverized. After that, it was dried in a vacuum at 100°C for 6 hours to obtain 111g of polyimide powder.

[0418] (Preparation of substrate S-1) 100 g of polyimide powder was dissolved in 670 g of N,N-dimethylacetamide (DMAc) to obtain a 13% by mass solution. The obtained solution was cast onto a stainless steel plate and dried with hot air at 130°C for 30 minutes. The film was then peeled off from the stainless steel plate and fixed to a frame with pins. The frame to which the film was fixed was placed in a vacuum oven and heated for 2 hours while gradually increasing the heating temperature from 100°C to 300°C, and then gradually cooled. After the cooled film was separated from the frame, it was further heat-treated at 300°C for 30 minutes as a final heat treatment step to obtain a substrate S-1 made of a polyimide film and having a thickness of 30 μm.

[0419] <Synthesis of polyorganosilsesquioxane> (Synthesis of compound (A)) In a 1000 ml flask (reaction vessel) equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen inlet tube, 297 mmol (73.2 g) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3 mmol (409 mg) of methyltrimethoxysilane, 7.39 g of triethylamine, and 370 g of MIBK (methyl isobutyl ketone) were mixed under a nitrogen stream, and 73.9 g of pure water was added dropwise using a dropping funnel over 30 minutes. The reaction solution was heated to 80°C, and the polycondensation reaction was carried out under a nitrogen stream for 10 hours. The reaction solution was then cooled, 300g of 5% by mass saline was added, and the organic layer was extracted. The organic layer was washed twice with 300g of 5% by mass saline and 300g of pure water, successively, and then concentrated under conditions of 1mmHg and 50°C to obtain a methyl isobutyl ketone (MIBK) solution containing 59.0% by mass of a colorless, transparent liquid product {a polyorganosilsesquioxane having an alicyclic epoxy group, compound (A) (compound in general formula (1) where Rb: 2-(3,4-epoxycyclohexyl)ethyl group, Rc: methyl group, q = 99, r = 1) as a solid content concentration of 59.8% by mass. The resulting compound (A) had a number average molecular weight (Mn) of 2310 and a dispersity (Mw / Mn) of 2.1. Note that 1mmHg is approximately 133.322 Pa.

[0420] (Synthesis of compound (B)) A methyl isobutyl ketone (MIBK) solution containing compound (B) (a compound in general formula (2) where Ra: 3-(acryloyloxy)propyl group, t=100, and u=0) at a solid content concentration of 62.0 mass% was obtained in the same manner as in the synthesis of compound (A), except that 297 mmol (73.2 g) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and 3 mmol (409 mg) of methyltrimethoxysilane were changed to 300 mmol (70.3 g) of 3-(acryloyloxy)propyltrimethoxysilane. The compound (B) thus obtained had a number average molecular weight (Mn) of 2130 and a polydispersity (Mw / Mn) of 1.2. The condensation rate was 97%.

[0421] (Synthesis of compound (C)) A methyl isobutyl ketone (MIBK) solution containing compound (C) (a compound in general formula (2) where Ra: 3-(methacryloyloxy)propyl group, t=100, and u=0) at a solid content concentration of 60.5% by mass was obtained in the same manner as in the synthesis of compound (A), except that 297 mmol (73.2 g) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and 3 mmol (409 mg) of methyltrimethoxysilane were changed to 300 mmol (74.5 g) of 3-(methacryloyloxy)propyltrimethoxysilane. The resulting compound (C) had a number average molecular weight (Mn) of 2050 and a polydispersity (Mw / Mn) of 1.1. The condensation rate was 97%.

[0422] (Synthesis of compound (D)) A methyl isobutyl ketone (MIBK) solution containing compound (D) (a compound represented by general formula (2) in which Ra is a 3-(acryloyloxy)propyl group, t=100, and u=0) at a solid content concentration of 61.3% by mass was obtained in the same manner as in the synthesis of compound (B), except that the reaction temperature was changed from 80°C to 50°C, the reaction time was changed from 10 hours to 5 hours under air instead of under a nitrogen stream. The compound (D) thus obtained had a number average molecular weight (Mn) of 1380 and a dispersity (Mw / Mn) of 1.2. The condensation rate was 70%.

[0423] [Example 1] <Preparation of hard coat layer forming composition> (Hardcoat layer forming composition HC-1) CPI-100P, leveling agent-1 and MIBK (methyl isobutyl ketone) were added to the MIBK solution containing the above compound (A), and the concentrations of each component were adjusted to the following concentrations, and the mixture was placed in a mixing tank and stirred. The resulting composition was filtered through a polypropylene filter with a pore size of 0.4 μm to obtain a hard coat layer forming composition HC-1.

[0424] Compound (A) 98.7 parts by mass CPI-100P 1.3 parts by mass Leveling agent-1 0.07 parts by weight Methyl isobutyl ketone 100.0 parts by mass

[0425] The compounds used in the composition for forming a hard coat layer are as follows. CPI-100P: Cationic photopolymerization initiator, manufactured by San-Apro Co., Ltd. Leveling agent-1: Polymer having the following structure (Mw=1600, composition ratio (molar ratio) of the following repeating units is the repeating unit on the left: the repeating unit on the right=59:41)

[0426] [ka]

[0427] <Preparation of Mixed Layer-Forming Composition> (Mixed layer forming composition M-1) The MIBK solution containing the compound (A) was replaced with a MEK (methyl ethyl ketone) solution, and DPHA, CPI-100P, Irgacure 127, leveling agent-1 and MEK were added, and the concentrations of the components were adjusted to the following concentrations, and the mixture was put into a mixing tank and stirred. The resulting composition was filtered through a polypropylene filter with a pore size of 0.4 μm to obtain a mixed layer forming composition M-1. In the mixed layer forming composition M-1, the mixing ratio of the compound (A) and DPHA is compound (A) / DPHA 50% by mass / 50% by mass.

[0428] Compound (A) 42.85 parts by mass DPHA 42.85 parts by mass CPI-100P 1.3 parts by mass Irgacure 127 5.0 parts by weight Leveling agent-2 8.0 parts by weight Methyl ethyl ketone 500.0 parts by mass

[0429] The compounds used in the mixed layer-forming composition are as follows. DPHA: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd. Irgacure 127: A radical photoinitiator, manufactured by BASF Leveling agent - 2: A polymer with the following structure (Mw = 20000, the composition ratio of the following repeating units is by mass)

[0430]

Chemical formula

[0431] <Preparation of the composition for forming the scratch-resistant layer> (Scratch-resistant layer-forming composition SR-1) Each component was charged into a mixing tank with the composition described below, stirred, and filtered through a polypropylene filter with a pore size of 0.4 μm to obtain the scratch-resistant layer-forming composition SR-1.

[0432] Compound (B) 96.2 parts by mass Irgacure 127 2.8 parts by mass RS-90 1.0 part by mass Methyl ethyl ketone 300.0 parts by mass

[0433] Note that the compounds used in the scratch-resistant layer-forming composition are as follows. RS-90: A lubricant, manufactured by DIC Corporation

[0434] <Fabrication of the hard coat film> The hard coat layer-forming composition HC-1 was applied onto the substrate S-1 using a die coater. After drying at 120 °C for 1 minute, under the condition of 25 °C, an ultraviolet ray with an illuminance of 18 mW / cm 2 , and an irradiation dose of 10 mJ / cm 2 was irradiated to semi-cure the hard coat layer.

[0435] A mixed layer forming composition was prepared by adding MEK to the mixed layer forming composition M-1 to dilute the solid content concentration to 1 / 10, and the mixed layer forming composition was applied onto the semi-cured hard coat layer using a die coater. After drying at 120°C for 1 minute, the composition was exposed to light at an illuminance of 18mW / cm2 using an air-cooled mercury lamp at 25°C and an oxygen concentration of 1%. 2 , irradiation amount 10mJ / cm 2 The mixed layer was semi-cured by irradiating it with ultraviolet light of 1000 nm to provide a mixed layer on the hard coat layer. On the semi-cured mixed layer, the composition for forming an abrasion-resistant layer, SR-1, was applied using a die coater. After drying at 120°C for 1 minute, the composition was irradiated with an air-cooled mercury lamp at an illuminance of 60 mW / cm under conditions of 25°C and an oxygen concentration of 100 ppm (parts per million). 2 , irradiation amount 600mJ / cm 2 After irradiating the specimen with ultraviolet light, the specimen was further irradiated with an air-cooled mercury lamp at an illuminance of 60 mW / cm under conditions of 80°C and an oxygen concentration of 100 ppm. 2 , irradiation amount 600mJ / cm 2 The hard coat layer, the mixed layer, and the scratch-resistant layer were completely cured by irradiating them with ultraviolet rays of 17.0 μm in thickness. The obtained film was then heat-treated at 120° C. for 1 hour to obtain hard coat film 1 having a 17.0 μm thick hard coat layer, a 0.1 μm thick mixed layer, and a 1.0 μm thick scratch-resistant layer in that order.

[0436] [Example 2] A hard coat film 2 was obtained in the same manner as in Example 1, except that the compound (B) in the composition for forming an abrasion-resistant layer SR-1 was changed to the compound (C).

[0437] [Example 3] A hard coat film 3 was obtained in the same manner as in Example 1, except that the compound (B) in the composition for forming an abrasion-resistant layer SR-1 was changed to the compound (D).

[0438] [Example 4] <Preparation of silica particles> In a 200L reactor equipped with a stirrer, a dropping device and a thermometer, 89.46 kg of pure water and 0.10 kg of 28% by mass ammonia water were charged, and the liquid temperature was adjusted to 90°C while stirring. While maintaining the liquid temperature in the reactor at 90°C, 10.44 kg of tetramethoxysilane was dropped from the dropping device over 114 minutes, and after the dropwise addition was completed, the liquid was stirred for another 120 minutes while maintaining the liquid temperature at the above temperature, thereby carrying out hydrolysis and condensation of tetramethoxysilane. The resulting colloidal solution was concentrated to 38.8 kg under reduced pressure of 13.3 kPa using a rotary evaporator, and SiO 2 Silica particles P-1 having a concentration of 10.0 mass % were obtained. The average primary particle size of the silica particles P-1 was 15 nm. 300g of silica particles P-1 were charged into a glass reactor with an internal volume of 1L equipped with a stirrer. A solution of 2.3g of 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) dissolved in 20g of methyl alcohol was added dropwise and mixed. Then, the mixture was heated at 95°C for about 2 hours while being mixed and stirred. After cooling, 100g of 1-methoxy-2-propanol was added, and the by-product methanol was distilled off under reduced pressure. Furthermore, 300g of 1-methoxy-2-propanol was added in several portions, and water was distilled off under reduced pressure by azeotropy so that the solid content was 60% by mass, to obtain silica particles P-2. The solid content was calculated from the weight change before and after heating at 150°C for 30 minutes.

[0439] <Preparation of hard coat layer forming composition> (Hard coat layer forming composition HC-2) The components were mixed in the following composition (mass %) to prepare a hard coat layer-forming composition HC-2. The composition of the silica particles is based on a dispersion having a solid content of 60%. A-400 10.8 parts by mass Irgacure 184 0.6 parts by weight Silica particles P-2 47.7 parts by mass 1-Methoxy-2-propanol 40.9 parts by mass Leveling agent-2 0.10 parts by weight

[0440] The compounds used in the hard coat layer-forming composition HC-2 are as follows. A-400: Polyethylene glycol #400 diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) Irgacure 184: Radical photopolymerization initiator, manufactured by BASF

[0441] <Preparation of hard coat film> The composition for forming a hard coat layer HC-2 was applied onto the substrate S-1 using a die coater. After drying at 100° C. for 30 seconds, the composition was irradiated with an air-cooled mercury lamp at 25° C. with an illuminance of 18 mW / cm 2 2 , irradiation amount 10mJ / cm 2 The hard coat layer was semi-cured by irradiating it with ultraviolet light of 1000 nm.

[0442] The scratch-resistant layer-forming composition SR-1 was applied onto the semi-cured hard coat layer using a die coater. After drying at 120°C for 1 minute, the coating was irradiated with an air-cooled mercury lamp at an illuminance of 60 mW / cm under conditions of 25°C and an oxygen concentration of 100 ppm (parts per million). 2 , irradiation amount 600mJ / cm 2 After irradiating the specimen with ultraviolet light, the specimen was further irradiated with an air-cooled mercury lamp at an illuminance of 60 mW / cm under conditions of 80°C and an oxygen concentration of 100 ppm. 2 , irradiation amount 600mJ / cm 2 The hard coat layer and the scratch-resistant layer were completely cured by irradiating them with ultraviolet rays of 1000 nm. The obtained film was then heat-treated at 120° C. for 1 hour to obtain hard coat film 3 having a scratch-resistant layer of 1.0 μm thickness on a hard coat layer of 17.0 μm thickness.

[0443] [Example 5] <Preparation of hard coat layer forming composition> (Hard coat layer forming composition HC-3) The components were mixed in the following composition (mass %) to prepare a hard coat layer-forming composition HC-3. DPCA20 96.9 parts by mass Irgacure 184 3.0 parts by weight 1-Methoxy-2-propanol 100.0 parts by mass Leveling agent - 2: 0.10 parts by mass

[0444] The compounds used in the composition HC - 3 for forming the hard coat layer are as follows. DPCA20: KAYARAD DPCA20, the following compound. Manufactured by Nippon Kayaku Co., Ltd.

[0445] [Chemical formula]

[0446] [Production of hard coat film] A hard coat film 4 was obtained in the same manner as in Example 3, except that the composition HC - 2 for forming the hard coat layer was changed to HC - 3 and the thickness of the abrasion - resistant layer was set to 3.0 μm.

[0447] [Comparative Examples 1 and 2] Hard coat films of Comparative Examples 1 and 2 were obtained in the same manner as in Example 1, except that the compound (B) in the composition SR - 1 for forming the abrasion - resistant layer was changed to DPHA and DPCA60, respectively. DPCA60: Caprolactone - modified dipentaerythritol hexaacrylate, trade name KAYARAD DPCA60 (manufactured by Nippon Kayaku Co., Ltd.)

[0448] [Comparative Example 3] A hard coat film of Comparative Example 3 was obtained in the same manner as in Example 4, except that the compound (B) in the composition SR - 1 for forming the abrasion - resistant layer was changed to DPHA.

[0449] [Comparative Example 4] A hard coat film of Comparative Example 4 was obtained in the same manner as in Example 5, except that the compound (B) in the composition SR - 1 for forming the abrasion - resistant layer was changed to DPHA.

[0450] [Evaluation of abrasion - resistant layer] Each of the compositions for forming an abrasion-resistant layer was applied onto the substrate S-1 using a die coater. After drying at 120° C. for 1 minute, the composition was irradiated with an air-cooled mercury lamp at 25° C. and an oxygen concentration of 100 ppm at an illuminance of 60 mW / cm 2 . 2 , irradiation amount 600mJ / cm 2 After irradiating the specimen with ultraviolet light, the specimen was further irradiated with an air-cooled mercury lamp at an illuminance of 60 mW / cm under conditions of 80°C and an oxygen concentration of 100 ppm. 2 , irradiation amount 600mJ / cm 2 By irradiating the film with ultraviolet light of 10.0 .mu.m, an abrasion-resistant film having an abrasion-resistant layer of 10.0 .mu.m was obtained.

[0451] (Response rate) In the above scratch-resistant layer film, the carbonyl group peak (1660-1800 cm) was detected by the ATR (Attenuated Total Reflection) method of surface IR (infrared spectroscopy) measurement. -1 ) area and double bond peak height (808 cm -1 The surface IR measurement was also performed on the same sample prepared without UV irradiation to obtain the value (Q101) obtained by dividing the double bond peak height by the carbonyl group peak area. The surface hardening rate was calculated from these values ​​using the following formula 1. Formula 1 Surface hardening rate = (1-(P101 / Q101)) x 100 (%)

[0452] (Elasticity and recovery rate) The substrate side of each scratch-resistant layer film was bonded to glass using Aron Alpha (registered trademark) (manufactured by Toa Gosei Co., Ltd.), and hardness was measured under the following conditions using a HM2000 hardness tester (manufactured by Fisher Instruments, diamond Knoop indenter). Maximum load: 50mN Load application time: 10 seconds Creep: 5 seconds Load unloading time: 10 seconds Number of measurements: 10 The elastic modulus was calculated from the unloading curve in the above measurement, and the recovery rate is the recovery rate relative to the maximum indentation depth in the above measurement at the end of the measurement (i.e., load 0). The elastic modulus and recovery rate were averaged over 10 measurements.

[0453] [Evaluation of hard coat film] The prepared hard coat films were evaluated by the following methods.

[0454] (Pencil hardness) The measurements were performed in accordance with JIS K 5600-5-4 (1999) and rated on the following four-level scale. A: Pencil hardness is 6H or higher. B: Pencil hardness is 5H or more and less than 6H. C: Pencil hardness is 4H or more and less than 5H. D: Pencil hardness is less than 4H.

[0455] (Repeated bending resistance) A sample film having a width of 15 mm and a length of 150 mm was cut out from the hard coat film produced in each of the Examples and Comparative Examples, and allowed to stand at a temperature of 25° C. and a relative humidity of 65% for at least 1 hour. Thereafter, a folding endurance test was carried out repeatedly with the substrate facing outward using a folding endurance tester (manufactured by Imoto Manufacturing Co., Ltd., IMC-0755 model, bending radius of curvature 1.0 mm). The sample film was evaluated according to the following criteria based on the number of times it was folded until it cracked or broke. A: More than 800,000 times B: 500,000 or more times, but less than 800,000 times C: 100,000 or more times, but less than 500,000 times D: Less than 100,000 times

[0456] (Scratch resistance) The surface of the hard coat film produced in each of the Examples and Comparative Examples opposite to the substrate was subjected to a rubbing test using a rubbing tester under the following conditions to provide an index of scratch resistance. Evaluation environment conditions: 25°C, relative humidity 60% Rubbing material: Steel wool (Nippon Steel Wool Co., Ltd., Grade No. 0000) Wrap the tester's scraping tip (1cm x 1cm) that comes into contact with the sample and secure it in place with a band. Travel distance (one way): 13cm, Scrub speed: 13cm / sec. Load: 1000g / cm 2 Tip contact area: 1cm x 1cm, Number of rubs: 100, 1000, 5000, 10000 After the test, oil-based black ink was applied to the side of the hard coat film opposite to the side that had been rubbed in each of the Examples and Comparative Examples, and the side was visually observed using reflected light. The number of rubs required until the part that had been in contact with the steel wool was scratched was counted, and the result was evaluated on the following five-point scale. A: It will not get scratched even if rubbed 10,000 times. B: It will not get scratched even if rubbed 5,000 times, but it will get scratched before rubbed 10,000 times. C: No scratches even after 1000 rubs, but scratches occur within 5000 rubs. D: No scratches even after 100 rubs, but scratches occur before 1000 rubs. E: Scratches will appear within 100 rubs.

[0457] The evaluation results are shown in Table 1 below.

[0458] [Table 1]

[0459] As shown in Table 1, the hard coat films of the Examples were very excellent in repeated bending resistance, and had high hardness and excellent scratch resistance. On the other hand, the hard coat films of Comparative Examples 1, 3, and 4 did not reach the level of repeated bending resistance targeted in the present invention. This is believed to be because the elastic modulus of the scratch-resistant layer was not sufficiently low. In addition, the hard coat film of Comparative Example 2 had very good repeated bending resistance, but was inferior in scratch resistance to the Examples.

Claims

1. A hard coat film having a substrate, a hard coat layer, and a scratch-resistant layer in this order, The thickness of the scratch-resistant layer is 1.0 μm to 10 μm, The scratch-resistant layer contains a cured product of a polyorganosilsesquioxane compound (c1) having a group containing a radically polymerizable double bond, The scratch-resistant layer is a hard coat film that does not include a fine uneven structure having an uneven height of 50 to 1000 nm and an uneven period of 10 to 400 nm.

2. A hard coat film as described in claim 1, wherein the hard coat layer contains a cured product of polyorganosilsesquioxane (a1) having an epoxy group.

3. A hard coat film having a substrate, a hard coat layer, and a scratch-resistant layer in this order, The thickness of the scratch-resistant layer is 1.0 μm to 10 μm, The scratch-resistant layer contains a cured product of a polyorganosilsesquioxane compound (c1) having a group containing a radically polymerizable double bond, The hard coat film, wherein the hard coat layer contains a cured product of polyorganosilsesquioxane (a1) having an epoxy group.

4. A hard coat film as described in claim 2 or 3, wherein the epoxy group is an alicyclic epoxy group.

5. 5. The hard coat film according to claim 1, wherein the group containing a radically polymerizable double bond is a group containing a (meth)acryloyl group.

6. 6. The hard coat film according to claim 1, wherein the group containing a radically polymerizable double bond is a group containing an acryloyl group.

7. The hard coat film according to any one of claims 1 to 6, wherein the condensation rate of the polyorganosilsesquioxane compound (c1) having a group containing a radically polymerizable double bond is 50% or more.

8. The hard coat film according to any one of claims 1 to 7, wherein the scratch-resistant layer contains a cured product of a fluorine-containing compound.

9. A mixed layer is provided between the hard coat layer and the scratch-resistant layer, The hard coat film according to any one of claims 1 to 8, wherein the mixed layer contains a cured product of a compound (b1) having an epoxy group and a cured product of a compound (b2) having two or more (meth)acryloyl groups in one molecule.

10. An article comprising the hard coat film according to any one of claims 1 to 9.

11. An image display device comprising the hard coat film according to any one of claims 1 to 9 as a surface protective film.

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