Hard coat film, article provided with 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 the 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 (PDP), electroluminescence displays (ELD), fluorescent displays (VFD), field emission displays (FED), and liquid crystal displays (LCD), 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] Japanese Patent Application Publication No. 2017-228238 [Patent Document 2] Japanese Patent Application Publication No. 2017-177772 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 bent (excellent in repeated bending resistance), and in particular, there is a strong demand for optical films that can balance hardness and scratch resistance with repeated bending resistance. The inventors of the present invention have conducted studies and 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 balance between the above-mentioned required performances. An object of the present invention is to provide a hard-coated film that has excellent resistance to repeated bending, high hardness, and excellent scratch resistance, and to provide an article and an image display device that include the hard-coated film. [Means for solving the problem]

[0006] The present inventors have conducted extensive research and have 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 an abrasion-resistant layer in this order, The scratch-resistant layer has a thickness of 1.0 μm to 10 μm, 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 hard coat film according to [1], wherein the group containing a radically polymerizable double bond is a group containing a (meth)acryloyl group. [3] The hard coat film according to [1] or [2], wherein the group containing a radically polymerizable double bond is a group containing an acryloyl group. [4] The hard coat film according to any one of [1] to [3], wherein the condensation rate of the polyorganosilsesquioxane compound (c1) having a group containing a radically polymerizable double bond is 50% or more. [5] The hard coat film according to any one of [1] to [4], wherein the scratch-resistant layer contains a cured product of a fluorine-containing compound. [6] The hard coat film according to any one of [1] to [5], wherein the hard coat layer contains a cured product of polyorganosilsesquioxane (a1) having an epoxy group. [7] a mixed layer is provided between the hard coat layer and the scratch-resistant layer, The hard coat film according to any one of [1] to [6], 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. [8] An article comprising the hard coat film according to any one of [1] to [7]. [9] An image display device comprising the hard coat film according to any one of [1] to [7] as a surface protective film. The present invention relates to the above items [1] to [9], but other items are also described in this specification for reference.

[0007] <1> A hard coat film having a substrate, a hard coat layer, and an abrasion-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> 10. The hard coat film according to claim 1, wherein the hard coat film is a hard coat film having a thickness of 100 nm or less. <5> The scratch-resistant layer contains a cured product of a fluorine-containing compound. <1> ~ <4> 10. The hard coat film according to claim 1, wherein the hard coat film is a hard coat film having a thickness of 100 nm or less. <6> The hard coat layer contains a cured product of polyorganosilsesquioxane (a1) having an epoxy group. <1> ~ <5> 10. The hard coat film according to claim 1, wherein the hard coat film is a hard coat film having a thickness of 100 nm or less. <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> 10. The hard coat film according to claim 1, wherein the hard coat film is a hard coat film having a thickness of 100 nm or less. <8> <1> ~ <7> 10. An article comprising the hard coat film according to any one of claims 1 to 9. <9> <1> ~ <7> 10. An image display device comprising the hard coat film according to any one of claims 1 to 9 as a surface protective film. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a hard-coated film that has excellent resistance to repeated bending, high hardness, and excellent scratch resistance, as well as an article and an image display device that include the hard-coated film. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, 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, characteristic value, etc., the expression "(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 expression "(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 an abrasion-resistant layer in this order, The abrasion-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-coated film with excellent repeated bending resistance, the present inventors first inferred that the repeated bending resistance of the hard-coated film could be improved by reducing the compressive stress applied to the scratch-resistant layer in the hard-coated film during a bending test using a folding endurance tester. As a result of further investigation, it was confirmed that reducing the elastic modulus of the scratch-resistant layer is effective in reducing the compressive stress. In other words, it was inferred that the repeated bending resistance of the hard-coated film could be improved by reducing the elastic modulus of the scratch-resistant layer. On the other hand, the scratch resistance of a hard coat film is thought to correlate with the crosslink density of the polymerizable compound, which is the matrix-forming component of the scratch-resistant layer. To reduce the elastic modulus of the scratch-resistant layer, it is generally necessary to increase the crosslinking group equivalent weight of the polymerizable compound (e.g., a polyfunctional (meth)acrylate compound), which is the matrix-forming component of the scratch-resistant layer, or to reduce the crosslinking group reaction rate. This reduces the crosslink density and the scratch resistance. Furthermore, there is a concern that a decrease in the elastic modulus of the scratch-resistant layer may cause a decrease in pencil hardness. Therefore, in order to realize a scratch-resistant layer that reduces the elastic modulus of the scratch-resistant layer without 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 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. The crosslinked structure formed by siloxane bonds is more flexible than the crosslinked structure obtained by polymerization of the radically polymerizable double bonds. Therefore, it is believed that it is possible to reduce the elastic modulus of the scratch-resistant layer while still exhibiting the scratch resistance due to the high crosslinking density provided by the two types of crosslinked structures. Furthermore, it is believed 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 be described below.

[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) The polymer is preferably one that is excellent in optical transparency, mechanical strength, thermal stability, and the like.

[0015] Examples of polymers include polycarbonate polymers, polyester polymers such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), styrene polymers such as polystyrene and acrylonitrile-styrene copolymers (AS resins), etc. Other examples include polyolefins such as polyethylene and polypropylene, polyolefin polymers such as norbornene resins and ethylene-propylene copolymers, (meth)acrylic polymers such as polymethyl methacrylate, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamides, imide polymers, sulfone polymers, polyethersulfone polymers, polyetheretherketone polymers, polyphenylene sulfide polymers, vinylidene chloride polymers, vinyl alcohol polymers, vinyl butyral polymers, arylate polymers, polyoxymethylene polymers, epoxy polymers, cellulose 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 high number of bending cycles to break as measured by an MIT testing machine in accordance with JIS (Japanese Industrial Standards) P8115 (2001) and a relatively high hardness. For example, aromatic polyamides such as those described in Example 1 of Japanese Patent No. 5699454 and polyimides described in Japanese Patent Publication Nos. 2015-508345 and 2016-521216 can be preferably used as the substrate.

[0017] The substrate 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 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 a rubber-like elastomer, a brittleness improver, a plasticizer, and a slide-ring polymer. Specifically, the softening material is described in paragraph number JP 2016-167043 A. <0051> ~ <0114> The softening materials described in the above can be suitably used.

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

[0020] There are no particular restrictions 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 all of the polymer may be softening material (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 intended use. These additives may be solid or oily. That is, there are no particular limitations on their melting or boiling points. The additives may be added at any time during the process of preparing the substrate, or a step 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 exhibited. Other additives include those listed in paragraph number JP 2016-167043 A. <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] (ultraviolet absorber) Examples of UV absorbers include benzotriazole compounds, triazine compounds, and benzoxazine compounds. Benzotriazole compounds are compounds having a benzotriazole ring. Specific examples include the various benzotriazole-based UV absorbers described in paragraph 0033 of JP 2013-111835 A. Triazine compounds are compounds having a triazine ring. Specific examples include the various triazine-based UV absorbers described in paragraph 0033 of JP 2013-111835 A. Examples of benzoxazine compounds include those described in paragraph 0031 of JP 2014-209162 A. The content of the UV absorber in the substrate is, for example, approximately 0.1 to 10 parts by mass per 100 parts by mass of the polymer contained in the substrate, but is not particularly limited. For UV absorbers, see paragraph 0032 of JP 2013-111835 A. In the present invention, UV absorbers with high heat resistance and low volatility are preferred. Examples of such ultraviolet absorbers include UVSORB101 (manufactured by Fujifilm Fine Chemicals Co., Ltd.), TINUVIN 360, TINUVIN 460, TINUVIN 1577 (manufactured by BASF), LA-F70, LA-31, LA-46 (manufactured by ADEKA Corporation), and the like. can be done.

[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 polymer) A substrate containing an imide polymer can be preferably used as the substrate. In this specification, an imide polymer refers to a polymer containing at least one repeating structural unit represented by formula (PI), formula (a), formula (a'), or formula (b). In particular, it is preferable that the repeating structural unit represented by formula (PI) is the main structural unit of the imide polymer from the viewpoint of film strength and transparency. The repeating structural unit represented by formula (PI) accounts for 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 especially more preferably 98 mol% or more of the total repeating structural units of the imide 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, and A 2 represents a divalent organic group. 3 represents a tetravalent organic group, and A 3 represents a divalent organic group. 4 and A 4 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 an acyclic aliphatic group, a cyclic aliphatic group, and an aromatic group. From the viewpoint of the transparency and flexibility of a 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 fused polycyclic aromatic group, and a non-fused polycyclic aromatic group having two or more aromatic rings, which are linked to each other directly or via a bonding group. From the viewpoint of the transparency of the resin film and the 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 fused polycyclic aromatic group having a fluorine-based substituent, or a non-fused polycyclic aromatic group having a fluorine-based substituent. In this specification, the term "fluorine-based substituent" refers to 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, saturated or unsaturated cycloalkyl groups, saturated or unsaturated heterocycloalkyl groups, aryl groups, heteroaryl groups, arylalkyl groups, alkylaryl groups, heteroalkylaryl groups, and groups having any two of these groups (which may be the same) linked to each other directly or via a bonding group. Examples of the bonding group include -O-, alkylene groups having 1 to 10 carbon atoms, -SO2-, -CO-, and -CO-NR- (wherein R represents an alkyl group having 1 to 3 carbon atoms, such as methyl, ethyl, or propyl, 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 even more 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 formulas (20), (21), (22), (23), (24), (25), and (26). * in the formulas indicates a bond. Z in formula (26) represents a single bond, -O-, -CH2-, -C(CH3)2-, -Ar-O-Ar-, -Ar-CH2-Ar-, -Ar-C(CH3)2-Ar-, or -Ar-SO2-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 in 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, fused polycyclic aromatic groups, and non-fused polycyclic aromatic groups having two or more aromatic rings that are linked to each other directly or via a bonding group. From the viewpoints of transparency of the resin film and suppression of coloration, it is preferable that a fluorine-based substituent be introduced into the organic group of A.

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

[0035] The divalent organic group represented by A usually has 2 to 40 carbon atoms, preferably 5 to 32 carbon atoms, more preferably 12 to 28 carbon atoms, and even more preferably 24 to 27 carbon atoms.

[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 are each independently a single bond, -O-, -CH2-, -C(CH3)2-, -SO2-, -CO- or -CO-NR- (R is 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). 1 and Z 2 , and Z 2 and Z 3 are preferably located at the meta or para position relative to each ring. 1 and the terminal single bond, Z 2 and the terminal single bond, and Z 3 and the terminal single bond are preferably at the meta or para position, respectively. 1 and Z 3 is -O- and Z 2 is -CH2-, -C(CH3)2- or -SO2-. One or more hydrogen atoms of these groups may be substituted with a fluorine-based substituent.

[0037] [ka]

[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 sulfonic acid 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 G include groups in which one of the four bonds in the groups represented by formulae (20) to (26) given as specific examples of G has been 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 A include groups in which any two of the four bonds of the groups represented by formulas (20) to (26) given as specific examples of G are replaced with hydrogen atoms. 4 can be selected from the same groups as A in formula (PI).

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

[0043] Examples of the tetracarboxylic acid compound include aromatic tetracarboxylic acid compounds, alicyclic tetracarboxylic acid compounds, and acyclic aliphatic tetracarboxylic acid compounds. Two or more of these may be used in combination. The tetracarboxylic acid compound is preferably a tetracarboxylic acid dianhydride. Examples of the tetracarboxylic acid dianhydride include aromatic tetracarboxylic acid dianhydrides, alicyclic tetracarboxylic acid dianhydrides, and acyclic aliphatic tetracarboxylic acid dianhydrides.

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

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

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

[0047] Examples of the dicarboxylic acid compound include aromatic dicarboxylic acids, alicyclic dicarboxylic acids, acyclic aliphatic dicarboxylic acids, and their analogous 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 analogous acid chloride compounds. Two or more dicarboxylic acid compounds may be used in combination.

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

[0049] Examples of 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 polymer in a solvent and the transparency and flexibility of a substrate containing the imide polymer, the diamines are preferably selected from alicyclic diamines and aromatic diamines having a fluorine-based substituent.

[0050] Use of such an imide-based polymer makes it easy to obtain a resin film that has particularly excellent flexibility, high light transmittance (for example, 85% or more, preferably 88% or more for light of 550 nm), low yellowness (YI value of 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, and 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). A high weight-average molecular weight of the imide-based polymer tends to provide high flexibility, but if the weight-average molecular weight of the imide-based polymer is too high, the viscosity of the varnish tends to increase and 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, wrinkles, etc. that occur in the resin film and can improve the transparency of the substrate containing the imide-based polymer. Fluorine atoms are preferred as halogen atoms. 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 an imide-based polymer may contain one or more ultraviolet absorbers. The ultraviolet absorber may be appropriately selected from those commonly used as ultraviolet absorbers in the field of resin materials. The ultraviolet absorber may contain a compound that absorbs light with a wavelength of 400 nm or less. Examples of ultraviolet absorbers 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. As used herein, the term "benzophenone-based compound" refers to a derivative of a compound to which the term "benzophenone-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 absorber 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 absorber in these amounts, the weather resistance of the resin film 10 can be improved.

[0055] The substrate containing an 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 an imide-based polymer, the tensile modulus of the substrate containing an imide-based polymer can be easily set to 4.0 GPa or more. However, the method for controlling the tensile modulus of the substrate containing an imide-based polymer is not limited to the addition 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 viewpoint of the 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 size of silica particles in a substrate containing an imide-based polymer can be determined by observation with a transmission electron microscope (TEM). The primary particle size of silica particles can be the unidirectional diameter measured with a transmission electron microscope (TEM). The average primary particle size can be determined by measuring the primary particle size at 10 points using TEM observation and averaging the results. The particle distribution of silica particles before forming a substrate containing an imide-based polymer can be determined using a commercially available laser diffraction particle size distribution analyzer.

[0059] In a substrate containing an imide polymer, the blending ratio of the imide polymer to the inorganic material, where the total of both is 10, is preferably 1:9 to 10:0 by mass, more preferably 3:7 to 10:0, even more preferably 3:7 to 8:2, and even more preferably 3:7 to 7:3. The proportion of the inorganic material relative to the total mass of the imide polymer and the inorganic material is usually 20% by mass or more, preferably 30% by mass or more, and usually 90% by mass or less, preferably 70% by mass or less. When the blending ratio of the imide polymer to the inorganic material (silicon material) is within the above range, the transparency and mechanical strength of the substrate containing the imide polymer tend to be improved. Furthermore, the tensile modulus of the substrate containing the imide polymer can easily be made 4.0 GPa or more.

[0060] The substrate containing an imide-based polymer may further contain components other than the imide-based polymer and inorganic materials, provided that the transparency and flexibility are not significantly impaired. Examples of 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 proportion of components other than the imide-based polymer and inorganic materials is preferably more than 0% and not more than 20% by mass, more preferably more than 0% and not more than 10% by mass, relative to 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 of silicon atoms to nitrogen atoms, Si / N, 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] When the Si / N ratio on the main surface 10a of the substrate containing an imide-based polymer is 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] (Base material thickness) The thickness of the substrate is more preferably 100 μm or less, even 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 surfaces when bent becomes smaller, making it less likely that cracks will occur, and the substrate will not break even after multiple bends. 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 for preparing substrate) The substrate may be formed into a film by thermally melting a thermoplastic polymer, or may be formed into a film by solution casting (solvent casting) from a solution in which the polymer is uniformly dissolved. In the case of thermal melt casting, the softening material and various additives described above can be added during the thermal melting process. On the other hand, when the substrate is produced by the solution casting process, the softening material and various additives described above can be added to the polymer solution (hereinafter also referred to as dope) in each preparation step. The addition may be performed at any time during the dope preparation process, or a step of adding and preparing the additives may be added as the final preparation step in the dope preparation process.

[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 preferred. By using such a protective film, adhesion of dust can be prevented when peeling off the protective film and forming the hard coat layer.

[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 the group consisting of 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, and a cured product of compound (a3) having a polymerizable functional group, and inorganic fine particles. From the viewpoints of pencil hardness and repeated bending resistance, it is particularly preferable to contain a cured product of polyorganosilsesquioxane (A) having a polymerizable group.

[0067] (Polyorganosilsesquioxane (A) having a polymerizable group) The polymerizable group in the polyorganosilsesquioxane (A) having a polymerizable group is not particularly limited, but is preferably a polymerizable group capable of radical polymerization or cation polymerization. The radical polymerizable group may be a commonly known radical polymerizable group, and a preferred example is a (meth)acryloyl group. The cation polymerizable group may be a commonly known cation polymerizable group, and specific examples include an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro orthoester group, and a vinyloxy group. Among these, an alicyclic ether group and a vinyloxy group are preferred, with an epoxy group, an oxetanyl group, and a vinyloxy group being particularly preferred, and an epoxy group being the 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 irradiating with ionizing radiation.

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

[0070] [ka]

[0071] In 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 general formula (1), where q + r = 100, q is greater than 0, and r is 0 or greater. When general formula (1) contains multiple Rb and Rc, the multiple Rb and Rc may be the same or different. When general formula (1) contains multiple Rc, the multiple Rc may form a bond with each other.

[0072] [SiO 1.5 ] represents a structural portion formed of siloxane bonds (Si—O—Si) in polyorganosilsesquioxane. Polyorganosilsesquioxane is a network 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 structures described above, but preferably contains a large amount of ladder structures. The formation of the ladder structure allows the hard coat film to maintain good deformation recovery. The formation of the ladder structure is confirmed by measuring the FT-IR (Fourier Transform Infrared Spectroscopy) spectrum at 1020-1050 cm -1 This can be qualitatively confirmed by the presence or absence of absorption due to Si-O-Si stretching, which is characteristic of the ladder structure, that appears near the surface.

[0073] In the 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 the 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 even more preferably a group represented by the above formula (1b).

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

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

[0079] [ka]

[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, and a substituted or unsubstituted aralkyl group.

[0081] The alkyl group represented by Rc includes alkyl groups having 1 to 10 carbon atoms, such as a straight-chain or branched-chain alkyl group, such as a methyl group, an ethyl group, a propyl group, an n-butyl group, an isopropyl group, an isobutyl group, an s-butyl group, a t-butyl group, and an isopentyl group. The cycloalkyl group represented by Rc includes a cycloalkyl group having 3 to 15 carbon atoms, such as a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. The alkenyl group represented by Rc includes alkenyl groups having 2 to 10 carbon atoms, such as straight-chain or branched-chain alkenyl groups such as vinyl, allyl, and isopropenyl groups. The aryl group represented by Rc includes aryl groups having 6 to 15 carbon atoms, such as a phenyl group, a tolyl group, and a 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 the hydrogen atoms or part or all of the main chain skeleton of the above-mentioned alkyl group, cycloalkyl group, alkenyl group, aryl group, and aralkyl group are 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 acrylic group, a methacrylic group, a mercapto group, and a hydroxyl group.

[0083] Rc is preferably a substituted or unsubstituted alkyl group, 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] The group (Rc2) formed by two Rc's bonding together is preferably an alkylene group formed by bonding the substituted or unsubstituted alkyl groups represented by the above Rc's.

[0086] Examples of the alkylene group represented by Rc2 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] The alkylene group represented by Rc2 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] The group (Rc3) formed by bonding three Rc's together is preferably a trivalent group in which one arbitrary hydrogen atom is removed from the alkylene group represented by the above Rc2.

[0089] In addition, Rc in general formula (1) is derived from a group (a group other than an alkoxy group or a halogen atom; for example, Rc1 to Rc3 in the hydrolyzable silane compounds represented by the formulas (C1) to (C3) described below) bonded to a silicon atom in the hydrolyzable silane compound used as a raw material for polyorganosilsesquioxane.

[0090] In the 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 greater 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, and therefore the hardness and repeated bending resistance can be maintained at a good level. q / (q+r) is more preferably from 0.7 to 1.0, even more preferably from 0.9 to 1.0, and particularly preferably from 0.95 to 1.0.

[0091] In 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. 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) is preferably 500 to 6,000, more preferably 1,000 to 4,500, and even more preferably 1,500 to 3,000, as determined by gel permeation chromatography (GPC) and converted into standard polystyrene.

[0093] The polyorganosilsesquioxane (a1) has a molecular weight dispersity (Mw / Mn) of, for example, 1.0 to 4.0, preferably 1.1 to 3.7, more preferably 1.2 to 3.0, and even more preferably 1.3 to 2.5, as calculated using standard polystyrene standards by GPC, 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 apparatus and under the following conditions. Measuring device: Product name "LC-20AD" (Shimadzu Corporation) Columns: 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 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 the formula 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 structural unit having Rb.

[0100] [ka]

[0101] [ka]

[0102] [ka]

[0103] Rc1 in formula (C1) has the same meaning as Rc in general formula (1) above, and preferred examples are also the same. Rc2 in formula (C2) has the same meaning as the group (Rc2) formed by bonding two Rc's together in general formula (1) above, and preferred examples are also the same. Rc3 in formula (C3) has the same meaning as the group (Rc3) formed by bonding three Rc's together in general formula (1) above, 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) and (C1) to (C3). Examples of the hydrolyzable silane compound include hydrolyzable trifunctional silane compounds, hydrolyzable monofunctional silane compounds, and hydrolyzable bifunctional silane compounds other than the compounds represented by the above formulas (B) and (C1) to (C3).

[0106] When Rc is derived from Rc1 to Rc3 in the hydrolyzable silane compounds represented by the above formulas (C1) to (C3), q / (q+r) in 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, to set q / (q+r) to 0.5 to 1.0, the value represented by the following (Z2) may be set to 0.5 to 1.0, and these compounds may be produced by a method of hydrolyzing and condensing them. (Z2) = (molar amount) of compound represented by formula (B) / {(molar amount) of compound represented by formula (B) + (molar amount) of compound represented by formula (C1) + (molar amount) of compound represented by formula (C2) × 2 + (molar amount) of compound represented by formula (C3) × 3}

[0107] The amount and composition of the hydrolyzable silane compound used can be adjusted appropriately 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 sequentially. When the reactions are carried out sequentially, the order of the reactions is not particularly limited.

[0109] The hydrolysis and condensation reaction of the hydrolyzable silane compound can be carried out either 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 adjusted appropriately within 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 and the like.

[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 (e.g., acetates) such as lithium acetate, sodium acetate, potassium acetate, and cesium acetate; magnesium acetate alkali metal alkoxides such as lithium methoxide, sodium methoxide, sodium ethoxide, sodium isopropoxide, potassium ethoxide, and potassium t-butoxide; alkali metal phenoxides such as sodium phenoxide; amines (tertiary amines, etc.) such as triethylamine, N-methylpiperidine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and 1,5-diazabicyclo[4.3.0]non-5-ene; and nitrogen-containing aromatic heterocyclic compounds such as pyridine, 2,2'-bipyridyl, and 1,10-phenanthroline. The catalyst may be used alone or in combination of two or more. The catalyst may also be used in a state of being dissolved or dispersed in water or a solvent. The catalyst is preferably a base catalyst. Use of a base catalyst can increase the condensation rate of the polyorganosilsesquioxane, and can maintain a good deformation recovery rate when cured.

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

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

[0115] When carrying out the hydrolysis and condensation reaction of the hydrolyzable silane compound, it is particularly important to select reaction conditions that result in a condensation rate of 80% or higher for the polyorganosilsesquioxane (a1). The reaction temperature for 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 higher. The reaction time for 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 increased or reduced pressure. The atmosphere in which the hydrolysis and condensation reaction is carried out may be, for example, a nitrogen atmosphere, an inert gas atmosphere such as an argon atmosphere, or air in the presence of oxygen, but an inert gas atmosphere is preferred.

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

[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 film hardness, 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 calculations.

[0118] In the cured product of the polyorganosilsesquioxane (a1) having epoxy groups, the epoxy groups are 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 groups in the cured product of the polyorganosilsesquioxane (a1) is preferably 40% or more from the viewpoint of film hardness, 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 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 types with different structures.

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

[0121] When the hard coat layer of the present invention contains a cured product of a polyorganosilsesquioxane (A) having a polymerizable group as the cured product of the polymerizable compound, it may further contain a dispersant, an antifouling agent, an antistatic agent, an ultraviolet absorber, an antioxidant, etc. The type of antistatic agent is not particularly limited, and ion-conductive or electron-conductive antistatic agents 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.

[0122] The hard coat layer in the present invention may also 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 with different structures.

[0126] When the hard coat layer in the present invention contains a cured product of a polyfunctional (meth)acrylate compound (a2) as the cured product of the polymerizable compound, the content of the cured product of the polyfunctional (meth)acrylate compound (a2) is preferably 50% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 100% by mass or less, and even more preferably 80% by mass or more and 100% by mass or less, 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. When the hard coat layer of 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 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. M The indentation modulus 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 is indented by 2% of the thickness of the matrix layer in an indentation test.

[0129] The matrix (a3) is preferably a polymer (cured product) obtained by polymerizing a matrix (a3)-forming composition containing a compound (a3) having a polymerizable functional group by irradiation with ionizing radiation or heating. M In order to keep the value within the above range, the polymerizable functional group equivalent in the composition for forming the matrix (a3) is preferably at least 250. If the polymerizable functional group equivalent in the composition for forming the matrix (a3) is too large, the chemical bonding with the functional groups modified on the surface of the inorganic fine particles (described later) decreases, which may deteriorate the hardness and resistance to repeated bending. However, this can be compensated for by selecting an appropriate average primary particle size of the inorganic fine particles and a surface modifier.

[0130] The polymerizable functional group equivalent weight e in the composition for forming the matrix (a3) is calculated from the following formula (4): In the formula, the mass ratios of component 1, component 2, ..., component n contained in the composition for forming the matrix (a3) are represented by R1, R2, ..., R n , the weight average molecular weights of each component are M1, M2, ..., M N , the number of polymerizable functional groups in one molecule of each component is C1, C2, ..., C n It 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, and as the polymerizable functional group (polymerizable group), those that 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, and 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 suitable photopolymerizable monomers include (meth)acrylic acid diesters of ethylene oxide or propylene oxide adducts such as 2,2-bis{4-(acryloxydiethoxy)phenyl}propane and 2,2-bis{4-(acryloxypolypropoxy)phenyl}propane. Furthermore, epoxy(meth)acrylates, urethane(meth)acrylates, and polyester(meth)acrylates are also suitable photopolymerizable monomers.

[0135] In order to ensure that the polymerizable functional group equivalent in the composition for forming the matrix (a3) is 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 1 to 3, and particularly preferably 2. When the compound (a3) having a polymerizable functional group is an oligomer or polymer, the polymerizable functional group may be present at the end of the main chain 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 2500), UV-2000B (molecular weight 13000, number of functional groups 2, functional group equivalent 6500), UV-2750B (molecular weight 3000, functional group equivalent 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 weight 554), UA-160™ (molecular weight 2700, number of functional groups 2, functional group equivalent weight 1350), UA-290™ (molecular weight 2900, number of functional groups 2, functional group equivalent weight 1450), UA-4200 (molecular weight 1000, number of functional groups 2, functional group equivalent weight 500), UA-4400 (molecular weight 1400, number of functional groups 2, functional group equivalent weight 700), etc.

[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, and coumarins. 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 also 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 0.5 to 8 mass %, more preferably 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 described 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 ionically conductive or electronically conductive antistatic agents can be preferably used. A specific example of an electronically conductive antistatic agent that can be preferably used is Sepulgida (manufactured by Shin-Etsu Polymer Co., Ltd.), which uses a polythiophene conductive polymer.

[0141] (Inorganic fine particles) The hardness of the hard coat layer can be increased by adding inorganic fine particles. 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 these, silica particles and zirconia particles are preferred from the viewpoint of ease of modification.

[0142] The surfaces of inorganic fine particles are preferably treated with a surface modifier containing an organic segment. The surface modifier preferably contains, in the same molecule, a functional group capable of bonding with or adsorbing to inorganic fine particles and a functional group having high affinity for organic components. Surface modifiers having functional groups capable of bonding with or adsorbing to inorganic fine particles include metal alkoxide surface modifiers such as silane, aluminum, titanium, and zirconium, and surface modifiers having anionic groups such as phosphate groups, sulfate groups, sulfonate groups, and carboxylate groups. Among these, silane alkoxide surface modifiers (silane coupling agents) are preferred from the viewpoint of ease of modification. Furthermore, functional groups with high affinity for organic components may simply be those that combine hydrophilicity with the matrix component, but functional groups capable of chemically bonding with the matrix component are preferred, particularly ethylenically unsaturated double bond groups or ring-opening polymerizable groups. In the present invention, a preferred inorganic fine particle surface modifier is a curable resin having, in the same molecule, a metal alkoxide or anionic group and an ethylenically unsaturated double bond group or ring-opening polymerizable group. The number of ethylenically unsaturated double bond groups or ring-opening polymerizable groups in one molecule is preferably 1.0 or more and 5.0 or less, and more preferably 1.1 or more and 3.0 or less. 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 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, and 4-(meth)acryloxybutyltriethoxysilane; and silane coupling agents having a ring-opening polymerizable group, such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane. More specifically, examples include KBM-303, KBM-403, KBM-503, and KBM-5103 (all manufactured by Shin-Etsu Chemical Co., Ltd.), and silane coupling agents C-1 and C-2 represented by the following structural formulas.

[0144] [ka]

[0145] [ka]

[0146] Inorganic particles have a surface area of 1 nm 2 It is preferable that 0.2 to 4.0 surface modifiers are bonded or adsorbed per 1 nm 2 0.5 to 3.0 per nm is more preferable, and 1 nm 2 0.8 to 2.0 pieces per unit is more preferable.

[0147] The surface modification of these inorganic fine particles is preferably carried out in a solution. After synthesizing the inorganic fine particles in a solution, a surface modifier is added and stirred; When mechanically finely dispersing the inorganic fine particles, a surface modifier is added and stirred together; After finely dispersing the inorganic fine particles, a surface modifier is added and stirred; Alternatively, the surface modification may be carried out before finely dispersing the inorganic fine particles (if necessary, by heating or drying, followed by heating or pH change), and then finely dispersing. A highly polar organic solvent is preferred as the solution in which the surface modifier is dissolved. 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 determined by observing the cross-section of a thin-section sample obtained by slicing the hard coat film using a transmission electron microscope (TEM) at an appropriate magnification (approximately 400,000x), 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 of the long and short diameters is considered to be the diameter of the primary particle. Thin-section samples can be prepared using a microtome method using an ultramicrotome cross-section cutting device 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 using a TEM as described 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 two or more kinds are used in combination, it is preferable to use particles with different particle diameters from the viewpoint of increasing the volume filling rate of the particles in the hard coat layer.

[0150] When 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 volume ratio of the inorganic fine particles in the hard coat layer is preferably 50% by 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 irregular or other shapes other than spherical.

[0152] When 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% to 100% by mass, more preferably from 70% to 100% by mass, and even more preferably from 80% 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 described 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 ion-conductive or electron-conductive antistatic agents 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.

[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 1,000 to 50,000, and having at least one selected from a fluorine atom, a silicon atom, and a linear or branched alkyl group having three or more carbon atoms, can be preferably used. Hereinafter, a monomer having two or more groups having a radically polymerizable double bond will also be referred to as "monomer (K1)". Furthermore, a polymer obtained by polymerizing a monomer (K1) having two or more groups with a radically polymerizable double bond, having a weight average molecular weight of 1,000 to 50,000, 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 radically polymerizable double bond. When the monomer (K1) contains two or more groups having a radically 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 radically polymerizable double bond contained in the monomer (K1) is not particularly limited, and the two or more groups having a radically polymerizable double bond contained in the monomer (K1) may be the same or different.

[0157] The number of groups having a radically polymerizable double bond in the monomer (K1) is preferably 3 or more, more preferably 3 to 9, and even more preferably 3 to 6. By having 3 or more groups having a radically polymerizable double bond, the branched structure of the polymer (X) becomes a highly branched structure, reducing entanglement between molecular chains of the polymer (X), improving compatibility with curable components and solubility in various organic solvents, and improving the uniform coatability of the composition and the surface condition of the resulting coating film. Furthermore, by having 9 or fewer groups having a radically polymerizable double bond, the molecular weight can be prevented from becoming too high, and solubility in solvents 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 a radically polymerizable double bond 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 general formula (Z3) or (Z4) above 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, which improves the compatibility of the polymer (X) with the curable component and the like contained in the composition containing the polymer (X). 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 even more preferably contained in the polymer (X) as an isocyanuric ring. That is, the polymer (X) preferably has at least one bond 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, 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 formulae (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 the general formula (NII), R 21 and R 22 Each independently represents a hydrogen atom or a methyl group. 21 represents a divalent to hexavalent linking group. n21 represents an integer of 1 to 5. When n21 represents an integer of 2 or more, multiple R 22 may be the same or different.

[0173] [ka]

[0174] In the general formula (NIII), L 31 and L 32 each independently represents a divalent to tetravalent linking group, L 33 represents a divalent linking group, and R 31 and R 32 each independently represents 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, multiple R 31 may be the same or different. When n32 represents an integer of 2 or more, multiple R 32 may be the same or different.

[0175] [ka]

[0176] In the general formula (NIV), Y 41 represents a divalent to hexavalent linking group, and R 41 represents a hydrogen atom or a methyl group, and 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 2 to 6. When n41 represents an integer of 2 or more, multiple R 41 may be the same or different, and multiple 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, 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 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, and 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 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 linking groups include those obtained by removing any one hydrogen atom from a divalent linking group represented by the 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. Preferably, n11 to n13 represent 1.

[0184] The compound represented by 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-mentioned 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 same applies to 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 formula: L 33 represents a divalent linking group, and the above-mentioned L 11 , L 12 and L 13 is the same as the divalent linking group represented by 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, and R 41 represents a hydrogen atom or a methyl group, and 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, and 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 represents a trivalent to hexavalent linking group, the same applies to the above-mentioned 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 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 preferred, and an alkyl group having 1 to 4 carbon atoms is more preferred. 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 above general formula (NIV) can be synthesized according to the method described in WO 2016 / 92844.

[0202] [ka]

[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, multiple 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.

[0204] Y 51 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.

[0205] 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.

[0206] The alkylene group, cycloalkylene group, or arylene group may have a substituent, and 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 represents a trivalent to hexavalent linking group, the same applies to the above-mentioned 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 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 preferred, and an alkyl group having 1 to 4 carbon atoms is more preferred. 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).

[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 The Nippon Synthetic Chemical Industry Co., Ltd. Examples of these include UV-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. Other 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 Hicoop AU-2010 and AU-2020 manufactured by Tokushiki.

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

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[0225]

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[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 including 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, resulting in better uniform coating properties. In addition, the migration of the polymer (X) to the coating surface is further improved, resulting in better surface condition of the coating film.

[0227] The linear or branched alkyl group having 3 or more carbon atoms is preferably a linear or branched alkyl group having 3 to 30 carbon atoms, more preferably a linear or branched alkyl group having 4 to 20 carbon atoms.

[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. 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 then the monomer (K1) and the monomer (K2) may be copolymerized 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 that the polymer (X) is obtained by copolymerizing the monomer (K1) and the monomer (K2) 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.

[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) as 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 formulae (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, and 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 group 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 viewpoint 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, and R 2s It is particularly preferred that half or more of the carbon atoms contained in the group have fluorine atoms as substituents.

[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, and X1 represents a hydrogen atom or a fluorine atom.

[0240] R in general formula (s11) 1s is 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 to 10, and more preferably an integer of 1 to 5. na is preferably an integer of 4 to 12, and more preferably an integer of 4 to 10. X represents a hydrogen atom or a fluorine atom, and is preferably a fluorine atom.

[0241] Examples of the monomer represented by 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, Examples of suitable perfluoroalkyl groups include 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, and 3-(perfluoro-7-methyloctyl)-2-hydroxypropyl (meth)acrylate.

[0242] [ka]

[0243] In general formula (s2), R 1s represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and 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 is 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, 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 even more preferably an integer of 30 to 200.

[0246] As the monomer represented by the general formula (s2), commercially available products may be used, such as polysiloxane macromers containing a (meth)acryloyl group at one end (for example, Silaplane FM-0721, Silaplane FM-0725, Silaplane FM-0711 (all trade names, manufactured by JNC Corporation), AK-5, AK-30, A Examples of suitable acrylic acid esters include K-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, and 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, and R 8s represents a linear or branched alkyl group having 3 or more carbon atoms.

[0249] R in general formula (s3) 1s is R in general formula (s1). 1s The same applies to preferred examples. R 8s 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, 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, and 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 represents 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 polymer (X) is a copolymer of monomer (K1) and monomer (K2), the ratio of the two can be adjusted appropriately depending on the type of monomer used. However, from the viewpoint of improving the surface condition and solvent extractability, the content of monomer (K2) relative to the total amount of monomers is preferably 20 to 90 mol%, more preferably 40 to 80 mol%. By adjusting it to 20 mol% or more, it is possible to maintain good surface condition, and by adjusting it to 90 mol% or less, it is possible to maintain good solvent extractability. By adjusting it to 40 to 80 mol%, it is possible to maintain a good balance between improving the surface condition of polymer (X) and solvent extractability.

[0256] The polymer (X) may also 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 1,000 to 50,000. By setting the weight-average molecular weight to 50,000 or less, the polymer (X) becomes soluble in general-purpose organic solvents, and therefore 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. This enables the polymer (X) to be coated with a uniform surface condition on various general-purpose substrates such as triacetyl cellulose (TAC), polyethylene terephthalate (PET), polycarbonate (PC), and polymethyl methacrylate resin (PMMA). Furthermore, by setting the Mw to 1,000 or more, the effect of improving the surface condition is enhanced. 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 it to stand 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 1,000 to 30,000, further preferably 1,000 to 8,000, and particularly preferably 1,000 to 5,000.

[0259] The molecular weight distribution (Mw / Mn) of the polymer (X) is preferably from 1.00 to 5.00, 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 to the composition (also referred to as the OH content).

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

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

[0264] [Content (g) of polymer (X) / Content (g) of polyorganosilsesquioxane having a polymerizable group] × (content ratio (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 groups in the polyorganosilsesquioxane (A) having a polymerizable group, resulting in good solvent extractability of the polymer (X).

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

[0267] As 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, methyl 2-methoxyacetate, methyl 2-ethoxyacetate, ethyl 2-ethoxyacetate, ethyl 2-ethoxypropionate, 2-methoxyethanol, 2-propoxyethanol, and 2-butoxyethanol. Examples of suitable solvents 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 solvents may be used alone or in combination of two or more.

[0268] As the radical polymerization initiator, known radical polymerization initiators 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 the monomer (k trM : chain transfer reaction rate constant to monomer), f: initiator efficiency, M I : Molecular weight of monomer

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

[0273] The polymer (X) can be solubilized in a general-purpose organic solvent (such as 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 3 to 40% by mass, more preferably 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 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 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] When the hard coat layer contains a cured product of the 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% by mass relative 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% by mass, the deformation recovery of the hard coat film is improved, resulting in increased hardness.

[0282] (film thickness) The thickness of the hard coat layer is not particularly limited, but is preferably 1 to 100 μm, more preferably 5 to 50 μm, and even more preferably 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 microtoming using an ultramicrotome, or by cross-sectional processing 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 polyorganosilsesquioxane (a1) having an epoxy group, it is preferable to have a mixed layer containing 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. 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, and the polyorganosilsesquioxane (a1) having an epoxy group used in forming the above-mentioned hard coat layer.

[0285] Examples of epoxy compounds containing an alicyclic ring include known compounds having one or more alicyclic rings and one or more epoxy groups in the molecule, but are not particularly limited to the following: (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), etc.

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

[0287] [ka]

[0288] In the 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 some or all of the carbon-carbon double bonds have been epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and groups in which multiple of these groups are linked together.

[0289] Examples of the divalent hydrocarbon group include a substituted or unsubstituted, straight-chain or branched-chain alkylene group having 1 to 18 carbon atoms, and a substituted or unsubstituted divalent 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 an "epoxidized alkenylene group") include linear or branched alkenylene groups having 2 to 8 carbon atoms, such as vinylene, propenylene, 1-butenylene, 2-butenylene, butadienylene, pentenylene, hexenylene, heptenylene, and octenylene. 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 having 2 to 4 carbon atoms in which all of the carbon-carbon double bonds have been epoxidized.

[0291] Representative examples of the alicyclic epoxy compound represented by formula (i) above include 3,4,3',4'-diepoxybicyclohexane and compounds represented by formulas (i-1) to (i-10) below. In formulas (i-5) and (i-7) below, l and m each represent an integer of 1 to 30. R' in formula (i-5) below 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 formulas (i-9) and (i-10) below, 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 compounds 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 a p-valent alcohol, and p and n each represent a natural number. Examples of the p-valent alcohol [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, the n's 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)].

[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 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 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 the epoxy compounds include hydrogenated compounds of bisphenol F type epoxy compounds such as [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 epibis-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 epibis-type glycidyl ether epoxy resins obtained by further addition reaction of these epibis-type glycidyl ether epoxy resins with the above-mentioned bisphenols; phenols [e.g., phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol B, etc.]; Examples include novolak alkyl type glycidyl ether epoxy resins obtained by condensing polyhydric alcohols obtained by the condensation reaction of polyphenols (e.g., phenol F, bisphenol S) with aldehydes (e.g., formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, salicylaldehyde) with epihalohydrin; and 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 these phenol skeletons, either directly or via an alkyleneoxy group.

[0299] Examples of the aliphatic epoxy compounds 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 polyalkadiene), 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 also be polyether polyol, polyester polyol, polycarbonate polyol, polyolefin polyol, or 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 in the hard coat layer described above.

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

[0302] The content of the cured epoxy compound (b1) 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, and even more preferably 25% by mass or more and 75% by mass or less, 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 group containing a radically polymerizable double bond, which will be described later.

[0304] Examples of the polyfunctional (meth)acrylate compound (b2) include esters of polyhydric alcohols 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, and pentaerythritol hexa(meth)acrylate. However, in terms of high crosslinking, pentaerythritol triacrylate, pentaerythritol tetraacrylate, or dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, or mixtures thereof are preferred. Furthermore, 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 with different structures.

[0306] The content of the cured product of the polyfunctional (meth)acrylate compound (b2) in the mixed layer is preferably 10 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, 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, or a cured product of another polymerizable compound. The type of antistatic agent is not particularly limited, and an ionically or electronically conductive antistatic agent can be preferably used. A specific example of an electronically 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 cured products of other polymerizable compounds include cured products of compounds having an epoxy group and a (meth)acryloyl group in one molecule. Specific examples of such compounds include Cyclomer M100 manufactured by Daicel, Light Ester G (trade name) manufactured by Kyoeisha Chemical Co., Ltd., 4HBAGE manufactured by Nippon Kasei Chemical Co., Ltd., SP series (trade name) such as SP-1506, 500, SP-1507, 480 manufactured by Showa Polymer, VR series (trade name) such as VR-77, and EA-1010 / ECA, EA-11020, EA-1025, EA-6310 / ECA 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. This is particularly preferred in that the epoxy groups of the polyorganosilsesquioxane (a1) in the hard coat layer and the epoxy groups 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 and enabling the exertion of higher scratch resistance.

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

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

[0312] Examples of the group containing a radically polymerizable double bond that the polyorganosilsesquioxane (c1) has 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 preferably has at least a siloxane structural 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 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 general formula (2), where t + u = 100, t is greater than 0, and u is 0 or greater. When general formula (2) contains multiple Ra and Rc, the multiple Ra and Rc may be the same or different. When general formula (2) contains multiple Rc, the multiple Rc may form a bond with each other.

[0316] [SiO 1.5 ] represents a structural portion formed of siloxane bonds (Si—O—Si) in polyorganosilsesquioxane. [SiO 1.5 The structural portion represented by the symbol "]" is not particularly limited and may be any of a random structure, a ladder structure, a cage structure, etc. From the viewpoint of pencil hardness, it is preferable that the ladder structure is contained in large amounts. 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 confirmed by measuring the FT-IR (Fourier Transform Infrared Spectroscopy) at 1020-1050 cm -1 This can be qualitatively confirmed by the presence or absence of absorption due to Si-O-Si stretching, which is characteristic of the ladder structure, that appears near the surface.

[0317] In the general 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 =CH2(1a)

[0319] In general formula (1a), * represents a linking portion with 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 preferably, for example, 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), and 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 with a valence of na+1, and na represents an integer of 2 or more.

[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 combining these. The substituted or unsubstituted alkylene group includes R 11a Examples of the substituted or unsubstituted alkylene group 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 is R in general formula (1a) 12a The same applies to preferred examples. na preferably represents an integer of 2 to 4, and more preferably 2 or 3.

[0330] L 3a represents a n+1-valent linking group, and preferably represents a n+1-valent hydrocarbon group. 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 general formula (2) is derived from a group (a group other than an alkoxy group or a halogen atom; for example, Ra in the hydrolyzable silane compound represented by formula (A) described later) bonded to a silicon atom in the hydrolyzable trifunctional silane compound used as a raw material for polyorganosilsesquioxane.

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

[0333] [ka]

[0334] In the general formula (2), Rc represents a monovalent group. The monovalent group represented by Rc in general formula (2) has the same definition as Rc in 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 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] In general formula (2), the group (Rc2) formed by two Rc's bonding to each other and the group (Rc3) formed by three Rc's bonding to each other have the same meaning as the group (Rc2) formed by two Rc's bonding to each other and the group (Rc3) formed by three Rc's bonding to each other in general formula (1) above, and preferred groups are also the same.

[0337] In addition, Rc in general formula (2) is derived from a group (a group other than an alkoxy group or a halogen atom; for example, Rc1 to Rc3 in the hydrolyzable silane compounds represented by the above-mentioned formulas (C1) to (C3)) bonded to a silicon atom in the hydrolyzable silane compound used as a raw material for polyorganosilsesquioxane.

[0338] In the 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), crosslinking between polyorganosilsesquioxane molecules is sufficiently formed, thereby maintaining good scratch resistance. t / (t+u) is more preferably from 0.7 to 1.0, even more preferably from 0.9 to 1.0, and particularly preferably from 0.95 to 1.0.

[0339] In 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. 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) is preferably 500 to 6,000, more preferably 1,000 to 4,500, and even more preferably 1,500 to 3,000, as determined by gel permeation chromatography (GPC) and converted into standard polystyrene.

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

[0342] The weight average molecular weight and 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 structural unit containing a (meth)acryloyl group as the hydrolyzable silane compound. When u in 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 the formula 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 structural 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). Examples of the hydrolyzable silane compound include hydrolyzable trifunctional silane compounds, hydrolyzable monofunctional silane compounds, hydrolyzable difunctional silane compounds, and hydrolyzable tetrafunctional silane compounds other than the compounds represented by the above formulas (A) and (C1) to (C3). Specific examples include tetraalkoxysilanes, dialkoxysilanes, and monoalkoxysilanes.

[0349] When Rc is derived from Rc1 to Rc3 in the hydrolyzable silane compounds represented by the above formulas (C1) to (C3), t / (t+u) in 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, to set t / (t+u) to 0.5 to 1.0, the value represented by the following (Z3) may be set to 0.5 to 1.0, and these compounds may be produced by a method of hydrolyzing and condensing them. (Z3) = (molar amount) of compound represented by formula (A) / {(molar amount) of compound represented by formula (A) + (molar amount) of compound represented by formula (C1) + (molar amount) of compound represented by formula (C2) × 2 + (molar amount) of compound represented by formula (C3) × 3}

[0350] The amount and composition of the hydrolyzable silane compound used can be adjusted appropriately depending on the desired structure of the polyorganosilsesquioxane (c1). The polyorganosilsesquioxane (c1) preferably contains 70 mol% or more and 100 mol% or less of the component derived from the compound represented by formula (A), and more preferably 75 mol% or more and 100 mol% or less of the component derived from the compound represented by formula (A). 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 hydrolysis and condensation reaction, it is preferable to neutralize the catalyst to suppress polymerization of the (meth)acryloyl group. Furthermore, the polyorganosilsesquioxane (c1) may be separated and purified by, for example, water washing, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination thereof.

[0353] The polyorganosilsesquioxane (c1) may be used alone or in combination of two or more types with 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 setting the content of the cured product of polyorganosilsesquioxane (c1) to 50% or more, it is possible to maintain good deformation recovery of the hard coat film, which is preferable.

[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 film hardness, 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 calculations. 29 In the Si NMR spectrum, each silicon atom exhibits a signal (peak) at a different position (chemical shift) depending on the bonding state of the silicon atom. Therefore, 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, a slipping agent, and the like. The hollow particles are a component used to reduce the refractive index of the scratch-resistant layer and provide anti-reflection properties. The amount of hollow particles added can be varied depending on the type of hollow particles used, but is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 80% by mass. 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 the 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 a monomer, oligomer, or 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 substituents may be the same or different, and preferably there are multiple 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 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, or a group in which any hydrogen atom in these groups has been substituted with a fluorine atom is 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, more preferably a group having 1 to 10 carbon atoms. The (per)fluoroalkyl group may be a straight-chain structure (e.g., -CFCF, -CH(CF)H, -CH(CF)CF, -CHCH(CF)H), a branched structure (e.g., -CH(CF), -CHCF(CF), -CH(CH)CFCF, -CH(CH)(CF)CFH), 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 -CH2OCH2CF2CF3, -CH2CH2OCH2C4F8H, -CH2CH2OCH2CH2C8F 17, -CH2CH2OCF2CF2OCF2CF2H, and a fluorocycloalkyl group having 4 to 20 carbon atoms and 4 or more fluorine atoms. Examples of the perfluoropolyether group include, for example, -(CF2O) pf -(CF2CF2O) qf -, -[CF(CF3)CF2O] pf -[CF(CF3)] qf -, -(CF2CF2CF2O) pf -, -(CF2CF2O) pf - and more. The above pf and qf each independently represent an integer of 0 to 20, provided that pf+qf is an integer of 1 or more. The total of pf and qf is preferably 1-83, more preferably 1-43, and even more preferably 5-23. The above fluorine-containing compound is -(CF2O) from the viewpoint of excellent scratch resistance. pf -(CF2CF2O) qf It is particularly preferred that the hydroxyl group has a perfluoropolyether group represented by the formula:

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

[0365] There are no particular restrictions on the fluorine atom content of the fluorine-containing compound, but it is preferably 20% by mass or more, more preferably 30 to 70% by mass, and even more preferably 40 to 70% by mass.

[0366] Preferred examples of fluorine-containing compounds include R-2020, M-2020, R-3833, M-3833 and Optool DAC (all trade names) manufactured by Daikin Chemical Industries, Ltd., and Megafac F-171, F-172, F-179A, RS-78, RS-90, Defensa MCF-300 and MCF-323 (all trade names) manufactured by DIC Corporation, but are not limited to these.

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

[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 by 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 even 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 mass %, more preferably 0.1 to 5 mass %, further preferably 0.5 to 5 mass %, and particularly preferably 0.5 to 2 mass %, based on the total mass of the scratch-resistant layer.

[0370] The 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> The hard coat film of the present invention may further have other layers in addition to the hard coat layer, the scratch-resistant layer, and the mixed layer. For example, preferred embodiments include a hard coat layer on both sides of the substrate, an easy-adhesion layer between the substrate and the hard coat layer for improving adhesion, and an antistatic layer for imparting antistatic properties, and the hard coat film may have a plurality of these.

[0372] [Method for producing hard coat film] The method for producing the hard coat film of the present invention is not particularly limited, but one preferred embodiment is a method (embodiment A) in which a hard coat layer-forming composition is applied to a substrate and semi-cured, an abrasion-resistant layer-forming composition is applied to the semi-cured hard coat layer, and then each layer is fully cured. In embodiment A, when the hard coat film of the present invention further has a mixed layer, it is preferable to apply a mixed layer-forming composition to the semi-cured hard coat layer, semi-curing it, apply an abrasion-resistant layer-forming composition to the semi-cured mixed layer, and then fully cure each layer. Another preferred embodiment is a method for 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, and then fully curing each layer. For example, an uncured hard coat layer is formed on a substrate, and a laminate is separately prepared in which an uncured abrasion-resistant layer is formed on a temporary support, 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 lamination surface, and then fully curing each layer and removing the temporary support (embodiment B). Another example is a method (embodiment C) in which a hard coat-forming composition and an abrasion-resistant layer-forming composition are multi-layer coated on a substrate, forming a mixed layer at the interface between the two, and then fully curing each layer.

[0373] The above-mentioned Aspect A will be described in detail below, 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, Aspect A is a production method including the following steps (I) to (VI). (I) A step of forming a coating film (i) by applying a composition for forming a hard coat layer containing the polyorganosilsesquioxane (a1) having an epoxy group onto a substrate. (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), coating film (ii), and coating film (iii) to a full curing treatment.

[0374] <Process (I)> Step (I) is a step of applying a composition for forming a hard coat layer, which contains the aforementioned polyorganosilsesquioxane (a1) having an epoxy group, onto a substrate to form 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. The solid content is generally about 10 to 90% by mass, preferably about 20 to 80% by mass, and particularly preferably about 40 to 70% by mass.

[0375] <Polymerization initiator> The polyorganosilsesquioxane (a1) contains a cationically polymerizable group (epoxy group). The hard coat layer-forming composition preferably contains a cationic photopolymerization initiator to initiate and progress the polymerization reaction of the polyorganosilsesquioxane (a1) by light irradiation. Only one cationic photopolymerization initiator may be used, or two or more different types with 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 capable of generating cations as active species upon irradiation with light, and known cationic photopolymerization initiators can be used without any limitations. Specific examples include known sulfonium salts, ammonium salts, iodonium salts (e.g., diaryliodonium salts), triarylsulfonium salts, diazonium salts, and iminium salts. More specific 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. Cationic photopolymerization initiators can be synthesized by known methods and are also commercially available. 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. Furthermore, iodonium salts are most preferred from the viewpoint of weather resistance.

[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] [ka]

[0381] [ka]

[0382] The content of the polymerization initiator in the hard coat layer-forming composition is not particularly limited, and may be appropriately adjusted within a range in which the polymerization reaction (cationic polymerization) of the polyorganosilsesquioxane (a1) proceeds satisfactorily. For example, the content 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, relative to 100 parts by mass of the polyorganosilsesquioxane (a1).

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

[0384] (solvent) As a solvent that can be included as an optional component, an organic solvent is preferred, and one or more organic solvents can be used by mixing them in any ratio. Specific examples of organic solvents 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; aromatic compounds such as toluene and xylene; glycol ethers such as propylene glycol monomethyl ether; acetate esters such as methyl acetate, ethyl acetate, and butyl acetate; and diacetone alcohol. The amount of 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, per 100 parts by mass of the polyorganosilsesquioxane (a1) and the polymerization initiator combined.

[0385] (additives) The composition may further contain one or more known additives, if necessary. Examples of such additives include dispersants, leveling agents, antifouling agents, antistatic agents, UV 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 commonly used in polymerizable compositions may be used. The type of antistatic agent is not particularly limited, and ionically or electronically conductive antistatic agents are preferably used. A specific example of an electronically conductive antistatic agent is Sepulgida (manufactured by Shin-Etsu Polymer Co., Ltd.), which uses a polythiophene conductive polymer. Furthermore, the amount of additives added to the composition may be adjusted as needed and is not particularly limited.

[0386] <Method for 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 known methods 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 2 can be cured by an ultraviolet lamp. 2 ~1000mJ / cm 2 It is preferable to cure the curable compound by irradiating it with ultraviolet light at an irradiation dose 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, adjusting the oxygen concentration to 0.1 to 2.0% by volume is preferred because it allows for the formation of a semi-cured state in which surface functionality remains. Furthermore, when a component susceptible to curing inhibition (a compound having a (meth)acryloyl group) is not contained, replacing the atmosphere during curing with dry nitrogen is preferred because it eliminates the effect of the epoxy group reacting with water vapor in the air.

[0390] A drying treatment may be carried out as necessary after step (I) or before step (II), or after step (II) or before step (III), or both. The drying treatment may be carried out 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), unreacted epoxy groups in the polyorganosilsesquioxane (a1) contained in the hard coat layer-forming composition and the epoxy compound contained in the mixed layer-forming composition form bonds in steps (IV) and (VI) described below. This bond formation allows the hard coat film of the present invention to have a highly adhesive laminate structure, enabling it to exhibit higher scratch resistance.

[0392] <Process (III)> Step (III) is a step of forming a coating film (ii) by 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). The mixed layer-forming composition is a composition for forming the mixed layer described above. 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), the polyfunctional (meth)acrylate compound (b2), and, if necessary, various additives and a polymerization initiator in a suitable solvent. The solid content is generally about 2 to 90% by mass, preferably about 2 to 80% by mass, and particularly preferably about 2 to 70% by 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. Note that only one type of radical photopolymerization initiator may be used, or two or more types with different structures may be used in combination. This also applies to cationic photopolymerization initiators. Each photopolymerization initiator will be explained below 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 known radical photopolymerization initiators may be used without any limitations. 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, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo- benzophenones such as (4-benzoylbenzyl)trimethylammonium chloride, (4-isopropylbenzyl)trimethylammonium bromide, and (4-benzoylbenzyl)trimethylammonium chloride; thioxanthones such as 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H-thioxanthone-9-one mesochloride;Examples of suitable initiators include acylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. Furthermore, as an auxiliary for the radical photopolymerization initiator, 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. The above radical photopolymerization initiators and auxiliaries 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 that allows the polymerization reaction (radical polymerization) of the radical polymerizable compound to proceed smoothly. 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] Examples of the cationic photopolymerization initiator include the cationic photopolymerization initiators 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 that allows the polymerization reaction (cationic polymerization) of the cationic polymerizable compound to proceed smoothly. 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> The mixed layer-forming composition may further contain one or more optional components in addition to the epoxy compound, the polyfunctional (meth)acrylate compound (b2), and the polymerization initiator. Specific examples of the optional components include solvents and various additives that can be used in the hard coat layer-forming composition.

[0398] <Method for preparing the composition> The mixed layer-forming composition 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.

[0399] The method for applying the mixed layer-forming composition is not particularly limited, and any known method can be used.

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

[0401] The coating film is preferably cured by irradiating the coating film with ionizing radiation.

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

[0403] If necessary, a drying treatment may be carried out after step (III) and before step (IV), or after step (IV) and before step (V), or both.

[0404] By semi-curing the coating film (ii) in step (IV), the unreacted (meth)acryloyl group in the polyfunctional (meth)acrylate compound (b2) contained in the mixed layer-forming composition and the radically polymerizable double bond-containing group in the polyorganosilsesquioxane (c1) having a radically polymerizable double bond-containing group contained in the scratch-resistant layer-forming composition form a bond in step (VI) described below. Also, the epoxy compound (b1) contained in the mixed layer-forming composition and the unreacted epoxy group in the polyorganosilsesquioxane (c1) contained in the scratch-resistant layer-forming composition form a bond in step (VI) described below. By forming the bond, the hard coat film of the present invention has a highly adhesive laminate structure, enabling it to exhibit higher scratch resistance. Although the oxygen concentration during curing is not particularly limited, it is preferable to adjust the oxygen concentration to 0.1 to 2.0% by volume. By setting the oxygen concentration within the above range, the semi-curing can be adjusted.

[0405] <Process (V)> Step (V) is a step of applying a composition for forming an abrasion-resistant layer containing the polyorganosilsesquioxane (c1) having a group containing a radically polymerizable double bond onto the semi-cured coating film (ii) to form a coating film (iii). The composition for forming an abrasion-resistant layer is a composition for forming the above-mentioned abrasion-resistant layer. The composition for forming the scratch-resistant layer is usually in the form of a liquid. The composition for forming the scratch-resistant layer is preferably prepared by dissolving or dispersing the polyorganosilsesquioxane (c1) and, if necessary, various additives and a polymerization initiator in a suitable solvent. The solid content is generally about 2 to 90% by mass, preferably about 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 a polyorganosilsesquioxane (c1) having a group containing a radically polymerizable double bond. In order to initiate and progress the polymerization reaction of the polyorganosilsesquioxane (c1) by light irradiation, the composition for forming an abrasion-resistant layer preferably contains a radical photopolymerization initiator. Note that only one type of radical photopolymerization initiator may be used, or two or more types with 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 the 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 that allows the polymerization reaction (radical polymerization) of the radical polymerizable compound to proceed smoothly. 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 solvents and various additives that can be used in the hard coat layer-forming composition.

[0409] <Method for 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), coating film (ii), and coating film (iii) to a full curing treatment.

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

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

[0415] The present invention also relates to an article provided with the hard coat film of the present invention, and an image display device provided with the 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. [Example]

[0416] The present invention will be explained 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) A 1 L reactor equipped with a stirrer, nitrogen injector, dropping funnel, temperature controller, and condenser was charged with 832 g of N,N-dimethylacetamide (DMAc) under nitrogen flow, and the temperature of the reactor was then raised to 25°C. 64.046 g (0.2 mol) of bistrifluoromethylbenzidine (TFDB) was then added and dissolved. While maintaining the resulting solution at 25°C, 31.09 g (0.07 mol) of 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) and 8.83 g (0.03 mol) of biphenyltetracarboxylic dianhydride (BPDA) were added and stirred for a certain period of time to allow the reaction to proceed. 20.302 g (0.1 mol) of terephthaloyl chloride (TPC) was then added to obtain a polyamic acid solution with a solids concentration of 13% by mass. Next, 25.6 g of pyridine and 33.1 g of acetic anhydride were added to this polyamic acid solution and stirred for 30 minutes, then stirred at 70°C for an additional hour, and then cooled to room temperature. 20 L of methanol was added, and the precipitated solid was filtered and pulverized. It was then dried in a vacuum at 100°C for 6 hours, yielding 111 g 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 resulting 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 with the film fixed thereto was placed in a vacuum oven and heated for 2 hours while gradually increasing the heating temperature from 100°C to 300°C, after which it was gradually cooled. After cooling, the film was separated from the frame and further heat-treated at 300°C for 30 minutes as a final heat treatment step to obtain a 30 μm-thick substrate S-1 made of a polyimide film.

[0419] <Synthesis of Polyorganosilsesquioxane> (Synthesis of Compound (A)) A 1000 mL flask (reaction vessel) equipped with a thermometer, stirrer, reflux condenser, and nitrogen inlet tube was mixed with 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) under a nitrogen stream, and 73.9 g of purified water was added dropwise using a dropping funnel over 30 minutes. The reaction mixture 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, and 300 g of 5% by mass saline was added to extract the organic layer. The organic layer was washed twice, successively, with 300 g of 5% by mass saline and 300 g of pure water, and then concentrated at 1 mmHg and 50 ° C. to obtain a colorless, transparent, liquid product (a polyorganosilsesquioxane having an alicyclic epoxy group, compound (A) (a compound in which Rb: 2-(3,4-epoxycyclohexyl)ethyl group, Rc: methyl group, q = 99, r = 1 in the general formula (1)) containing 59.0% by mass as a solids concentration in methyl isobutyl ketone (MIBK). The compound (A) thus obtained had a number average molecular weight (Mn) of 2310 and a dispersity (Mw / Mn) of 2.1. Note that 1 mmHg is approximately 133.322 Pa.

[0420] (Synthesis of Compound (B)) A methyl isobutyl ketone (MIBK) solution containing compound (B) (a compound represented by general formula (2) in which Ra is a 3-(acryloyloxy)propyl group, t=100, and u=0) at a solids 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 dispersity (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 represented by general formula (2) in which Ra is a 3-(methacryloyloxy)propyl group, t=100, and u=0) at a solids concentration of 60.5 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 compound (C) thus obtained had a number average molecular weight (Mn) of 2050 and a dispersity (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 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 atmospheric air instead of 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> (Hard Coat Layer Forming Composition HC-1) CPI-100P, leveling agent-1, and MIBK (methyl isobutyl ketone) were added to the MIBK solution containing the compound (A), and the concentrations of the components 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 give composition HC-1 for forming a hard coat layer.

[0424] Compound (A) 98.7 parts by mass CPI-100P 1.3 parts by mass Leveling agent-1 0.07 parts by mass 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: left repeating unit: right repeating unit=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 solvent-substituted with a MEK (methyl ethyl ketone) solution, and DPHA, CPI-100P, Irgacure 127, leveling agent-1, and MEK were added. 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 mixed layer-forming composition M-1. In the mixed layer-forming composition M-1, the mixing ratio of compound (A) and DPHA was 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 mass Leveling agent-2 8.0 parts by mass 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: Radical photopolymerization initiator, manufactured by BASF Leveling agent-2: Polymer with the following structure (Mw=20,000, composition ratio of the following repeating units is by mass)

[0430] [ka]

[0431] <Preparation of composition for forming scratch-resistant layer> (Scratch resistant layer forming composition SR-1) The components according to the formulation shown below were placed in a mixing tank, stirred, and filtered through a polypropylene filter with a pore size of 0.4 μm to give a composition for forming an abrasion-resistant layer, SR-1.

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

[0433] The compounds used in the composition for forming the scratch-resistant layer are as follows: RS-90: Slip agent, manufactured by DIC Corporation

[0434] <Preparation of hard coat film> The hard coat layer-forming composition HC-1 was applied onto the substrate S-1 using a die coater, dried at 120°C for 1 minute, and then irradiated with an air-cooled mercury lamp at 25°C with an illuminance of 18 mW / cm. 2 , irradiation amount 10mJ / cm 2 The hard coat layer was semi-cured by irradiating it with ultraviolet light of 1000 kJ / cm.

[0435] The mixed layer-forming composition M-1 was diluted to 1 / 10 by adding MEK to prepare a mixed layer-forming composition. 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 applied to the semi-cured hard coat layer using an air-cooled mercury lamp at 25°C and an oxygen concentration of 1%, with an illuminance of 18 mW / cm. 2 , irradiation amount 10mJ / cm 2 The mixed layer was semi-cured by irradiating it with ultraviolet light of 1000 kJ / cm 2 , thereby providing the mixed layer on the hard coat layer. The scratch-resistant layer-forming composition SR-1 was applied onto the semi-cured mixed 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 with ultraviolet light, the sample 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, mixed layer, and scratch-resistant layer were completely cured by irradiating them with ultraviolet light of 1000 W. The resulting 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 this 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> A 200 L reactor equipped with a stirrer, dropping device, and thermometer was charged with 89.46 kg of pure water and 0.10 kg of 28 wt% aqueous ammonia, 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 added dropwise from the dropping device over 114 minutes. After the addition was completed, the liquid temperature was maintained at the above temperature for an additional 120 minutes while stirring, thereby carrying out hydrolysis and condensation of tetramethoxysilane. The resulting colloidal solution was concentrated to 38.8 kg under a reduced pressure of 13.3 kPa using a rotary evaporator, yielding silica particles P-1 with a SiO2 concentration of 10.0 wt%. The average primary particle size of the silica particles P-1 was 15 nm. 300 g of silica particles P-1 were placed in a 1 L glass reactor equipped with a stirrer. A solution of 2.3 g of 3-methacryloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) dissolved in 20 g of methyl alcohol was added dropwise and mixed. The mixture was then heated at 95°C for approximately 2 hours while stirring. After cooling, 100 g of 1-methoxy-2-propanol was added, and the by-product methanol was distilled off under reduced pressure. Another 300 g of 1-methoxy-2-propanol was added in several portions, and water was distilled off under reduced pressure by azeotropy to a solid content of 60% by mass, yielding 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 ratio (mass %) to prepare a hard coat layer-forming composition HC-2. The composition of the silica particles is based on a dispersion with a solid content of 60%. A-400 10.8 parts by mass Irgacure 184 0.6 parts by mass 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 mass

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

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

[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 with ultraviolet light, the sample 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 light of 1000 W. The resulting film was then heat-treated at 120°C for 1 hour to obtain hard coat film 3 having a 1.0 μm thick scratch-resistant layer on a 17.0 μm thick hard coat layer.

[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 (% by mass) to prepare a hard coat layer-forming composition HC-3. DPCA20 96.9 parts by mass Irgacure 184 3.0 parts by mass 1-Methoxy-2-propanol 100.0 parts by mass Leveling agent-2 0.10 parts by mass

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

[0445] [ka]

[0446] <Preparation of hard coat film> A hard coat film 4 was obtained in the same manner as in Example 3, except that the hard coat layer-forming composition HC-2 was changed to HC-3 and the thickness of the scratch-resistant layer was changed 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 for forming an abrasion-resistant layer SR-1 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 for forming an abrasion-resistant layer SR-1 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 for forming an abrasion-resistant layer SR-1 was changed to DPHA.

[0450] [Evaluation of scratch-resistant layer] Each of the compositions for forming an abrasion-resistant layer was applied to the substrate S-1 using a die coater. After drying at 120°C for 1 minute, the abrasion-resistant layer was irradiated at an illuminance of 60 mW / cm using an air-cooled mercury lamp at 25°C and an oxygen concentration of 100 ppm. 2 , irradiation amount 600mJ / cm 2 After irradiating with ultraviolet light, the sample 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 μm, an abrasion-resistant film having an abrasion-resistant layer of 10.0 μm 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 peak height of the double bond was measured (near the peak area of the carbonyl group) and the value (P101) was calculated by dividing the peak height of the double bond by the peak area of the carbonyl group. The same surface IR measurement was also performed on the same sample prepared without UV irradiation to calculate the value (Q101) by dividing the peak height of the double bond by the peak area of the carbonyl group. 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] (Elastic modulus and recovery rate) The substrate side of each scratch-resistant film and the glass were attached with Aron Alpha (registered trademark) (manufactured by Toa Gosei Co., Ltd.). The 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 represents the recovery rate relative to the maximum indentation depth at the end of the measurement (i.e., load 0) in relation to the depth. The elastic modulus and recovery rate were averaged over 10 measurements.

[0453] [Evaluation of hard-coated films] The hard coat films thus produced were evaluated by the following methods.

[0454] (Pencil hardness) Measurements were carried out in accordance with JIS K 5600-5-4 (1999) and the results were evaluated using 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 15 mm wide and 150 mm long was cut out from the hard-coated film produced in each Example and Comparative Example, and allowed to stand at a temperature of 25°C and a relative humidity of 65% for at least 1 hour. Then, using a folding endurance tester (manufactured by Imoto Machinery Co., Ltd., IMC-0755 model, bending radius 1.0 mm), repeated bending endurance tests were performed with the substrate facing outward. The sample film was evaluated according to the following criteria based on the number of times it could be folded until it cracked or broke. A: Over 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, and the result was used as an index of scratch resistance. Evaluation environment conditions: 25°C, relative humidity 60% Rubbing material: Steel wool (manufactured by Nippon Steel Wool Co., Ltd., Grade No. 0000) Wrap it around the rubbing tip (1 cm x 1 cm) of the tester that comes into contact with the sample and secure it 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-coated film opposite to the side that had been rubbed in each of the Examples and Comparative Examples, and the surface 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 evaluated using the following five-point scale. A: It won't get scratched even if rubbed 10,000 times. B: It will not get scratched even after 5,000 rubs, but it will get scratched by 10,000 rubs. C: No scratches even after 1000 rubs, but scratches appear before 5000 rubs. D: No scratches even after 100 rubs, but scratches appear before 1000 rubs. E: Scratches 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-coated films of the Examples were very good in repeated bending resistance, had high hardness, and were excellent in abrasion resistance. On the other hand, the hard-coated films of Comparative Examples 1, 3, and 4 did not reach the level of repeated bending resistance targeted in the present invention. This is thought to be because the elastic modulus of the abrasion-resistant layer was not sufficiently low. Furthermore, the hard-coated film of Comparative Example 2 had very good repeated bending resistance, but its abrasion resistance was inferior to that of the Examples.

Claims

1. A hard coat film having a substrate, a hard coat layer, and an abrasion-resistant layer in this order, The thickness of the scratch-resistant layer is 1.0 μm to 10 μm, A 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. 2. 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.

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

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

5. 5. The hard coat film according to claim 1, wherein the scratch-resistant layer contains a cured product of a fluorine-containing compound.

6. 6. The hard coat film according to claim 1, wherein the hard coat layer contains a cured product of polyorganosilsesquioxane (a1) having an epoxy group.

7. 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 6, 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.

8. An article comprising the hard coat film according to any one of claims 1 to 7.

9. An image display device comprising the hard coat film according to any one of claims 1 to 7 as a surface protective film.

Images