Hard coat film, article provided with hard coat film, and image display device

Abstract

This invention provides a hard coating film with excellent scratch resistance, high hardness, and excellent resistance to repeated bending, an article having the hard coating film, and an image display device. The hard coating film sequentially comprises a substrate, a hard coating layer, and a hybrid layer. The hard coating layer contains a cured product of a polyorganosilicone sesquioxane (a1) having an epoxy group, and the hybrid 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.

Description

[0001] This application is a divisional application of the invention patent application filed on March 4, 2019, with application number 201980025500.1 and entitled "Hard Coating Film, Article Having Hard Coating Film and Image Display Device". Technical Field

[0002] The present invention relates to a hard coating film, an article having a hard coating film, and an image display device. Background Technology

[0003] In image display devices such as display devices using cathode ray tubes (CRTs), plasma displays (PDPs), electroluminescent displays (ELDs), fluorescent displays (VFDs), field emission displays (FEDs), and liquid crystal displays (LCDs), in order to prevent damage to the display surface, it is preferable to provide an optical film (hard coating) with a hard coating on the substrate.

[0004] For example, Patent Document 1 describes a film having a hard coating, which is formed from a curable composition containing a polyorganosilicone sesquioxane having an epoxy group and a compound having two or more (meth)acryloyl groups in one molecule on a substrate.

[0005] Furthermore, Patent Document 2 describes a film on a glass substrate having a high refractive index layer and a low refractive index layer composed of a cured product comprising a composition including polyorganosiloxane, metal oxide particles, and a polyfunctional (meth)acrylate compound.

[0006] Previous technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2016-160342 Patent Document 2: Japanese Patent Application Publication No. 2012-220556 Summary of the Invention

[0007] The technical problem to be solved by the invention In recent years, the demand for flexible displays, such as in smartphones, has been increasing. As a result, there is a need for optical films that are not easily broken even when repeatedly bent (with excellent resistance to repeated bending). In particular, there is a strong demand for optical films that can balance hardness, scratch resistance, and resistance to repeated bending.

[0008] The inventors have discovered that the membranes described in Patent Document 1 and Patent Document 2 cannot simultaneously achieve hardness, scratch resistance, and resistance to repeated bending.

[0009] The objective of this invention is to provide a hard coating film with excellent scratch resistance, high hardness, and excellent resistance to repeated bending, an article having the above-mentioned hard coating film, and an image display device.

[0010] means for solving technical problems Through in-depth research, the inventors discovered that the above-mentioned problems can be solved by the following method.

[0011] <1> A hard coating film, comprising a substrate, a hard coating layer, and a mixing layer in sequence. The aforementioned hard coating contains a cured product of an epoxy-based polyorganosilyl sesquioxane (a1). The above-mentioned mixed layer contains a cured compound (b1) having an epoxy group and a cured compound (b2) having two or more (meth)acryloyl groups in one molecule.

[0012] <2> The hard coating film according to <1>, wherein the thickness of the above-mentioned mixed layer is 0.05μm to 10μm.

[0013] <3> The hard coating film according to <1> or <2>, wherein, The surface of the above-mentioned mixed layer, on the side opposite to the hard coating side, has a scratch-resistant layer. The aforementioned scratch-resistant layer comprises a cured compound (c1) having two or more (meth)acryloyl groups in one molecule.

[0014] <4> According to the hard coating film described in <3>, the total thickness of the above-mentioned mixed layer and the above-mentioned scratch-resistant layer is 0.1 μm to 10 μm.

[0015] <5> The hard coating film according to any one of <1> to <4>, wherein the above-mentioned epoxy-containing polyorganosilicone sesquioxane (a1) is an alicyclic epoxy-containing polyorganosilicone sesquioxane.

[0016] <6> The hard coating film according to any one of <1> to <5>, wherein the above-mentioned epoxy compound (b1) is an epoxy polysilicon sesquioxane.

[0017] <7> According to the hard coating film described in <6>, the above-mentioned epoxy compound (b1) is a polyorganosilyl sesquioxane having an alicyclic epoxy group.

[0018] <8> The hard coating according to any one of <1> to <7>, wherein, The content of the cured compound (b2) having two or more (meth)acryloyl groups in one molecule in the above mixed layer is 10% by mass or more relative to the total amount of the cured compound (b1) having an epoxy group and the cured compound (b2) having two or more (meth)acryloyl groups in one molecule.

[0019] <9> The hard coating according to any one of <1> to <8>, wherein, The above-mentioned hard coating does not contain cured products containing (meth)acrylyl groups, or the content of cured products containing (meth)acrylyl groups is less than 10% by mass relative to the total amount of the above-mentioned cured products of epoxy-containing polysilicon sesquioxane (a1) and the above-mentioned cured products containing (meth)acrylyl groups.

[0020] <10> The hard coating film according to any one of <1> to <9>, wherein the substrate comprises an imide polymer.

[0021] <11> An article having any one of <1> to <10> hard coating.

[0022] <12> An image display device comprising, as any one of <1> to <10>, a hard coating film as a surface protective film.

[0023] Invention Effects According to the present invention, a hard coating film with excellent scratch resistance, high hardness and excellent resistance to repeated bending, an article having the above-mentioned hard coating film and an image display device can be provided. Detailed Implementation

[0024] The following describes in detail the methods for carrying out the present invention, but the present invention is not limited thereto. Furthermore, in this specification, when numerical values ​​represent physical property values, characteristic values, etc., the phrase "(numerical value 1) to (numerical value 2)" means "(numerical value 1) or more and (numerical value 2) or less." Also, in this specification, the phrase "(meth)acrylate" means "at least one of acrylate and methacrylate." The same applies to "(meth)acrylic acid," "(meth)acryloyl," etc.

[0025] [Hard coating] The hard coating film of the present invention comprises, in sequence, a substrate, a hard coating layer, and a mixing layer. The aforementioned hard coating contains a cured product of an epoxy-based polyorganosilyl sesquioxane (a1). The above-mentioned mixed layer contains a cured compound (b1) having an epoxy group and a cured compound (b2) having two or more (meth)acryloyl groups in one molecule.

[0026] The mechanism by which the hard coating of the present invention exhibits excellent scratch resistance, high hardness, and excellent resistance to repeated bending is not yet clear, but the inventors speculate as follows.

[0027] The hard coating of the present invention contains a cured product of a polyorganosilyl sesquioxane (a1) having epoxy groups. The cured product of (a1) has an inorganic structure (a structure formed by siloxane bonds) formed by the polymerization reaction of epoxy groups into an organic cross-linked network. It is believed that the deformation recovery of the hard coating of the present invention is thus improved, resulting in high pencil hardness.

[0028] Furthermore, it is believed that by having the cured material of (a1) in the hard coating, the elastic modulus of the hard coating will not become too high, and it can maintain moderate softness, thus exhibiting excellent resistance to repeated bending.

[0029] Furthermore, the hard coating film of the present invention has a mixed layer containing a cured compound (b1) having an epoxy group and a cured compound (b2) having two or more (meth)acryloyl groups in one molecule. It is believed that the hard coating film of the present invention exhibits excellent scratch resistance through a structure formed by the intertwining of the cured compounds (b1) and (b2) to form an IPN (Interpenetrating polymer networks) structure. Moreover, it is believed that when a scratch-resistant layer containing a cured compound (c1) having two or more (meth)acryloyl groups in one molecule is applied to the surface of the mixed layer opposite to the hard coating layer, the interlayer adhesion is good, resulting in excellent scratch resistance, since the mixed layer can form covalent bonds with both the hard coating layer and the scratch-resistant layer.

[0030] <Substrate> The substrate of the hard coating film of the present invention will be described.

[0031] The transmittance of the substrate in the visible light region is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. The substrate preferably contains a polymer.

[0032] (polymer) As a polymer, polymers with excellent optical transparency, mechanical strength, and thermal stability are preferred.

[0033] Examples of polymers include, for example, polycarbonate polymers, polyester polymers such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), styrene polymers such as polystyrene and acrylonitrile-styrene copolymer (AS resin), etc. Furthermore, 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, aromatic ester polymers, polyoxymethylene polymers, epoxy polymers, cellulose polymers represented by triacetyl cellulose, copolymers of the above polymers, and polymers obtained by mixing the above polymers.

[0034] In particular, amide polymers such as aromatic polyamides and imide polymers exhibit high fracture bending counts and relatively high hardness as measured by the MIT testing machine according to JIS (Japanese Industrial Standard) P8115 (2001), making them preferred as substrates. For example, aromatic polyamides as described in Example 1 of Japanese Patent No. 5699454, and polyimides described in Japanese Patent Publication No. 2015-508345, Japanese Patent Publication No. 2016-521216, and WO2017 / 014287 are preferred as substrates.

[0035] Furthermore, the substrate can also be formed into a cured layer of UV-curable or thermosetting resins such as acrylic, urethane, acrylate urethane, epoxy, and silicone.

[0036] (Flexible materials) The substrate may contain materials that further soften the aforementioned polymers. Flexible materials refer to compounds that increase the number of times a material can break and bend. As flexible materials, rubber-like elastomers, brittleness modifiers, plasticizers, slip ring polymers, etc., can be used.

[0037] As a flexible material, specifically, the flexible material described in paragraphs <0051> to <0114> of Japanese Patent Application Publication No. 2016-167043 is preferred.

[0038] Flexible materials can be mixed with polymers alone, or multiple materials can be mixed appropriately. They can also be used alone or simultaneously as a substrate without being mixed with polymers.

[0039] There is no particular limitation on the amount of these flexible materials mixed. A polymer with sufficient number of breaking bends can be used alone as the substrate of the membrane, or flexible materials can be mixed together, or all materials can be used as flexible materials (100%) to make it have sufficient number of breaking bends.

[0040] (Other additives) Depending on the application, various additives (e.g., UV absorbers, matting agents, antioxidants, peel accelerators, delay (optical anisotropy) modifiers, etc.) can be added to the substrate. These can be solids or oils. That is, their melting or boiling point is not particularly limited. Furthermore, regarding the timing of additive addition, it can be done at any point during the substrate manufacturing process, or it can be added during the material preparation process. Moreover, the amount of each material added is not particularly limited as long as its function is demonstrated.

[0041] As other additives, the additives described in paragraphs <0117> to <0122> of Japanese Patent Application Publication No. 2016-167043 are preferred.

[0042] The above-mentioned additives can be used alone or in combination of two or more.

[0043] (UV absorber) Examples of ultraviolet absorbers include benzotriazole compounds, triazine compounds, and benzoxazine compounds. Benzotriazole compounds are compounds having a benzotriazole ring; specific examples include various benzotriazole-based ultraviolet absorbers described in paragraph 0033 of Japanese Patent Application Publication No. 2013-111835. Triazine compounds are compounds having a triazine ring; specific examples include various triazine-based ultraviolet absorbers described in paragraph 0033 of Japanese Patent Application Publication No. 2013-111835. Benzoxazine compounds, for example, can be used as described in paragraph 0031 of Japanese Patent Application Publication No. 2014-209162. For example, the content of the ultraviolet absorber in the substrate is approximately 0.1 to 10 parts by mass relative to 100 parts by mass of the polymer contained in the substrate, but there is no particular limitation. Furthermore, regarding ultraviolet absorbers, reference can be made to paragraph 0032 of Japanese Patent Application Publication No. 2013-111835. In addition, in this invention, ultraviolet absorbers with high heat resistance and low volatility are preferred. Examples of relevant ultraviolet absorbers include UVSORB101 (manufactured by FUJIFILM WakoPure Chemical Corporation), TINUVIN 360, TINUVIN 460, TINUVIN 1577 (manufactured by BASF Corporation), LA-F70, LA-31, and LA-46 (manufactured by ADEKA Corporation).

[0044] From the perspective of transparency, the substrate is preferably a flexible material used in the substrate and the difference in refractive index between various additives and polymers is small.

[0045] (Substrate containing imide polymers) As a substrate, a substrate comprising an imide-based polymer is preferred. In this specification, an imide-based polymer refers to a polymer comprising at least one repeating structural unit represented by formula (PI), formula (a), formula (a'), and formula (b). Wherein, if the repeating structural unit represented by formula (PI) is the main structural unit of the imide-based polymer, it is preferred from the viewpoint of film strength and transparency. The repeating structural unit represented by formula (PI) relative to the total repeating structural units of the imide-based polymer is preferably 40 mol% or more, more preferably 50 mol% or more, further preferably 70 mol% or more, particularly preferably 90 mol% or more, and even more preferably 98 mol%.

[0046] [Chemical Formula 1] In formula (PI), G represents a tetravalent organic group, and A represents a divalent organic group. In formula (a), G... 2 A represents a trivalent organic group.2 G represents a divalent organic group. In formula (a'), G... 3 A represents a tetravalent organic group. 3 G represents a divalent organic group. In formula (b), G... 4 and A 4 These represent divalent organic groups.

[0047] In formula (PI), the organic group represented by G (hereinafter sometimes referred to as the organic group of G) can be selected from the group consisting of acyclic aliphatic groups, cyclic aliphatic groups, and aromatic groups. From the viewpoint of transparency and flexibility of the substrate containing the imide polymer, the organic group of G is preferably a tetravalent cyclic aliphatic group or a tetravalent aromatic group. Examples of aromatic groups include monocyclic aromatic groups, fused polycyclic aromatic groups, and non-fused polycyclic aromatic groups having two or more aromatic rings that are directly or indirectly linked by a linker. From the viewpoint of transparency of the resin film and suppression of color change, the organic group of G is preferably a cyclic aliphatic group, a cyclic aliphatic group with fluorine substituents, a monocyclic aromatic group with fluorine substituents, a fused polycyclic aromatic group with fluorine substituents, or a non-fused polycyclic aromatic group with fluorine substituents. In this specification, a fluorine substituent refers to a group containing a fluorine atom. The fluorine substituents are preferably fluorine groups (fluorine atom, -F) and perfluoroalkyl groups, and more preferably fluorine groups and trifluoromethyl groups.

[0048] More specifically, the organic group of G is selected, for example, from saturated or unsaturated cycloalkyl, saturated or unsaturated heterocycloalkyl, aryl, heteroaryl, aralkyl, alkylaryl, heteroalkylaryl, and groups having any two of these groups (which may be the same) and which are directly or indirectly linked to each other by a linking group. Examples of linking groups include -O-, alkylene groups having 1 to 10 carbon atoms, -SO2-, -CO-, or -CO-NR- (where R represents alkyl or hydrogen atoms having 1 to 3 carbon atoms, such as methyl, ethyl, or propyl).

[0049] The number of carbon atoms in the tetravalent organic group represented by G is typically 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 or aromatic group, at least one of the carbon atoms constituting these groups can be replaced by a heteroatom. Examples of heteroatoms include O, N, or S.

[0050] Specific examples of G can be given by groups represented by the following formulas (20), (21), (22), (23), (24), (25), or (26). In the formulas... The Z in formula (26) represents a connecting 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 with 6 to 20 carbon atoms, such as a phenylene group. At least one of the hydrogen atoms in these groups may be substituted with a fluorine substituent.

[0051] [Chemical Formula 2] In formula (PI), the organic group represented by A (hereinafter sometimes referred to as the organic group of A) can be 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. As aromatic groups, examples include monocyclic aromatic groups, fused polycyclic aromatic groups, and non-fused polycyclic aromatic groups having two or more aromatic rings that are directly or indirectly linked by a linker. From the viewpoint of resin film transparency and suppression of coloration, it is preferable to introduce a fluorinated substituent into the organic group of A.

[0052] More specifically, the organic group of A is selected, for example, from saturated or unsaturated cycloalkyl, saturated or unsaturated heterocycloalkyl, aryl, heteroaryl, aralkyl, alkylaryl, heteroalkylaryl, and groups having any two of these groups (which may be the same) and which are directly or indirectly linked to each other by a linking group. Examples of heteroatoms include O, N, or S, and examples of linking groups include -O-, alkylene groups having 1 to 10 carbon atoms, -SO2-, -CO-, or -CO-NR- (R includes alkyl or hydrogen atoms having 1 to 3 carbon atoms, such as methyl, ethyl, or propyl).

[0053] The number of carbon atoms in the divalent organic group represented by A is usually 2 to 40, preferably 5 to 32, more preferably 12 to 28, and even more preferably 24 to 27.

[0054] As specific examples of A, groups represented by the following formulas (30), (31), (32), (33), or (34) can be cited. In the formulas... Indicates a connection key. Z 1 ~Z 3 Each of these groups independently represents a single bond, -O-, -CH2-, -C(CH3)2-, -SO2-, -CO-, or -CO-NR- (R represents an alkyl group with 1 to 3 carbon atoms, such as methyl, ethyl, or propyl, or a hydrogen atom). In the following groups, Z... 1 and Z 2 and Z 2 and Z 3Preferably, it is located in the meta or para position relative to each ring. Furthermore, Z 1 and terminal single bond, Z 2 and terminal single bonds and Z 3 The terminal single bonds are preferably located in the meta or para positions, respectively. In one example of A, Z 1 and Z 3 It is -O-, and Z 2 The groups are -CH2-, -C(CH3)2-, or -SO2-. One or more hydrogen atoms in these groups can be replaced by fluorine substituents.

[0055] [Chemical Formula 3] At least one hydrogen atom in at least one of the hydrogen atoms constituting A and G may be substituted by at least one functional group selected from the group consisting of fluorinated substituents, hydroxyl groups, sulfone groups, and alkyl groups having 1 to 10 carbon atoms. Furthermore, when the organic group of A and the organic group of G are respectively cyclic aliphatic groups or aromatic groups, it is preferable that at least one of A and G has a fluorinated substituent, and more preferably that both A and G have fluorinated substituents.

[0056] G in equation (a) 2 It is a trivalent organic group. This organic group is trivalent, and apart from this, it can be selected from the same group as the organic group of G in formula (PI). As G 2 Examples of G can be given as groups in which any one of the four bonds of the group represented by formulas (20) to (26) is replaced by a hydrogen atom. A2 in formula (a) can be selected from the same group as A in formula (PI).

[0057] G in equation (a') 3 It can be selected from the same group as G in formula (PI). A in formula (a') 3 It can be selected from the same group as A in formula (PI).

[0058] G in equation (b) 4 It is a divalent organic group. This organic group is divalent, and apart from this, it can be selected from the same organic group as G in formula (PI). As G 4 Examples of this can be given as G specifically, where any two of the four bonds of the group represented by equations (20) to (26) are replaced by hydrogen atoms. A in equation (b) 4 It can be selected from the same group as A in formula (PI).

[0059] The imide polymer contained in the substrate comprising the imide polymer can be a condensation polymer obtained by polycondensation of at least one of a diamine with a tetracarboxylic acid compound (including acyl chloride compounds and tetracarboxylic acid dianhydrides, etc.) or a tricarboxylic acid compound (including acyl chloride compounds and tricarboxylic acid anhydrides, etc.). Furthermore, the dicarboxylic acid compound (including acyl chloride compounds, etc., etc.) can also be polycondensed. Typically, the repeating structural unit represented by formula (PI) or formula (a') is derived from a diamine and a tetracarboxylic acid compound. Typically, the repeating structural unit represented by formula (a) is derived from a diamine and a tricarboxylic acid compound. Typically, the repeating structural unit represented by formula (b) is derived from a diamine and a dicarboxylic acid compound.

[0060] Examples of tetracarboxylic acid compounds include aromatic tetracarboxylic acid compounds, alicyclic tetracarboxylic acid compounds, and acyclic aliphatic tetracarboxylic acid compounds. Two or more of these can be used simultaneously. The preferred tetracarboxylic acid compound is a tetracarboxylic dianhydride. Examples of tetracarboxylic dianhydrides include aromatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and acyclic aliphatic tetracarboxylic dianhydrides.

[0061] From the viewpoint of the solubility of imide polymers in solvents, as well as the transparency and flexibility when forming a substrate, the tetracarboxylic acid compound is preferably an alicyclic tetracarboxylic acid compound or an aromatic tetracarboxylic acid compound. From the viewpoint of the transparency of the substrate containing the imide polymer and the suppression of coloring, the tetracarboxylic acid compound is preferably selected from alicyclic tetracarboxylic acid compounds having fluorine substituents and aromatic tetracarboxylic acid compounds having fluorine substituents, and more preferably alicyclic tetracarboxylic acid compounds having fluorine substituents.

[0062] Examples of tricarboxylic acid compounds include aromatic tricarboxylic acids, alicyclic tricarboxylic acids, acyclic aliphatic tricarboxylic acids, and similar acyl chloride compounds and acid anhydrides. The preferred tricarboxylic acid compound is selected from aromatic tricarboxylic acids, alicyclic tricarboxylic acids, acyclic aliphatic tricarboxylic acids, and similar acyl chloride compounds. Two or more tricarboxylic acid compounds may be used simultaneously.

[0063] From the viewpoint of the solubility of imide polymers in solvents, and the transparency and flexibility when forming a substrate containing an imide polymer, the tricarboxylic acid compound is preferably an alicyclic tricarboxylic acid compound or an aromatic tricarboxylic acid compound. From the viewpoint of the transparency of the substrate containing the imide polymer and the suppression of coloring, the tricarboxylic acid compound is more preferably an alicyclic tricarboxylic acid compound with fluorine substituents or an aromatic tricarboxylic acid compound with fluorine substituents.

[0064] Examples of dicarboxylic acid compounds include aromatic dicarboxylic acids, alicyclic dicarboxylic acids, noncyclic aliphatic dicarboxylic acids, and similar acyl chloride compounds and acid anhydrides. The preferred dicarboxylic acid compound is selected from aromatic dicarboxylic acids, alicyclic dicarboxylic acids, noncyclic aliphatic dicarboxylic acids, and similar acyl chloride compounds. Two or more dicarboxylic acid compounds may be used simultaneously.

[0065] From the viewpoint of the solubility of imide polymers in solvents, and the transparency and flexibility when forming a substrate containing an imide polymer, the dicarboxylic acid compound is preferably an alicyclic dicarboxylic acid compound or an aromatic dicarboxylic acid compound. From the viewpoint of the transparency of the substrate containing the imide polymer and the suppression of coloring, the dicarboxylic acid compound is further preferably an alicyclic dicarboxylic acid compound having fluorine substituents or an aromatic dicarboxylic acid compound having fluorine substituents.

[0066] Examples of diamines include aromatic diamines, alicyclic diamines, and aliphatic diamines, and two or more of these can be used simultaneously. Considering the solubility of imide polymers in solvents, as well as the transparency and flexibility when forming substrates containing imide polymers, diamines are preferably selected from alicyclic diamines and aromatic diamines with fluorine substituents.

[0067] If such imide polymers are used, resin films with particularly excellent flexibility and high light transmittance (e.g., more than 85% transmittance to light at 550 nm, preferably more than 88%), low yellowness (YI value, 5 or less, preferably 3 or less) and low haze (1.5% or less, preferably 1.0% or less) can be easily obtained.

[0068] Imide polymers can be copolymers comprising various types of the aforementioned repeating structural units. The weight-average molecular weight of polyimide polymers is typically 10,000 to 500,000. Preferably, the weight-average molecular weight of the imide polymer is 50,000 to 500,000, more preferably 70,000 to 400,000. The weight-average molecular weight is the equivalent molecular weight of standard polystyrene determined by gel permeation chromatography (GPC). A high weight-average molecular weight of the imide polymer tends to result in high flexibility, but an excessively high weight-average molecular weight tends to increase the viscosity of the varnish and reduce its processability.

[0069] The imide polymer may contain halogen atoms, such as fluorine atoms, which can be introduced through the aforementioned fluorine substituents. By including halogen atoms in the polyimide polymer, the elastic modulus of the substrate containing the imide polymer can be increased and the yellowness can be reduced. This suppresses scratches and wrinkles on the resin film and improves the transparency of the substrate containing the imide polymer. Fluorine atoms are preferred as halogen atoms. Based on the mass of the polyimide polymer, the content of halogen atoms in the polyimide polymer is preferably 1 to 40% by mass, more preferably 1 to 30% by mass.

[0070] The substrate containing the imide polymer may contain one or more ultraviolet absorbers. The ultraviolet absorbers can be suitably selected from substances commonly used as ultraviolet absorbers in the field of resin materials. The ultraviolet absorbers may include compounds that absorb light with wavelengths below 400 nm. Examples of ultraviolet absorbers suitable for combination with the imide polymer include, for instance, at least one compound selected from the group consisting of benzophenone compounds, salicylate compounds, benzotriazole compounds, and triazine compounds.

[0071] In this specification, "system compound" refers to a derivative of a compound labeled "system compound". For example, "benzophenone system compound" refers to a compound having benzophenone as the parent skeleton and substituents bonded to benzophenone.

[0072] The content of the ultraviolet absorber relative to the total mass of the resin film is typically 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, typically 10% by mass or less, preferably 8% by mass or less, more preferably 6% by mass or less. By including these amounts of ultraviolet absorber, the weather resistance of the resin film 10 can be improved.

[0073] The substrate containing the imide polymer may further contain inorganic materials such as inorganic particles. The inorganic material is preferably a silicon material containing silicon atoms. By including inorganic materials such as silicon in the substrate containing the imide polymer, it is easy to set the tensile modulus of the substrate containing the imide polymer to 4.0 GPa or higher. However, the method for controlling the tensile modulus of the substrate containing the imide polymer is not limited to the combination of inorganic materials.

[0074] 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 transparency and flexibility of substrates containing imide polymers.

[0075] The average uniform particle size of silica particles is typically below 100 nm. If the average uniform particle size of silica particles is below 100 nm, there is a tendency for increased transparency.

[0076] The average uniform particle size of silica particles in a substrate containing an imide-based polymer can be determined by observation using transmission electron microscopy (TEM). The primary particle size of the silica particles can be set as the directional diameter based on the TEM. The primary particle size is measured at 10 locations using TEM observation, and the average value is used as the average uniform particle size. The particle distribution of silica particles before the formation of the substrate containing the imide-based polymer can be determined using a commercially available laser diffraction particle size analyzer.

[0077] In a substrate containing an imide polymer, the mass ratio of the imide polymer to the inorganic material, where the total mass of both is 10, is preferably 1:9 to 10:0, more preferably 3:7 to 10:0, further preferably 3:7 to 8:2, and even more preferably 3:7 to 7:3. The total mass ratio of the inorganic material to the imide polymer and the inorganic material is typically 20% by mass or more, preferably 30% by mass or more, typically 90% by mass or less, and preferably 70% by mass or less. If the mass ratio of the imide polymer to the inorganic material (silicon material) is within the above range, the substrate containing the imide polymer tends to have improved transparency and mechanical strength. Furthermore, the tensile modulus of elasticity of the substrate containing the imide polymer can be easily set to 4.0 GPa or more.

[0078] The substrate containing the imide polymer may further contain components other than the imide polymer and inorganic materials, within a range that does not significantly impair transparency and flexibility. Examples of components other than the imide polymer and inorganic materials include, for instance, antioxidants, release agents, stabilizers, colorants such as bluing agents, flame retardants, lubricants, thickeners, and leveling agents. The mass ratio of components other than the imide polymer and inorganic materials to the resin film 10 is preferably more than 0% and less than 20% by mass, more preferably more than 0% and less than 10% by mass.

[0079] When the substrate containing the imide polymer contains both the imide polymer and silicon material, the atomic ratio of silicon atoms to nitrogen atoms, i.e., Si / N, on at least one main surface 10a is preferably 8 or more. This atomic ratio Si / N is calculated based on the amount of silicon atoms and nitrogen atoms present, obtained by evaluating the composition of the substrate containing the imide polymer using X-ray photoelectron spectroscopy (XPS).

[0080] By having a Si / N ratio of 8 or higher on the main surface 10a of the substrate containing the imide polymer, sufficient adhesion between the substrate and the functional layer 20 (described later) can be obtained. From the viewpoint of adhesion, a Si / N ratio of 9 or higher is more preferable, 10 or higher is even more preferable, 50 or lower is more preferable, and 40 or lower is even more preferable.

[0081] (Thickness of the substrate) The thickness of the substrate is more preferably 100 μm or less, further preferably 80 μm or less, and most preferably 50 μm or less. If the substrate thickness is reduced, the curvature difference between the surface and back side during bending decreases, making it less prone to cracking and preventing substrate breakage even after multiple bends. On the other hand, from the viewpoint of ease of substrate handling, the substrate thickness is preferably 3 μm or more, more preferably 5 μm or more, and most preferably 15 μm or more.

[0082] (Method for manufacturing the substrate) The substrate can be formed by hot-melting a thermoplastic polymer to create a film, or by solution casting (solution casting) using a solution in which the polymer is uniformly dissolved. During hot-melt film formation, the aforementioned flexible material and various additives can be added during the hot-melt process. Conversely, when preparing the substrate using the solution casting method, the aforementioned flexible material and various additives can be added to the polymer solution (hereinafter, also referred to as concentrate) in each preparation step. Furthermore, the timing of their addition can be arbitrary during the concentrate preparation step, or it can be performed by adding the additives and preparing the substrate in the final preparation step of the concentrate preparation step.

[0083] The coating film can be heated to dry and / or bake. The heating temperature is typically 50–350°C. Heating can be carried out under an inert atmosphere or reduced pressure. Heating the coating film allows the solvent to evaporate and be removed. The resin film can also be formed by a process including drying the coating film at 50–150°C and baking the dried coating film at 180–350°C.

[0084] Surface treatment can be applied to at least one main surface of the substrate.

[0085] A protective film can be adhered to one or both sides of the substrate to protect the surface or maintain the smoothness of the substrate. Preferably, the protective film is an adhesive layer containing an antistatic agent, laminated on one side of the support. Using such a protective film prevents dust adhesion when the protective film is peeled off to form a hard coating.

[0086] <Hard coating> The hard coating of the hard coating film of the present invention will be described.

[0087] The hard coating in this invention contains a cured product of a polyorganosilyl sesquioxane (a1) having an epoxy group.

[0088] Cured products of epoxy-containing polyorganosilicone silsesquioxanes (a1) are preferably cured by heating and / or irradiating with ionizing rays onto a curable composition containing epoxy-containing polyorganosilicone silsesquioxanes (a1).

[0089] (a1) Polyorganosilicone sesquioxane with epoxy groups The polyorganosilicone silsesquioxane (a1) having an epoxy group (also referred to as "polyorganosilicone silsesquioxane (a1)") has at least a siloxane structural unit containing an epoxy group, preferably a polyorganosilicone silsesquioxane represented by the following general formula (1).

[0090] [Chemical Formula 4] 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 greater than or equal to 0. When multiple Rb and Rc exist in general formula (1), they can be identical or different. When multiple Rc exist in general formula (1), they can form bonds with each other.

[0091] In general formula (1) [SiO 1.5 [] indicates the structural part of polyorganosilicon silsesquioxane composed of siloxane bonds (Si-O-Si).

[0092] Polyorganosilyl silsesquioxanes are network polymers or cluster polyhedra possessing siloxane structural units derived from hydrolyzable trifunctional silane compounds, capable of forming random, ladder, and cage-like structures through siloxane bonds. In this invention, [SiO 1.5 The structural portion represented can be any of the structures described above, but it is preferable to contain a large number of trapezoidal structures. By forming trapezoidal structures, the deformation recovery of the hard coating film can be well maintained. Regarding the formation of the trapezoidal structures, it is possible to determine the structure in the 1020-1050 cm⁻¹ range during FT-IR (Fourier Transform Infrared Spectroscopy) measurement. -1 The presence of trapezoidal structures in the vicinity is used for qualitative confirmation to determine whether there is absorption originating from characteristic Si-O-Si stretching.

[0093] In general formula (1), Rb represents a group containing an epoxy group.

[0094] Examples of groups containing epoxy groups include known groups having an ethylene oxide ring.

[0095] Rb is preferably a group represented by the following formulas (1b) to (4b).

[0096] [Chemical Formula 5] In the above equations (1b) to (4b), R represents the connection part with Si in general formula (1). 1b R 2b R 3b and R 4b Indicates substituted or unsubstituted alkylene groups.

[0097] As R 1b R 2b R 3b and R 4b The alkylene group represented is preferably a straight-chain or branched alkylene group having 1 to 10 carbon atoms. Examples include methylene, methylmethylene, dimethylmethylene, ethylene, isopropylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-decylene, etc.

[0098] As R 1b R 2b R 3b and R 4b Examples of substituents for alkylene groups include hydroxyl, carboxyl, alkoxy, aryl, heteroaryl, halogen, nitro, cyano, and silyl groups.

[0099] As R 1b R 2b R 3b and R 4b Preferably, it is a straight-chain alkylene group with 1 to 4 unsubstituted carbon atoms, or a branched alkylene group with 3 or 4 unsubstituted carbon atoms, more preferably ethylene, n-propylene, or isopropylene, and even more preferably ethylene or n-propylene.

[0100] The polyorganosilicon silsesquioxane (a1) preferably has an alicyclic epoxy group (a group with a fused ring structure having an epoxy group and an alicyclic group). Rb in general formula (1) is preferably an alicyclic epoxy group, more preferably a group having an epoxy cyclohexyl group, and even more preferably a group represented by the above formula (1b).

[0101] In addition, Rb in general formula (1) is derived from a group (other than alkoxy and halogen atoms) that is bonded to the silicon atom in a hydrolyzable trifunctional silane compound used as a raw material for polyorganosilicon silsesquioxane.

[0102] The following are specific examples of Rb, but the invention is not limited to these. In the following specific examples, This represents the connection part with Si in general formula (1).

[0103] [Chemical Formula 6] In general formula (1), Rc represents a monovalent group.

[0104] Examples of monovalent groups represented by Rc include hydrogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted aryl groups, or substituted or unsubstituted aralkyl groups.

[0105] As represented by Rc, alkyl groups having 1 to 10 carbon atoms can be cited, such as straight-chain or branched alkyl groups like methyl, ethyl, propyl, n-butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, and isopentyl.

[0106] Examples of cycloalkyl groups represented by Rc include those with 3 to 15 carbon atoms, such as cyclobutyl, cyclopentyl, and cyclohexyl.

[0107] Examples of alkenyl groups represented by Rc include alkenyl groups with 2 to 10 carbon atoms, such as vinyl, allyl, and isopropenyl alkenyl groups, which are straight-chain or branched.

[0108] Aryl groups represented by Rc can be categorized by the number of carbon atoms from 6 to 15, such as phenyl, tolyl, and naphthyl.

[0109] Aryl groups represented by Rc can be aryl groups with 7 to 20 carbon atoms, such as benzyl and phenethyl.

[0110] As the aforementioned substituted alkyl, substituted cycloalkyl, substituted alkenyl, substituted aryl, or substituted aralkyl groups, examples include hydrogen atoms or part or all of the main chain skeleton of each of the aforementioned alkyl, cycloalkyl, alkenyl, aryl, and aralkyl groups being selected from at least one substituted group selected from the group consisting of ether, ester, carbonyl, halogen (fluorine, etc.), acryloyl, methacryloyl, mercapto, and hydroxyl group.

[0111] Rc is preferably a substituted or unsubstituted alkyl group, more preferably an unsubstituted alkyl group having 1 to 10 carbon atoms.

[0112] When multiple Rcs exist in general formula (1), the multiple Rcs can form bonds with each other. It is preferred that two or three Rcs form bonds with each other, and more preferably two Rcs form bonds with each other.

[0113] As a group (Rc2) formed by the mutual bonding of two Rcs, it is preferably an alkylene group formed by the bonding of substituted or unsubstituted alkyl groups represented by the above Rcs.

[0114] Examples of straight-chain or branched alkylene groups represented by Rc2 include methylene, ethylene, propylene, isopropylene, n-butylene, isobutylene, sec-butylene, tert-butylene, n-pentylene, isopentylene, sec-pentylene, tert-pentylene, n-hexylene, isohexylene, sec-hexylene, tert-hexylene, n-heptylene, isoheptylene, sec-heptylene, tert-heptylene, n-octylene, isooctylene, sec-octylene, and tert-octylene.

[0115] As represented by Rc2, the alkylene group is preferably an unsubstituted alkylene group with 2 to 20 carbon atoms, more preferably an unsubstituted alkylene group with 2 to 20 carbon atoms, and even more preferably an unsubstituted alkylene group with 2 to 8 carbon atoms, especially preferably n-butylene, n-pentylene, n-hexylene, n-heptylene, or n-octylene.

[0116] As a group (Rc3) formed by the mutual bonding of 3 Rc atoms, it is preferably a trivalent group obtained by reducing any one hydrogen atom in the alkylene group represented by Rc2 above.

[0117] In addition, Rc in general formula (1) is derived from a group (other than alkoxy and halogen atoms) that is bonded to the silicon atom in a hydrolyzable silane compound used as a raw material for polyorganosilicon silsesquioxane. For example, Rc1 to Rc3 in hydrolyzable silane compounds represented by formulas (C1) to (C3) described later.

[0118] In general formula (1), q is greater than 0 and r is greater than or equal to 0.

[0119] q / (q+r) is preferably 0.5 to 1.0. By setting the number of groups represented by Rb to more than half of the total number of groups represented by Rb or Rc contained in the polyorganosilicon silsesquioxane (a1), a network made of organic crosslinking groups is fully formed, thus maintaining various properties such as hardness and resistance to repeated bending well.

[0120] The value of q / (q+r) is more preferably 0.7 to 1.0, even more preferably 0.9 to 1.0, and especially preferably 0.95 to 1.0.

[0121] In general formula (1), it is also preferable that there are multiple Rcs and that the multiple Rcs form bonds with each other. In this case, r / (q+r) is preferably 0.005 to 0.20.

[0122] r / (q+r) is more preferably 0.005 to 0.10, even more preferably 0.005 to 0.05, and particularly preferably 0.005 to 0.025.

[0123] The number-average molecular weight (Mn) of the polyorganosilyl sesquioxane (a1) converted from standard polystyrene by gel permeation chromatography (GPC) is preferably 500 to 6000, more preferably 1000 to 4500, and even more preferably 1500 to 3000.

[0124] The molecular weight dispersion (Mw / Mn) of the polyorganosilyl silsesquioxane (a1) based on GPC standard polystyrene conversion is, for example, 1.0 to 4.0, preferably 1.1 to 3.7, more preferably 1.2 to 3.0, even more preferably 1.3 to 2.5, and particularly preferably 1.45 to 1.80. Furthermore, Mn represents the number-average molecular weight.

[0125] The weight-average molecular weight and molecular weight dispersion of polyorganosilicon sesquioxane (a1) were determined using the following apparatus and under the following conditions.

[0126] Measuring apparatus: Trade name "LC-20AD" (manufactured by SHIMADZU CORPORATION) Pillars: Shodex KF-801 x 2, KF-802 and KF-803 (made by SHOWA DENKO KK) Measurement temperature: 40℃ Eluent: Tetrahydrofuran (THF), sample concentration 0.1–0.2% by mass Flow rate: 1 mL / min Detector: UV-VIS detector (trade name "SPD-20A", manufactured by SHIMADZU CORPORATION) Molecular weight: Conversion from standard polystyrene <Method for manufacturing polyorganosilicon silsesquioxane (a1)> Polyorganosilyl silsesquioxane (a1) can be manufactured by known manufacturing methods without particular limitation, and can be manufactured by hydrolyzing and condensing one or more hydrolyzable silane compounds. As the aforementioned hydrolyzable silane compound, it is preferable to use a hydrolyzable trifunctional silane compound (a compound represented by the following formula (B)) for forming siloxane structural units containing epoxy groups.

[0127] When r is greater than 0 in general formula (1), it is preferable to use a compound represented by the following formula (C1), (C2) or (C3) as a hydrolyzable silane compound.

[0128] [Chemical Formula 7] The meaning of Rb in formula (B) is the same as that of Rb in the general formula (1) above, and the preferred examples are also the same.

[0129] X in equation (B) 2 It represents an alkoxy or halogen atom.

[0130] As X 2 Alkoxy groups, for example, include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, and other alkoxy groups with 1 to 4 carbon atoms.

[0131] As X 2 Halogen atoms in the atom can be, for example, fluorine, chlorine, bromine, iodine, etc.

[0132] As X 2 Preferably alkoxy, more preferably methoxy or ethoxy. Additionally, 3 X's... 2 They can be the same or different.

[0133] The compound represented by the above formula (B) is a compound that forms a siloxane structural unit having Rb.

[0134] [Chemical Formula 8] [Chemical Formula 9] [Chemical Formula 10] The meaning of Rc1 in formula (C1) is the same as that of Rc in the above general formula (1), and the preferred examples are also the same.

[0135] The meaning of Rc2 in formula (C2) is the same as that of the group (Rc2) formed by the mutual bonding of two Rcs in the above general formula (1), and the preferred examples are also the same.

[0136] The meaning of Rc3 in formula (C3) is the same as that of the group (Rc3) formed by the mutual bonding of the three Rcs in the above general formula (1), and the preferred examples are also the same.

[0137] X in equations (C1) to (C3) above 3 The meaning is the same as X in the above formula (B). 2 The same, and the preferred examples are also the same. Multiple X 3 They can be the same or different.

[0138] As the aforementioned hydrolyzable silane compounds, hydrolyzable silane compounds other than those represented by formulas (B), (C1) to (C3) can be used simultaneously. For example, examples include hydrolyzable trifunctional silane compounds, hydrolyzable monofunctional silane compounds, and hydrolyzable difunctional silane compounds other than those represented by formulas (B), (C1) to (C3).

[0139] When Rc originates from Rc1 to Rc3 in the hydrolyzable silane compounds represented by the above formulas (C1) to (C3), in order to adjust q / (q+r) in the general formula (1), the proportion (molar ratio) of the compounds represented by the above formulas (B) and (C1) to (C3) can be adjusted.

[0140] Specifically, for example, in order to set q / (q+r) to 0.5 to 1.0, the value represented by (Z2) below can be set to 0.5 to 1.0, and these compounds can be manufactured by hydrolysis and condensation.

[0141] (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} The amount and composition of the above-mentioned hydrolyzable silane compounds can be appropriately adjusted according to the desired structure of the polyorganosilicon silsesquioxane (a1).

[0142] Furthermore, the hydrolysis and condensation reactions of the aforementioned hydrolyzable silane compounds can occur simultaneously or in stages. When the reactions are carried out in stages, the order of the reactions is not particularly limited.

[0143] The hydrolysis and condensation reactions of the above-mentioned hydrolyzable silane compounds can be carried out in the presence of a solvent or in the absence of a solvent, but are preferably carried out in the presence of a solvent.

[0144] Examples of solvents mentioned above 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, isopropanol, and butanol.

[0145] Ketones or ethers are preferred as the solvents mentioned above. Furthermore, one solvent can be used alone, or two or more solvents can be used in combination.

[0146] There is no particular limitation on the amount of solvent used. It can be appropriately adjusted within the range of 0 to 2000 parts by mass relative to 100 parts by mass of the total amount of hydrolyzable silane compound, depending on the desired reaction time, etc.

[0147] The hydrolysis and condensation reactions of the above-mentioned hydrolyzable silane compounds are preferably carried out in the presence of a catalyst and water. The catalyst can be an acid catalyst or a base catalyst.

[0148] Examples of acid catalysts include inorganic 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 ferric chloride.

[0149] Examples of alkaline catalysts include, for instance, 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; bicarbonates of alkali metals such as lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, and cesium bicarbonate; and organic acid salts of alkali metals such as lithium acetate, sodium acetate, potassium acetate, and cesium acetate (e.g., acetic acid). Salts); organic acid salts of alkaline earth metals such as magnesium acetate (e.g., acetates); alkali metal alkoxides such as lithium methoxide, sodium methoxide, sodium ethoxide, sodium isopropoxide, potassium ethoxide, potassium tert-butoxide; alkali metal phenolates such as sodium phenolate; amines (tertiary amines, etc.) such as triethylamine, N-methylpiperidine, 1,8-diazabicyclo[5.4.0]undecane-7-ene, and 1,5-diazabicyclo[4.3.0]non-5-ene; nitrogen-containing aromatic heterocyclic compounds such as pyridine, 2,2'-bipyridine, and 1,10-phenanthroline.

[0150] Furthermore, a single catalyst can be used alone, or two or more catalysts can be used in combination. Additionally, the catalyst can be used in a dissolved or dispersed state in water or other solvents.

[0151] There is no particular limitation on the amount of the catalyst used, which can be appropriately adjusted in the range of 0.002 to 0.200 moles relative to 1 mole of the total amount of hydrolyzable silane compound.

[0152] The amount of water used in the above hydrolysis and condensation reactions is not particularly limited, and can be appropriately adjusted in the range of 0.5 to 20 moles relative to 1 mole of the total amount of hydrolyzable silane compound.

[0153] There are no particular restrictions on the method of adding water described above. The total amount of water used can be added all at once, or it can be added in several installments. When adding water in several installments, it can be added continuously or intermittently.

[0154] For the reaction conditions in carrying out the hydrolysis and condensation reaction of the above-mentioned hydrolyzable silane compound, it is particularly important to select reaction conditions in which the condensation rate of the polyorganosilicone silsesquioxane (a1) is 80% or more. The reaction temperature of the above-mentioned 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, it is possible to control the condensation rate to 80% or more. Furthermore, the reaction time of the above-mentioned hydrolysis and condensation reaction is, for example, 0.1 to 10 hours, preferably 1.5 to 8 hours. Furthermore, the above-mentioned hydrolysis and condensation reaction can be carried out under normal pressure, or under pressure or reduced pressure. In addition, the atmosphere in which the above-mentioned hydrolysis and condensation reaction is carried out can be, for example, an inert gas atmosphere such as nitrogen atmosphere, an inert gas atmosphere such as argon atmosphere, or an oxygen atmosphere such as air, but an inert gas atmosphere is preferred.

[0155] Polyorganosilicone silsesquioxane (a1) can be obtained through the hydrolysis and condensation reactions of the aforementioned hydrolyzable silane compounds. Preferably, after the hydrolysis and condensation reactions are completed, the catalyst is neutralized to inhibit ring-opening of the epoxy groups. Furthermore, the polyorganosilicone silsesquioxane (a1) can be separated and purified, for example, by methods such as water washing, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or combinations thereof.

[0156] In the hard coating of the hard coating film of the present invention, the condensation rate of the polyorganosilicon silsesquioxane (a1) is preferably 80% or more from the viewpoint of film hardness. The condensation rate is more preferably 90% or more, and even more preferably 95% or more.

[0157] The aforementioned condensation rate can be determined by testing a hard coating sample containing a cured polysilicon sesquioxane (a1). 29 Si NMR (nuclear magnetic resonance) spectroscopy is used to determine and calculate the result.

[0158] In the cured form of polyorganosilyl sesquioxane (a1) with epoxy groups, the epoxy groups are preferably opened by a polymerization reaction.

[0159] In the hard coating of the hard coating film of the present invention, the ring-opening rate of the epoxy groups of the cured polyorganosilyl sesquioxane (a1) is preferably 40% or more from the viewpoint of film hardness. More preferably, the ring-opening rate is 50% or more, and even more preferably 60% or more.

[0160] The above ring-opening rate can be calculated as follows: FT-IR (Fourier Transform Infrared Spectroscopy) single-reflection (ATR) measurements were performed on samples of the hard coating forming composition containing polyorganosilicon silsesquioxane (a1) before and after complete curing and heat treatment, and the result was calculated based on the change in peak height derived from the epoxy group.

[0161] Polyorganosilicon silsesquioxane (a1) can be used in one form or in two or more forms with different structures.

[0162] The content of the cured polyorganosilicon silsesquioxane (a1) relative to the total mass of the hard coating 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.

[0163] (Other additives) Hard coatings may contain other components than those mentioned above, such as dispersants, leveling agents, antifouling agents, antistatic agents, ultraviolet absorbers, antioxidants, etc.

[0164] Furthermore, the hard coating may or may not contain a cured compound having a (meth)acrylyl group. Preferably, the hard coating does not contain a cured compound having a (meth)acrylyl group, or if it does, the content of the cured compound having a (meth)acrylyl group is less than 10% by mass relative to the total amount of the cured polysilicon silsesquioxane (a1) and (meth)acrylate compounds. By setting the content of the cured (meth)acrylate compounds in the hard coating to less than 10% by mass, the deformation recovery of the hard coating film is improved, resulting in higher hardness.

[0165] Furthermore, there are no particular limitations on the type of antistatic agent; antistatic agents with ionic or electronic conductivity can be preferred. As a specific example of an electronically conductive antistatic agent, SEPLEGYDA (manufactured by Shin-Etsu Polymer Co., Ltd.), which utilizes polythiophene conductive polymers, can be preferred.

[0166] (film thickness) The thickness of the hard coating 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.

[0167] The thickness of the hard coating is calculated by observing the cross-section of the hard coating using an optical microscope. The cross-sectional specimen can be prepared by slicing using an ultramicrotome with a cross-section cutting device, or by cross-sectioning using a focused ion beam (FIB) device.

[0168] <Mixed Layer> The mixed layer of the hard coating film of the present invention contains a cured compound (b1) having an epoxy group and a cured compound (b2) having two or more (meth)acryloyl groups in one molecule.

[0169] Cured products of compounds (b1) having epoxy groups and compounds (b2) having two or more (meth)acryloyl groups in one molecule are preferably cured by heating and / or irradiating with ionizing rays onto a curable composition containing compounds (b1) having epoxy groups and compounds (b2) having two or more (meth)acryloyl groups in one molecule.

[0170] (Compounds with epoxy groups (b1)) As a compound with an epoxy group (b1) (also called "epoxy compound (b1)"), compounds having one or more epoxy groups (ethylene oxide rings) in the molecule can be used, without particular limitation, and examples include epoxy compounds containing alicyclic rings, aromatic epoxy compounds, aliphatic epoxy compounds, and epoxy-containing polyorganosilicon sesquioxanes (a1) used to form the above-mentioned hard coating.

[0171] As epoxide compounds containing alicyclic rings, examples include known compounds having one or more alicyclic rings and one or more epoxy groups within the molecule. Without particular limitation, examples include: (1) Compounds with alicyclic epoxy groups; (2) Compounds in which the epoxy group is directly bonded to the alicyclic ring via a single bond; (3) Compounds that have an alicyclic ring and a glycidyl ether group in the molecule (glycidyl ether type epoxy compounds), etc.

[0172] As a compound having an alicyclic epoxy group as described in (1) above, a compound represented by the following formula (i) can be cited.

[0173] [Chemical Formula 11] In formula (i) above, Y represents a single bond or a linking group (a divalent group having one or more atoms). Examples of such linking groups include divalent hydrocarbon groups, alkenyl groups in which part or all of the carbon-carbon double bond is epoxidized, carbonyl groups, ether bonds, ester bonds, carbonate groups, amide groups, and groups formed by linking multiple of these.

[0174] Examples of the aforementioned divalent hydrocarbon groups include straight-chain or branched alkylene groups with 1 to 18 carbon atoms, whether substituted or unsubstituted, and substituted or unsubstituted divalent alicyclic hydrocarbon groups. Examples of alkylene groups with 1 to 18 carbon atoms include methylene, methylmethylene, dimethylmethylene, ethylene, isopropylene, and n-propylene. Examples of the aforementioned divalent alicyclic hydrocarbon groups include 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, and divalent cyclohexylene (including cycloalkylene groups).

[0175] Examples of alkenyl groups (sometimes called "epoxidized alkenyl groups") in which part or all of the aforementioned carbon-carbon double bonds are epoxidized include, for example, straight-chain or branched alkenyl groups with 2 to 8 carbon atoms, such as vinylidene, propenyl, 1-butenyl, 2-butenyl, butadienyl, pentenyl, hexenyl, heptenyl, and octenyl. In particular, alkenyl groups in which all of the carbon-carbon double bonds are epoxidized are preferred, and alkenyl groups with 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized are more preferred.

[0176] Examples of alicyclic epoxide compounds represented by formula (i) above include 3,4,3',4'-dicyclohexane and compounds represented by formulas (i-1) to (i-10) below. Furthermore, in formulas (i-5) and (i-7) below, l and m represent integers from 1 to 30. In formula (i-5) below, R' is an alkylene group having 1 to 8 carbon atoms, preferably a straight-chain or branched alkylene group having 1 to 3 carbon atoms, such as methylene, ethylene, n-propylene, or isopropylene. In formulas (i-9) and (i-10) below, n1 to n6 represent integers from 1 to 30. Furthermore, examples of alicyclic epoxy compounds 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)ethylene oxide, and bis(3,4-epoxycyclohexylmethyl) ether.

[0177] [Chemical Formula 12] [Chemical Formula 13] As compounds in which the epoxy group of (2) above is directly bonded to the alicyclic ring via a single bond, examples include compounds represented by the following formula (ii).

[0178] [Chemical Formula 14] In formula (ii), R” is a group (p-valent organic group) formed by removing p hydroxyl groups (-OH) from the structural formula of a p-valent alcohol, and p and n represent natural numbers. Examples of p-valent alcohols [R””OH)p] include polyols such as 2,2-bis(hydroxymethyl)-1-butanol (alcohols with 1 to 15 carbon atoms). p is preferably 1 to 6, and n is preferably 1 to 30. When p is 2 or more, n in the groups inside the parentheses (outer) can be the same or different. Specifically, examples of compounds represented by formula (ii) above include the 1,2-epoxy-4-(2-epoxyethylene)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol [e.g., trade name "EHPE3150" (manufactured by Daicel Corporation)].

[0179] As compounds having an alicyclic and glycidyl ether group within the molecule described in (3) above, examples include glycidyl ethers of alicyclic alcohols (especially alicyclic polyols). More specifically, examples include compounds that hydrogenate bisphenol A type epoxides, such as 2,2-bis[4-(2,3-epoxypropoxy)cyclohexyl]propane and 2,2-bis[3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]propane (hydrogenated bisphenol A type epoxides); 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[o ... Compounds of bisphenol F type epoxy compounds hydrogenated from [3,5-dimethyl-4-(2,3-epoxypropoxy)cyclohexyl]methane, etc. (hydrogenated bisphenol F type epoxy compounds); hydrogenated biphenol type epoxy compounds; hydrogenated phenol phenolic varnish type epoxy compounds; hydrogenated cresol phenolic varnish type epoxy compounds; hydrogenated cresol phenolic varnish type epoxy compounds of bisphenol A; hydrogenated naphthalene type epoxy compounds; hydrogenated epoxy compounds of epoxy compounds obtained from triphenolmethane; hydrogenated epoxy compounds of the following aromatic epoxy compounds, etc.

[0180] Examples of the aforementioned aromatic epoxy compounds include, for instance, Epi-Bis type glycidyl ether epoxy resins, which are obtained through the condensation reaction of bisphenols [e.g., bisphenol A, bisphenol F, bisphenol S, fluorenebisphenol, etc.] with epichlorohydrin; high molecular weight Epi-Bis type glycidyl ether epoxy resins, which are obtained by further adding these Epi-Bis type glycidyl ether epoxy resins to the aforementioned bisphenols; and phenolic varnish / alkyl type glycidyl ether epoxy resins, obtained by further adding phenols to... [For example, phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, bisphenol S, etc.] undergo a condensation reaction with aldehydes [for example, formaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, salicylaldehyde, etc.] to obtain polyols, and then further condense these polyols with epichlorohydrin to obtain epoxides, having two phenol skeletons bonded at the 9 position of the fluorene ring and having glycidyl groups directly or via alkoxide groups bonded to oxygen atoms on the oxygen atoms of the hydroxyl groups of these phenol skeletons after the hydrogen atoms have been removed.

[0181] Examples of the aforementioned aliphatic epoxides include, for example, glycidyl ethers of alcohols (where s is a natural number) that do not have an s-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.]; epoxides of oils containing double bonds, such as epoxidized linseed oil, epoxidized soybean oil, and epoxidized castor oil; and epoxides of polyolefins (including polydiolefins), such as epoxidized polybutadiene. In addition, examples of alcohols that do not possess an s-valent cyclic structure include monohydric alcohols such as methanol, ethanol, 1-propanol, isopropanol, 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 trivalent or higher polyhydric alcohols such as glycerol, diglycerol, erythritol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and sorbitol. Furthermore, s-valent alcohols can be polyether polyols, polyester polyols, polycarbonate polyols, and polyolefin polyols.

[0182] The epoxy compound (b1) is preferably a polyorganosilicone silsesquioxane having an epoxy group, and as a preferred range, it is the same as the polyorganosilicone silsesquioxane (a1) with an epoxy group in the aforementioned hard coating.

[0183] Epoxide (b1) can be used in a single form or in two or more forms with different structures.

[0184] The content of the cured epoxy compound (b1) relative to the total mass of the mixed layer 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.

[0185] (a compound having more than two (meth)acryloyl groups in one molecule (b2)) 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.

[0186] The multifunctional (meth)acrylate compound (b2) can be a crosslinking monomer, a crosslinking oligomer, or a crosslinking polymer.

[0187] As a polyfunctional (meth)acrylate compound (b2), esters of polyols and (meth)acrylates can be cited. Specifically, examples include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexane acrylate, pentaerythritol hexane (meth)acrylate, etc. However, from the viewpoint of high crosslinking, pentaerythritol triacrylate, pentaerythritol tetraacrylate, or dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, or mixtures thereof are preferred.

[0188] The polyfunctional (meth)acrylate compound (b2) can be used in isolation or in combination with two or more compounds with different structures.

[0189] The content of the cured polyfunctional (meth)acrylate compound (b2) in the mixed layer is preferably 10% by mass or more relative to the total amount of the cured epoxy compound (b1) and the cured polyfunctional (meth)acrylate compound (b2). By setting the content of the cured polyfunctional (meth)acrylate compound (b2) in the mixed layer to the above range, the scratch resistance of the hard coating film can be improved.

[0190] The content of the cured polyfunctional (meth)acrylate compound (b2) in the mixed layer is preferably 10% to 90% by mass, more preferably 20% to 80% by mass, relative to the total amount of the cured epoxy compound (b1) and the cured polyfunctional (meth)acrylate compound (b2).

[0191] (Other additives) The mixed layer may contain components other than those mentioned above, such as dispersants, leveling agents, antifouling agents, antistatic agents, ultraviolet absorbers, antioxidants, and cured products of other polymeric compounds.

[0192] There are no particular limitations on the type of antistatic agent, but antistatic agents with ionic or electronic conductivity are preferred. As a specific example of an electronically conductive antistatic agent, SEPLEGYDA (manufactured by Shin-Etsu Polymer Co., Ltd.), which utilizes the conductive polymer polythiophene, is a preferred choice.

[0193] Cured products of other polymeric compounds include, for example, cured products of compounds having an epoxy group and a (meth)acryloyl group in one molecule. Specific examples of such compounds include CYCLOMERM100 manufactured by Daicel Corporation, LIGHT ESTER G manufactured by Kyoeisha Chemical Co., Ltd., 4HBAGE manufactured by Nihon Kasei Co., Ltd., the SP series (e.g., SP-1506, SP-500, SP-1507, SP-480) and VR series (e.g., VR-77) manufactured by SHOWA HIGHPOLYMER Co., Ltd., and EA-1010 / ECA, EA-11020, EA-1025, EA-6310 / ECA manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.

[0194] (film thickness) The thickness of the hybrid layer is preferably 0.05 μm to 10 μm. By setting it to 0.05 μm or more, the scratch resistance of the film is improved, and by setting it to 10 μm or less, the hardness and resistance to repeated bending are improved.

[0195] The thickness of the hybrid layer is more preferably 0.1 μm to 10 μm, further preferably 0.1 μm to 5 μm, and especially preferably 0.1 μm to 3 μm.

[0196] When the hard coating of the present invention further comprises a scratch-resistant layer as described later, the total thickness of the mixed layer and the scratch-resistant layer is preferably within the above-mentioned range.

[0197] In the hard coating of the present invention, the hard coating layer and the mixed layer are preferably bonded by covalent bonds. As a particularly preferred method, the epoxy groups of the polyorganosilicon silsesquioxane (a1) in the hard coating layer and the epoxy groups of the epoxy compound (b1) in the mixed layer form bonds at the interface of the two layers, resulting in a highly adhesive laminated structure that can exhibit higher scratch resistance.

[0198] <Other Layers> In addition to the hard coating layer and the hybrid layer, the hard coating film of the present invention may further have other layers. For example, preferred embodiments include having a hard coating layer on both sides of the substrate, having an easy-adhesive layer between the substrate and the hard coating layer to improve adhesion, having an antistatic layer to impart antistatic properties, having one or more antireflective layers laminated on the hybrid layer to prevent reflection, having an antifouling layer to impart antifouling properties and an abrasion-resistant layer to impart abrasion resistance on the hybrid layer, and so on. Multiple of these may be provided.

[0199] The hard coating of the present invention preferably has a scratch-resistant layer on the surface of the mixed layer opposite to the hard coating layer, thereby further improving scratch resistance.

[0200] (Abrasion-resistant layer) The scratch-resistant layer preferably comprises a cured compound (c1) having two or more (meth)acryloyl groups in one molecule (also referred to as "polyfunctional (meth)acrylate compound (c1)").

[0201] The polyfunctional (meth)acrylate compound (c1) is the same as the aforementioned polyfunctional (meth)acrylate compound (b2), and the preferred range is also the same.

[0202] A single polyfunctional (meth)acrylate compound (c1) may be used, or two or more compounds with different structures may be used simultaneously.

[0203] The content of the cured polyfunctional (meth)acrylate compound (c1) relative to the total mass of the scratch-resistant layer is preferably 80% by mass or more, more preferably 85% by mass or more, and even more preferably 90% by mass or more.

[0204] (Other additives) The scratch-resistant layer may contain other components than those mentioned above, such as inorganic particles, leveling agents, antifouling agents, antistatic agents, lubricants, antioxidants, etc.

[0205] In particular, as a lubricant, it is preferable to contain the following fluorinated compounds.

[0206] Furthermore, there are no particular limitations on the type of antistatic agent; antistatic agents with ionic or electronic conductivity can be preferred. As a specific example of an electronically conductive antistatic agent, SEPLEGYDA (manufactured by Shin-Etsu Polymer Co., Ltd.), which utilizes polythiophene conductive polymers, can be preferred.

[0207] [Fluorine compounds] The fluorinated compound can be any of monomers, oligomers, or polymers. The fluorinated compound preferably has substituents that facilitate bonding or compatibility with the polyfunctional (meth)acrylate compound (c1) in the abrasion-resistant layer. These substituents can be the same or different, and preferably multiple substituents are present.

[0208] The substituent is preferably a polymerizable group, which can be a polymerizable reactive group exhibiting any one of free radical polymerization, cationic polymerization, anionic polymerization, condensation polymerization, and addition polymerization. Examples of preferred substituents include acryloyl, methacryloyl, vinyl, allyl, cinnamoyl, epoxy, oxetyl, hydroxyl, polyoxyalkylene, carboxyl, and amino groups. Among these, free radical polymerizable groups are preferred, and acryloyl and methacryloyl groups are particularly preferred.

[0209] Fluorinated compounds can be polymers of compounds that do not contain fluorine atoms, or they can be oligomers.

[0210] The fluorinated compounds mentioned above are preferably fluorinated compounds represented by the following general formula (F).

[0211] General formula (F): (R) f )-[(W)-(R) A ) nf ] mf (where R) f Indicates (per)fluoroalkyl or (per)fluoropolyether group, W indicates single bond or linker group, R A This indicates a polymerizable unsaturated group. nf represents an integer from 1 to 3. mf represents an integer from 1 to 3. In the general formula (F), R A This refers to a polymerizable unsaturated group. The polymerizable unsaturated group is preferably a group having unsaturated bonds capable of undergoing free radical polymerization upon irradiation with active energy rays such as ultraviolet light or electron beams (i.e., a free radical polymerizable group). Examples include (meth)acryloyl, (meth)acryloyloxy, vinyl, and allyl groups. (Methacryl), (meth)acryloyloxy, and groups obtained by replacing any hydrogen atom in these groups with a fluorine atom are preferred.

[0212] In general formula (F), R f It indicates (per)fluoroalkyl or (per)fluoropolyether group.

[0213] Here, (per)fluoroalkyl means at least one of fluoroalkyl and perfluoroalkyl, and (per)fluoropolyether means at least one of fluoropolyether and perfluoropolyether. From the viewpoint of scratch resistance, R is preferred. f It has a high fluorine content.

[0214] (All)fluoroalkyl groups are preferably groups with 1 to 20 carbon atoms, and more preferably groups with 1 to 10 carbon atoms.

[0215] (Per)fluoroalkyl groups can be straight-chain structures (e.g., -CF2CF3, -CH2(CF2)4H, -CH2(CF2)8CF3, -CH2CH2(CF2)4H), branched-chain structures (e.g., -CH(CF3)2, -CH2CF(CF3)2, -CH(CH3)CF2CF3, -CH(CH3)(CF2)5CF2H), or alicyclic structures (preferably 5-membered or 6-membered rings, such as perfluorocyclohexyl and perfluorocyclopentyl, and alkyl groups substituted by these groups).

[0216] (Per)fluoropolyether group refers to a (per)fluoroalkyl group containing an ether bond, which can be a monovalent group or a group with more than two valent bonds. Examples of fluoropolyether groups include -CH2OCH2CF2CF3, -CH2CH2OCH2C4F8H, and -CH2CH2OCH2CH2C8F. 17 Examples of perfluoropolyether groups include -CH2CH2OCF2CF2OCF2CF2H, and fluorocycloalkyl groups with 4 to 20 carbon atoms having 4 or more fluorine atoms. Furthermore, -(CF2O) can be cited as an example of a perfluoropolyether group. pf -(CF2CF2O) qf -、-[CF(CF3)CF2O] pf -[CF (CF3)] qf -、-(CF2CF2CF2O) pf -、-(CF2CF2O) pf -wait.

[0217] The above pf and qf independently represent integers from 0 to 20. Among them, pf+qf is an integer greater than or equal to 1.

[0218] The total pf and qf is preferably 1 to 83, more preferably 1 to 43, and even more preferably 5 to 23.

[0219] From the viewpoint of excellent scratch resistance, the above-mentioned fluorinated compounds are particularly preferred to have a composition of -(CF2O). pf -(CF2CF2O) qf - indicates a perfluoropolyether group.

[0220] In this invention, the fluorinated compound preferably has a perfluoropolyether group and has multiple polymerizable unsaturated groups in one molecule.

[0221] In the general formula (F), W represents a linking group. Examples of W include alkylene, arylene, and heteroalkylene groups, as well as linking groups obtained by combining these groups. These linking groups may also have functional groups such as oxygen, carbonyl, carbonyloxy, carbonylimino, and sulfonamide groups, as well as functional groups obtained by combining these groups.

[0222] As W, ethylene is preferred, and more preferably ethylene bonded to a carbonyl imino group.

[0223] There is no particular limitation on the fluorine atom content of the fluorine-containing compound, but it is preferred to be 20% by mass or more, more preferably 30 to 70% by mass, and even more preferably 40 to 70% by mass.

[0224] Examples of preferred fluorinated compounds include, but are not limited to, DAIKIN INDUSTRIES, LTD.'s R-2020, M-2020, R-3833, M-3833 and OPTOOL DAC (trade names), and DIC Corporation's MEGAFACE F-171, F-172, F-179A, RS-78, RS-90, DEFENSA MCF-300 and MCF-323 (trade names).

[0225] From the viewpoint of scratch resistance, in the general formula (F), the product of nf and mf (nf×mf) is preferably 2 or more, and more preferably 4 or more.

[0226] (Molecular weight of fluorine-containing compounds) The weight-average molecular weight (Mw) of fluorinated compounds with polymerizable unsaturated groups can be determined using size exclusion chromatography, such as gel permeation chromatography (GPC).

[0227] The Mw of the fluorinated compound used in this 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.

[0228] (Amount of fluorine-containing compounds added) The amount of fluorinated compound added relative to the total mass of the scratch-resistant layer is preferably 0.01 to 5% by mass, more preferably 0.1 to 5% by mass, even more preferably 0.5 to 5% by mass, and especially preferably 0.5 to 2% by mass.

[0229] The thickness of the scratch-resistant layer is preferably 0.1 μm to 4 μm, more preferably 0.1 μm to 2 μm, and especially preferably 0.1 μm to 1 μm.

[0230] Furthermore, the combined thickness of the aforementioned hybrid layer and scratch-resistant layer is preferably 0.1 μm to 10 μm.

[0231] [Manufacturing method of hard coating film] The manufacturing method of the hard coating film of the present invention is not particularly limited. As one preferred method, one can exemplify a method of coating a hard coating layer forming composition onto a substrate and allowing it to partially cure, then coating a mixed layer forming composition onto the partially cured hard coating and finally fully curing each layer (method A). In method A, when the hard coating film of the present invention also has a scratch-resistant layer, it is preferable to coat the mixed layer forming composition and allow it to partially cure, then coat the scratch-resistant layer forming composition onto the partially cured mixed layer and finally fully cure each layer.

[0232] As another preferred method, one approach for forming a hybrid layer in a hard coating film involves stacking an uncured or semi-cured hard coating layer and a scratch-resistant layer on a substrate, mixing them at their interface to form a hybrid layer, and then fully curing each layer. For example, one method involves forming an uncured hard coating layer on a substrate, fabricating a laminate with an uncured scratch-resistant layer formed on a dummy support, bonding the laminate with the scratch-resistant layer side in contact with the hard coating layer, forming a hybrid layer based on interface mixing on the bonding surface, and then removing the dummy support after fully curing each layer (Method B). Furthermore, another method involves multi-coating a hard coating forming composition and a scratch-resistant layer forming composition onto a substrate, forming a hybrid layer at their interface, and then fully curing each layer (Method C), etc. Furthermore, examples include methods such as applying a hard coating forming composition to a substrate and allowing it to partially cure, applying a scratch-resistant layer forming composition to the partially cured hard coating and allowing it to penetrate to form a mixed layer, and then fully curing each layer (method D).

[0233] The following is a detailed explanation of methods A and D.

[0234] (Method A) Specifically, Method A is a manufacturing method that includes the following steps (I) to (IV).

[0235] (I) The process of forming a coating film (i) by coating a substrate with a hard coating composition comprising the aforementioned epoxy-containing polyorganosilyl sesquioxane (a1). (II) The process of semi-curing the above coating (i) (III) The step of forming coating (ii) by coating a mixed layer forming composition comprising the aforementioned epoxy compound (b1) and the aforementioned polyfunctional (meth)acrylate compound (b2) onto the aforementioned semi-cured coating (i). (IV) The process of fully curing the above coatings (i) and (ii). <Process (I)> Step (I) is a step of forming a coating film by coating a hard coating composition containing the aforementioned epoxy-containing polyorganosilyl sesquioxane (a1) onto a substrate.

[0236] Regarding the substrate, as previously stated.

[0237] The hard coating forming composition is a composition used to form the aforementioned hard coating.

[0238] The hard coating forming composition is typically in liquid form. Furthermore, the hard coating forming composition is preferably prepared by dissolving or dispersing polyorganosilyl silsesquioxane (a1) and various additives and polymerization initiators as needed in a suitable solvent. In this case, the concentration of the solid component is typically about 10–90% by mass, preferably 20–80% by mass, and particularly preferably about 40–70% by mass.

[0239] <Polymerization Initiator> The aforementioned polyorganosilicone silsesquioxane (a1) contains cationic polymerizable groups (epoxy groups). To initiate and carry out the polymerization reaction of the aforementioned polyorganosilicone silsesquioxane (a1) by light irradiation, the hard coating forming composition preferably contains a cationic photopolymerization initiator. Furthermore, only one cationic photopolymerization initiator may be used, or two or more with different structures may be used simultaneously.

[0240] The following section explains cationic photopolymerization initiators.

[0241] (Cationic photopolymerization initiator) As a cationic photopolymerization initiator, it can be a cationic photopolymerization initiator capable of generating cations as active species through light irradiation, and known cationic photopolymerization initiators can be used without any restrictions. Specific examples include known sulfonium salts, ammonium salts, iodine salts (e.g., diaryliodine salts), triarylsulfonium salts, diazonium salts, imine salts, etc. More specifically, examples include, for instance, the cationic photopolymerization initiator represented by formulas (25) to (28) shown in paragraphs 0050 to 0053 of Japanese Patent Application Publication No. 8-143806, and the cationic photopolymerization initiator exemplified as a cationic polymerization catalyst in paragraph 0020 of Japanese Patent Application Publication No. 8-283320. Furthermore, cationic photopolymerization initiators can be synthesized by known methods and can also be obtained as commercially available products. As commercially available products, examples 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; PHOTOINITIATOR2047 manufactured by Rhodia Company; UVI-6974 and UVI-6990 manufactured by Union Carbide Corporation; and CPI-10P manufactured by San-Apro Ltd.

[0242] As cationic photopolymerization initiators, considering factors such as the photoinitiator's sensitivity to light and the stability of the compound, diazonium salts, iodinated salts, sulfonium salts, and imine salts are preferred. Furthermore, considering weather resistance, iodinated salts are the most preferred.

[0243] Specific commercially available products that serve as iodide-based cationic photopolymerization initiators include, for example, B2380 manufactured by Tokyo Chemical Industry Co., Ltd., BBI-102 manufactured by Midori Kagaku 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 Kagaku Co., Ltd.

[0244] Furthermore, as specific examples of iodine salt compounds that can be used as cationic photopolymerization initiators, compounds FK-1 and FK-2 can also be cited.

[0245] [Chemical Formula 15] [Chemical Formula 16] The content of the polymerization initiator in the composition for forming the hard coating can be appropriately adjusted within a range that allows the polymerization reaction (cationic polymerization) of the above-mentioned polyorganosilicone silsesquioxane (a1) to proceed well, and there is no particular limitation. The content is preferably 1 to 20 parts by mass relative to 100 parts by mass of the above-mentioned polyorganosilicone silsesquioxane (a1), for example, in the range of 0.1 to 200 parts by mass, and more preferably in the range of 1 to 5 parts by mass.

[0246] <Any ingredient> In addition to the aforementioned polyorganosilyl silsesquioxane (a1) and polymerization initiator, the composition for forming a hard coating may further contain one or more other arbitrary components. Specific examples of arbitrary components include solvents and various additives.

[0247] (solvent) Organic solvents are preferred as solvents that can be included as any component, and one or more organic solvents can be mixed in any proportion. Specific examples of organic solvents include alcohols such as methanol, ethanol, propanol, n-butanol, and isobutanol; ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, and cyclohexanone; cellosolves such as ethyl cellosolves; aromatics such as toluene and xylene; ethylene glycol ethers such as propylene glycol monomethyl ether; acetates such as methyl acetate, ethyl acetate, and butyl acetate; and diacetone alcohol. The amount of solvent in the above composition can be appropriately adjusted within a range that ensures the coating suitability of the composition. For example, relative to 100 parts by mass of the above-mentioned polysiloxane (a1) and polymerization initiator, it can be set to 50 to 500 parts by mass, and preferably 80 to 200 parts by mass.

[0248] (additive) The above composition may also contain one or more known additives as needed. Examples of such additives include dispersants, leveling agents, antifouling agents, antistatic agents, ultraviolet absorbers, and antioxidants. For details regarding these additives, please refer, for example, to paragraphs 0032 to 0034 of Japanese Patent Application Publication No. 2012-229412. However, it is not limited to these; various additives commonly used in polymerizable compositions can be used. Furthermore, the amount of additive added to the composition can be appropriately adjusted and is not particularly limited.

[0249] <Preparation method of the composition> The hard coating forming composition used in this invention can be prepared by simultaneously or sequentially mixing the various components described above. The preparation method is not particularly limited, and a known mixer or similar device can be used during preparation.

[0250] There are no particular limitations on the coating method for the composition used to form the hard coating layer, and known methods can be used. Examples include dip coating, air knife coating, curtain coating, roller coating, wire rod coating, gravure coating, and die coating.

[0251] <Process (II)> Step (II) is a process of semi-curing the above coating (i).

[0252] There are no particular restrictions on the types of ionizing rays; examples include X-rays, electron beams, ultraviolet light, visible light, and infrared light, but ultraviolet light is preferred. For instance, if the coating is UV-curable, it is preferable to irradiate it with a 2mJ / cm² UV lamp. 2 ~1000mJ / cm 2 The curable compound is cured by exposure to ultraviolet light. A more preferred amount is 2 mJ / cm². 2 ~100mJ / cm 2 Further preferred is 5mJ / cm 2 ~50mJ / cm 2 As for types of ultraviolet lamps, metal halide lamps and high-pressure mercury lamps are preferred.

[0253] There are no particular restrictions on the oxygen concentration during curing, but when the product contains components that are easily inhibited by curing (compounds with (meth)acryloyl groups), adjusting the oxygen concentration to 0.1 to 2.0% by volume allows for the formation of a semi-cured state with residual surface functional groups, which is therefore preferable. Furthermore, when the product does not contain components that are easily inhibited by curing (compounds with (meth)acryloyl groups), replacing the curing atmosphere with dry nitrogen eliminates the influence of the reaction between epoxy groups and water vapor in the air, which is also preferable.

[0254] Drying can be performed as needed, either after step (I) and before step (II), or after step (II) and before step (III), or during both periods. Drying can be performed via hot air blowing, placement within a heating furnace, or conveying within a heating furnace. The heating temperature can be set to a temperature sufficient to dry and remove the solvent, and is not particularly limited. Here, heating temperature refers to the temperature of the hot air or the ambient temperature within the heating furnace.

[0255] By setting the curing of the coating (i) in step (II) to semi-curing, the unreacted epoxy groups in the polyorganosilyl sesquioxane (a1) included in the hard coating forming composition and the epoxy compound included in the mixed layer forming composition form bonds in the subsequent step (IV). By forming the above bonds, the hard coating of the present invention becomes a laminated structure with high adhesion and can exhibit higher scratch resistance.

[0256] <Process (III)> Step (III) is a step of forming a coating film (ii) by coating a mixed layer forming composition containing the epoxy compound (b1) and the polyfunctional (meth)acrylate compound (b2) onto the semi-cured coating film (i).

[0257] The composition for forming the hybrid layer is a composition used to form the aforementioned hybrid layer.

[0258] The composition for forming the mixed layer is typically in liquid form. Furthermore, the composition for forming the mixed layer is preferably prepared by dissolving or dispersing the aforementioned epoxy compound (b1), the aforementioned polyfunctional (meth)acrylate compound (b2), and various additives and polymerization initiators as needed, in a suitable solvent. In this case, the concentration of the solid components is typically about 2 to 90% by mass, preferably 2 to 80% by mass, and particularly preferably about 2 to 70% by mass.

[0259] (Polymerization initiator) The mixed-layer forming composition comprises an epoxy compound (b1) (a cationic polymerizable compound) and a polyfunctional (meth)acrylate compound (b2) (a free radical polymerizable compound). To initiate the polymerization of these compounds with different polymerization forms by light irradiation, the mixed-layer forming composition preferably comprises a free radical photopolymerization initiator and a cationic photopolymerization initiator. Furthermore, only one free radical photopolymerization initiator may be used, or two or more with different structures may be used simultaneously. The same applies to cationic photopolymerization initiators.

[0260] The following sections will describe each photopolymerization initiator in turn.

[0261] (Free radical photopolymerization initiator) As a free radical photopolymerization initiator, it can be a free radical photopolymerization initiator capable of generating free radicals as active species through light irradiation, and known free radical photopolymerization initiators can be used without any restrictions. Specific examples include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzyl dimethyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 1-hydroxycyclohexylphenylone, 2-methyl-2-morpholino(4-thiomethylphenyl)propane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl] Acetone oligomers, acetophenones such as 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propanoyl)-benzyl]phenyl}-2-methyl-propane-1-one; oxime esters such as 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyl oxime)], acetophenone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime); benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether. Benzoin derivatives such as ethers; benzophenone, methyl phthalate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N,N-dimethyl-N-[2-(1-oxo-2-propenoxy)ethyl]benzylmethane ammonium bromide, (4-benzoylbenzyl)trimethylammonium chloride and other benzophenone derivatives; 2-isopropylthioxanthone, 4-isopropyl... Thioxanone derivatives, including 2,4-diethylthioxanone, 2,4-dichlorothioxanone, 1-chloro-4-propoxythioxanone, 2-(3-dimethylamino-2-hydroxy)-3,4-dimethyl-9H-thioxanone-9-one methyl chloride, etc.; acylphosphine oxides, including 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, etc.; etc.

[0262] Furthermore, as an auxiliary agent for free radical photopolymerization initiators, triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (milchone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy) ester, isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanone, 2,4-diisopropylthioxanone, etc., can be used simultaneously.

[0263] The aforementioned free radical photopolymerization initiators and auxiliaries can be synthesized by known methods and are also available as commercially available products.

[0264] The content of the free radical photopolymerization initiator in the above-mentioned mixed layer forming composition can be appropriately adjusted within a range that allows the polymerization reaction (free radical polymerization) of the free radical polymerizable compound to proceed well, and there is no particular limitation. The content is preferably 0.5 to 10 parts by mass relative to 100 parts by mass of the free radical polymerizable compound contained in the above composition, for example, in the range of 0.1 to 20 parts by mass, more preferably in the range of 1 to 10 parts by mass.

[0265] Examples of cationic photopolymerization initiators include those that can be included in the above-mentioned hard coating forming composition.

[0266] The content of the cationic photopolymerization initiator in the above-mentioned mixed layer forming composition can be appropriately adjusted within a range that allows the polymerization reaction (cationic polymerization) of the cationic polymerizable compound to proceed well, and is not particularly limited. The content is preferably 1 to 150 parts by mass relative to 100 parts by mass of the cationic polymerizable compound, for example, in the range of 0.1 to 200 parts by mass, and more preferably in the range of 1 to 100 parts by mass.

[0267] <Any ingredient> In addition to the epoxy compound, the polyfunctional (meth)acrylate compound (b2), and the polymerization initiator, the above-mentioned composite composition for forming a mixed layer may further contain one or more other arbitrary components. Specific examples of these arbitrary components include solvents and various additives that can be used in the above-mentioned hard coating composition.

[0268] <Preparation method of the composition> The mixed layer forming composition used in this invention can be prepared by simultaneously or sequentially mixing the various components described above. The preparation method is not particularly limited, and a known mixer or similar device can be used during preparation.

[0269] As a coating method for the composition for forming the mixed layer, known methods can be used without particular limitation.

[0270] <Process (IV)> Step (IV) is a step of fully curing the above-mentioned coatings (i) and coatings (ii).

[0271] Regarding the curing of the coating, it is preferable to cure it by irradiating the coating side with ionizing rays.

[0272] Regarding the type of ionizing radiation, it is preferable to use ionizing radiation used in the above-described step (II) for curing the coating (i).

[0273] As for the irradiation dose of ionizing rays, for example, if the coating is UV-curable, it is preferable to irradiate it with a UV lamp at a dose of 10 mJ / cm². 2 ~6000mJ / cm 2 The curable compound is cured by exposure to ultraviolet light. A more preferred amount is 50 mJ / cm². 2 ~6000mJ / cm 2 Further preferred is 100 mJ / cm 2 ~6000mJ / cm 2 Furthermore, to promote the curing of the coating, it is preferable to combine heating with ionizing radiation irradiation. The heating temperature is preferably 40°C or higher and 140°C or lower, more preferably 60°C or higher and 140°C or lower. Moreover, multiple ionizing radiation irradiations are also preferred.

[0274] The oxygen concentration during curing is preferably 0 to 1.0% by volume, more preferably 0 to 0.1% by volume, and most preferably 0 to 0.05% by volume. By setting the oxygen concentration during curing to less than 1.0% by volume, it is less susceptible to curing inhibition caused by oxygen, thus resulting in a robust film.

[0275] Drying can be performed as needed after process (III) and before process (IV), or after process (IV), or during both periods.

[0276] In the above-mentioned method for manufacturing a hard coating film, it is also preferable to include a step of setting a layer other than the hard coating layer and the mixing layer, such as a scratch-resistant layer.

[0277] When setting the scratch-resistant layer, it is preferable to include the following steps (IV') to (VI) after the above steps (I) to (III).

[0278] (IV') A process of semi-curing the coating (ii) formed in step (III) above. (V) The step of forming a scratch-resistant layer composition containing a polyfunctional (meth)acrylate compound (c1) on the semi-cured coating (ii) to form a coating (iii). (VI) The process of fully curing the above coatings (i), (ii) and (iii). <Process (IV')> Step (IV') is a process of semi-curing the coating (ii) formed in step (III) above.

[0279] Regarding the curing of the coating, it is preferable to cure it by irradiating the coating side with ionizing rays.

[0280] Regarding the type and amount of ionizing radiation, the type and amount of ionizing radiation used in the semi-cured coating (i) in the above-mentioned process (II) can be preferred.

[0281] Drying can be performed as needed after process (III) and before process (IV'), or after process (IV') and before process (V), or during both periods.

[0282] By setting the curing of the coating (ii) in step (IV') to semi-curing, the unreacted (meth)acryloyl groups in the polyfunctional (meth)acrylate compound (b2) included in the mixed layer forming composition and the (meth)acryloyl groups in the polyfunctional (meth)acrylate compound (c1) included in the scratch-resistant layer forming composition form bonds in the subsequent step (VI). By forming the above bonds, the hard coating film of the present invention becomes a highly adhesive laminated structure and can exhibit higher scratch resistance.

[0283] There are no particular restrictions on the oxygen concentration during curing, but 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-cured state can be adjusted.

[0284] <Process (V)> Step (V) is a step of forming a coating (iii) by coating a scratch-resistant layer forming composition containing the above-mentioned polyfunctional (meth)acrylate compound (c1) onto the above-mentioned semi-cured coating (ii).

[0285] The abrasion-resistant layer forming composition is a composition used to form the aforementioned abrasion-resistant layer.

[0286] The abrasion-resistant layer forming composition is typically in liquid form. Furthermore, the abrasion-resistant layer forming composition is preferably prepared by dissolving or dispersing the aforementioned polyfunctional (meth)acrylate compound (c1) and various additives and polymerization initiators as needed in a suitable solvent. In this case, the concentration of the solid component is typically about 2 to 90% by mass, preferably 2 to 80% by mass, and particularly preferably about 2 to 70% by mass.

[0287] (Polymerization initiator) The abrasion-resistant layer forming composition comprises a polyfunctional (meth)acrylate compound (c1) (a free radical polymerizable compound). To initiate and carry out the polymerization reaction of the polyfunctional acrylate compound by light irradiation, the abrasion-resistant layer forming composition preferably comprises a free radical photopolymerization initiator. Furthermore, only one free radical photopolymerization initiator may be used, or two or more with different structures may be used simultaneously. Examples of free radical photopolymerization initiators that can be included in the above-described mixed layer forming composition include free radical photopolymerization initiators.

[0288] The content of the free radical photopolymerization initiator in the abrasion-resistant layer formation composition can be appropriately adjusted within a range that allows the polymerization reaction (free radical polymerization) of the free radical polymerizable compound to proceed well, and there is no particular limitation. The content is preferably 0.5 to 10 parts by mass relative to 100 parts by mass of the free radical polymerizable compound contained in the above composition, for example, in the range of 0.1 to 20 parts by mass, more preferably in the range of 1 to 10 parts by mass.

[0289] <Any ingredient> In addition to the aforementioned polyfunctional (meth)acrylate compound (c1) and polymerization initiator, the above-mentioned composition for forming a mixed layer may further contain one or more arbitrary components. Specific examples of arbitrary components include, in addition to the aforementioned fluorinated compounds, solvents and various additives that can be used in the above-mentioned hard coating composition.

[0290] <Preparation method of the composition> The abrasion-resistant layer forming composition used in this invention can be prepared by simultaneously or sequentially mixing the various components described above. The preparation method is not particularly limited, and a known mixer or similar device can be used during preparation.

[0291] As a coating method for the composition for forming a scratch-resistant layer, known methods can be used without particular limitation.

[0292] <Process (VI)> Step (VI) is a step of fully curing the above-mentioned coatings (i), (ii) and (iii).

[0293] Regarding the curing of the coating, it is preferable to cure it by irradiating the coating side with ionizing rays.

[0294] Regarding the type and amount of ionizing radiation, the ionizing radiation and the amount of radiation used in the above-mentioned process (IV) for curing the coating (i) and coating (ii) can be preferred.

[0295] Drying can be performed as needed, either after process (V) and before process (VI), or after process (VI), or during both periods.

[0296] (Method D) Specifically, method D is a manufacturing method that includes the following steps (I) to (IV'').

[0297] (I) The step of forming a coating film (i) by coating a hard coating composition comprising the aforementioned polymer and a polyorganosilyl sesquioxane (a1) comprising an epoxy group onto a substrate. (II) The process of semi-curing the above coating (i) (III') The process of forming a mixed layer (ii) and a coating film (iii) by applying and penetrating a composition for forming a scratch-resistant layer containing a polyfunctional (meth)acrylate compound (c1) onto the semi-cured coating film (i) described above. (IV'') A process of fully curing the above-mentioned coating (i), the mixed layer (ii) formed by penetration, and the coating (iii). <Process (I)> Step (I) is a step of forming a coating film (i) by coating a hard coating composition comprising the aforementioned polymer and a polyorganosilicone sesquioxane (a1) containing an epoxy group onto a substrate. The details of step (I) are as described in step (I) of method A.

[0298] <Process (II)> Step (II) is a process of semi-curing the coating (i) described above. The curing conditions and drying process for step (II) are as described in step (II) of method A.

[0299] In Method D, similarly to Method A, it is also preferable to set the curing of the coating (i) in step (II) as a semi-curing process. By setting the curing of the coating (i) as a semi-curing process, the composition for forming the abrasion-resistant layer containing the polyfunctional (meth)acrylate compound (c1) becomes easier to penetrate in step (III'), and a mixed layer is easily formed. By forming a mixed layer based on the above-described penetration, the hard coating of the present invention becomes a laminated structure with high interlayer adhesion and can exhibit higher abrasion resistance.

[0300] <Process (III)> Step (III') is a step of forming a mixed layer (ii) and a coating film (iii) by coating and penetrating a scratch-resistant layer-forming composition containing a polyfunctional (meth)acrylate compound (c1) onto the semi-cured coating film (i). The scratch-resistant layer-forming composition is a composition used to form the aforementioned scratch-resistant layer.

[0301] Regarding the polyfunctional (meth)acrylate compound (c1), solvent, and solid components in the composition for forming the scratch-resistant layer in step (III'), since they differ from those in method A, details will be provided below. The polymerization initiator and any components, and the methods for adjusting the composition, are as described in step (V) of method A.

[0302] (Polyfunctional (meth)acrylate compound (c1)) In method D, the polyfunctional (meth)acrylate compound (c1) preferably contains 20% or more of a polyfunctional (meth)acrylate compound with a molecular weight of 400 or less. By containing 20% ​​or more of a compound with a molecular weight of 400 or less, the composition for forming the scratch-resistant layer becomes easier to penetrate and form a mixed layer. There are no particular limitations on the polyfunctional (meth)acrylate compound with a molecular weight of 400 or less; specific examples include KAYARAD PET-30 (manufactured by Nippon Kayaku Co., Ltd.), KAYARAD TMPTA (manufactured by Nippon Kayaku Co., Ltd.), and pentaerythritol tetraacrylate (manufactured by SHIN-NAKAMURA CHEMICAL CO.,LTD.).

[0303] (solvent) Regarding the solvent in method D, from the viewpoint of facilitating the infiltration of the polyfunctional (meth)acrylate compound (c1) to form a mixed layer, a solvent with high affinity for the hard coating is preferred. The affinity between the solvent and the hard coating can be determined by the increase in haze of the hard coating when it is immersed in various solvents. That is, it can be determined that the greater the increase in haze, the higher the affinity of the solvent for the hard coating. In particular, when the hard coating is a polyorganosilicone silsesquioxane containing alicyclic epoxy groups, methyl acetate, toluene, and methyl ethyl ketone are preferred solvents with high affinity for the hard coating, and methyl acetate and toluene are more preferred.

[0304] (Concentration of solid components) The solid content of the scratch-resistant layer forming composition in Method D can be appropriately adjusted by the hard coating forming composition and the polyfunctional (meth)acrylate compound (c1), but is preferably 40% or less, more preferably 20% or less. By setting the solid content concentration to 40% or less, the scratch-resistant layer forming composition becomes easier to penetrate into the hard coating and easily forms a mixed layer (ii). By setting the solid content concentration to 20% or less, the hard coating film of the present invention easily becomes a laminated structure with high interlayer adhesion, and higher scratch resistance is easily obtained.

[0305] <Process (IV'')> Step (IV'') is a process of fully curing the above-mentioned coating (i), the mixed layer (ii) formed by penetration, and the coating (iii). The curing conditions and drying process of step (IV'') are as described in step (IV) of method A.

[0306] In method D, drying can also be performed as needed after step (III') and before step (IV''), or after step (IV''), or during both periods.

[0307] The present invention also relates to an article having the hard coating of the present invention described above, and an image display device having the hard coating of the present invention as a surface protective film. The hard coating of the present invention is particularly preferably applied to flexible displays such as smartphones.

[0308] Example The present invention will be further described in detail below through examples, but should not be construed as limiting the scope of the invention.

[0309] <Making of Substrate> (Manufacturing of polyimide powder) In a 1L reactor equipped with a stirrer, nitrogen injection device, dropping funnel, temperature regulator, and cooler, 832g of N,N-dimethylacetamide (DMAc) was added under a nitrogen gas flow, and the reactor temperature was set to 25°C. 64.046g (0.2mol) of bis(trifluoromethyl)benzidine (TFDB) was added and dissolved. While maintaining the obtained solution at 25°C, 31.09g (0.07mol) of 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) and 8.83g (0.03mol) of biphenyltetracarboxylic acid dianhydride (BPDA) were added, and the mixture was stirred for a certain period to allow the reaction to proceed. Then, 20.302g (0.1mol) of terephthaloyl chloride (TPC) was added, yielding a polyamic acid solution with a solid content of 13% by mass. Next, 25.6 g of pyridine and 33.1 g of acetic anhydride were added to the polyamic acid solution and stirred for 30 minutes. The mixture was then stirred further at 70°C for 1 hour and cooled to room temperature. 20 L of methanol was added, and the precipitated solid was filtered and pulverized. The solid was then vacuum dried at 100°C for 6 hours to obtain 111 g of polyimide powder.

[0310] (Fabrication of substrate S-1) 100g of polyimide powder was dissolved in 670g of N,N-dimethylacetamide (DMAc) to obtain a 13% by mass solution. The obtained solution was cast onto a stainless steel plate and dried with hot air at 130°C for 30 minutes. The film was then peeled off from the stainless steel plate, fixed to a frame with pins, and the frame with the film was placed in a vacuum oven. The temperature was gradually increased from 100°C to 300°C for 2 hours, followed by gradual cooling. After separating the cooled film from the frame, it was further heat-treated at 300°C for 30 minutes as a final heat treatment step, thereby obtaining a substrate S-1 containing a 30μm thick polyimide film.

[0311] (Fabrication of substrate S-2) The nitrogen-substituted polymerization tank contained the compound represented by formula (1), the compound represented by formula (2), the compound represented by formula (3), a catalyst, and a solvent (γ-butyrolactone and dimethylacetamide). The amounts added were: 75.0 g of the compound represented by formula (1), 36.5 g of the compound represented by formula (2), 76.4 g of the compound represented by formula (3), 1.5 g of the catalyst, 438.4 g of γ-butyrolactone, and 313.1 g of dimethylacetamide. The molar ratio of the compound represented by formula (2) to the compound represented by formula (3) was 3:7, and the molar ratio of the total of the compounds represented by formula (2) and (3) to the compound represented by formula (1) was 1.00:1.02.

[0312] [Chemical Formula 17] After stirring the mixture in the polymerization tank to dissolve the raw materials in the solvent, the mixture was heated to 100°C, then to 200°C, and held at that temperature for 4 hours, thereby polymerizing polyimide. During this heating process, water was removed from the liquid. Then, through purification and drying, polyimide (a polyimide polymer containing repeating structural units of the formula (PI)) was obtained.

[0313] Next, a γ-butyrolactone solution of polyimide with a concentration adjusted to 20% by mass, a dispersion of silica particles with a solid content concentration of 30% by mass dispersed in the γ-butyrolactone, a dimethylacetamide solution of an amino-containing alkoxysilane, and water were mixed and stirred for 30 minutes. This stirring was performed according to the method described in U.S. Patent No. 8,207,256B2.

[0314] The mass ratio of silica particles to polyimide is set to 60:40, the amount of amino-containing alkoxysilane is set to 1.67 parts by mass relative to 100 parts by mass of silica particles and polyimide, and the amount of water is set to 10 parts by mass relative to 100 parts by mass of silica particles and polyimide.

[0315] The mixed solution was coated onto a glass substrate and dried by heating at 50°C for 30 minutes and then at 140°C for 10 minutes. Afterward, the film was peeled off from the glass substrate, a metal frame was installed, and the film was heated at 210°C for 1 hour, thus obtaining a substrate S-2 with a thickness of 80 μm. The silica particle content in this resin film was 60% by mass. The yellowness (YI value) of the obtained resin film was 2.3.

[0316] <Synthesis of Polyorganosilicon Silsesquioxanes> (Synthesis of compound (A)) In a 1000 mL flask (reaction vessel) equipped with a thermometer, stirrer, reflux cooler, and nitrogen inlet tube, 300 mmol (73.9 g) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 7.39 g of triethylamine, and 370 g of MIBK (methyl isobutyl ketone) were mixed under a nitrogen gas flow. Using a dropping funnel, 73.9 g of pure water was added dropwise over 30 minutes. The reaction solution was heated to 80 °C and subjected to a polycondensation reaction under a nitrogen gas flow for 10 hours.

[0317] Then, the reaction solution was cooled, and 300g of 5% saline solution was added to extract the organic layer. The organic layer was washed twice with 300g of 5% saline solution and 300g of pure water, and then concentrated at 1mmHg and 50℃ to obtain a colorless and transparent liquid product {a polyorganosilicon sesquioxane with alicyclic epoxy group, namely compound (A) (Rb in general formula (1): 2-(3,4-epoxycyclohexyl)ethyl, q=100, r=0)} 87.0g as a solid component concentration of 59.8% by mass in a MIBK solution.

[0318] The analysis of the product showed that the number-average molecular weight was 2050 and the molecular weight dispersion was 1.9.

[0319] Additionally, 1 mmHg is approximately 133.322 Pa.

[0320] (Synthesis of compound (B)) In the synthesis of compound (A), 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane was replaced with 3-glycidoxypropyltrimethoxysilane. Otherwise, a methyl isobutyl ketone (MIBK) solution containing compound (B) (Rb in general formula (1): 3-glycidoxypropyl, q=100, r=0 for compound) with a solid content of 58.3% by mass was obtained by the same method as the synthesis of compound (A).

[0321] The obtained compound (B) has a number-average molecular weight (Mn) of 2190 and a dispersion (Mw / Mn) of 2.0.

[0322] (Synthesis of compound (C)) In the synthesis of compound (A), 300 mmol (73.9 g) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane was replaced with 297 mmol (73.2 g) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and 3 mmol (409 mg) of methyltrimethoxysilane. Otherwise, a methyl isobutyl ketone (MIBK) solution containing compound (C) (a compound of general formula (1) with Rb: 2-(3,4-epoxycyclohexyl)ethyl, Rc: methyl, q=99, r=1) at a solid content of 59.0% by mass was obtained by the same method as the synthesis of compound (A).

[0323] The number-average molecular weight (Mn) of the obtained compound (C) was 2310, and the dispersity (Mw / Mn) was 2.1.

[0324] [Example 1] <Preparation of compositions for hard coating> (Composition HC-1 for forming hard coating) CPI-100P, leveling agent-1, and MIBK (methyl isobutyl ketone) were added to a MIBK solution containing compound (A) described above, and the concentrations of each component were adjusted to the concentrations shown below. The solution was then placed in a mixing tank and stirred. The resulting composition was filtered through a polypropylene filter with a pore size of 0.4 μm, and thus used as composition HC-1 for forming a hard coating.

[0325] Compound (A) 98.7 parts by mass CPI-100P 1.3 parts by weight Leveling agent-1 0.01 parts by weight 100.0 parts by weight of methyl isobutyl ketone In addition, the compounds used in the composition for forming a hard coating are as follows.

[0326] CPI-100P: Cationic photopolymerization initiator, manufactured by San-Apro Ltd. Leveling agent-1: Polymer with the following structure (Mw=20000, the composition ratio of the repeating units below is by mass). [Chemical Formula 18] <Preparation of Compositions for Mixed Layer Formation> (Composition M-1 for forming mixed layers) Regarding the solvent, the MIBK solution containing compound (A) was replaced 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 levels, and the mixture was added to a mixing tank and stirred. The resulting composition was filtered through a polypropylene filter with a pore size of 0.4 μm and used as composition M-1 for forming a mixed layer. In composition M-1 for forming a mixed layer, the mixing ratio of compound (A) to DPHA was compound (A) / DPHA = 20% by mass / 80% by mass.

[0327] Compound (A) 17.14 parts by mass DPHA 68.56 parts by weight CPI-100P 1.3 parts by weight Irgacure127 5.0 parts by weight Leveling agent-1 8.0 parts by weight 500.0 parts by weight of methyl ethyl ketone In addition, the compounds used in the composition for forming the mixed layer are as follows.

[0328] DPHA: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd. Irgacure127: Free radical photopolymerization initiator, manufactured by BASF. <Preparation of Compositions for Forming Abrasion-Resistant Layers> (SR-1 composition for forming abrasion-resistant layer) Each component was added to a mixing tank with the composition described below and stirred. The mixture was then filtered through a polypropylene filter with a pore size of 0.4 μm, thereby obtaining composition SR-1 for forming a scratch-resistant layer.

[0329] DPHA 96.2 parts by weight Irgacure127 2.8 parts by weight RS-90 1.0 part by weight 300.0 parts by weight of methyl ethyl ketone (SR-2 composition for forming abrasion-resistant layer) Each component was added to a mixing tank with the composition described below and stirred. The mixture was then filtered through a polypropylene filter with a pore size of 0.4 μm, thereby obtaining composition SR-2 for forming a scratch-resistant layer.

[0330] DPHA 50.0 parts by weight PET30 46.2 parts by weight Irgacure127 2.8 parts by weight RS-90 1.0 part by weight 300.0 parts by weight of methyl acetate (SR-3 composition for forming abrasion-resistant layer) Each component was added to a mixing tank with the composition described below and stirred. The mixture was then filtered through a polypropylene filter with a pore size of 0.4 μm, thereby obtaining composition SR-3 for forming a scratch-resistant layer.

[0331] DPHA 50.0 parts by weight PET30 46.2 parts by weight Irgacure127 2.8 parts by weight RS-90 1.0 part by weight 300.0 parts by weight of methyl ethyl ketone (SR-4 composition for forming abrasion-resistant layer) Each component is added to a mixing tank with the composition described below and stirred. The mixture is then filtered through a polypropylene filter with a pore size of 0.4 μm, thereby obtaining composition SR-4 for forming a scratch-resistant layer.

[0332] DPHA 50.0 parts by weight PET30 46.2 parts by weight Irgacure127 2.8 parts by weight RS-90 1.0 part by weight 900.0 parts by weight of methyl ethyl ketone (SR-5 composition for forming abrasion-resistant layer) Each component is added to a mixing tank with the composition described below and stirred. The mixture is then filtered through a polypropylene filter with a pore size of 0.4 μm, thereby obtaining composition SR-5 for forming a scratch-resistant layer.

[0333] DPHA 96.2 parts by weight Irgacure127 2.8 parts by weight RS-90 1.0 part by weight 900.0 parts by weight of methyl ethyl ketone In addition, the compounds used in the composition for forming a scratch-resistant layer are as follows.

[0334] RS-90: Lubricant, manufactured by DIC Corporation. PET30: A mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, manufactured by Nippon Kayaku Co., Ltd. <Preparation of Hard Coating> Using a die-coating machine, a hard coating composition HC-1 was applied to substrate S-1. After drying at 120°C for 1 minute, the substrate was irradiated with an air-cooled mercury lamp at 25°C with an illuminance of 18 mW / cm². 2 The radiation dose is 10 mJ / cm. 2 The ultraviolet light causes the hard coating to partially cure.

[0335] Using a die coater, the composite composition M-1 for forming a mixed layer was applied onto the semi-cured hard coating. After drying at 120°C for 1 minute, it was irradiated with an air-cooled mercury lamp at 25°C and an oxygen concentration of 100 ppm (parts per million) at an illuminance of 60 mW / cm². 2 The radiation dose is 600 mJ / cm. 2 Following ultraviolet light, the mercury lamp was used to irradiate the area at 80°C and an oxygen concentration of 100 ppm, with an illuminance of 60 mW / cm². 2 The radiation dose is 600 mJ / cm. 2 The ultraviolet light was used to completely cure the hard coating and the hybrid layer. The resulting film was then heat-treated at 120°C for 1 hour to obtain a hard coating film 1 with a hybrid layer of 1.0 μm thickness on a hard coating of 11.0 μm thickness. Furthermore, a cross-sectional sample of the hard coating film was prepared using an ultrathin slicer, and the cross-section was observed using SEM to calculate the thickness of the hard coating and the hybrid layer.

[0336] [Examples 2-6] The mixing ratio of compound (A) to DPHA in the mixed layer forming composition M-1 or the film thickness of the mixed layer were changed as shown in Table 1. Otherwise, hard coating films 2 to 6 were obtained in the same manner as in Example 1.

[0337] [Example 7] A hard coating was applied to the substrate using the same method as in Example 1.

[0338] MEK was added to the mixed layer forming composition M-1 to prepare a mixed layer forming composition with a solid component concentration diluted to 1 / 10, and then applied to a semi-cured hard coating using a die coater. After drying at 120°C for 1 minute, the mixture was irradiated with an air-cooled mercury lamp at 25°C and an oxygen concentration of 1% at an illuminance of 18 mW / cm². 2 The radiation dose is 10 mJ / cm. 2 The ultraviolet light is used to semi-cur the hybrid layer, and the hybrid layer is then applied to the hard coating.

[0339] Using a die coater, the scratch-resistant layer-forming composition SR-1 was applied to the semi-cured mixed layer. After drying at 120°C for 1 minute, it was irradiated with an air-cooled mercury lamp at 25°C and an oxygen concentration of 100 ppm, with an illuminance of 60 mW / cm². 2 The radiation dose is 600 mJ / cm. 2 Following ultraviolet light, the mercury lamp was used to irradiate the area at 80°C and an oxygen concentration of 100 ppm, with an illuminance of 60 mW / cm². 2 The radiation dose is 600 mJ / cm. 2 The ultraviolet light was used to completely cure the hard coating, the hybrid layer, and the scratch-resistant layer. The resulting film was then heat-treated at 120°C for 1 hour to obtain a hard coating film 7 with a 1.0 μm thick scratch-resistant layer on a 0.1 μm thick hybrid layer. Furthermore, a cross-sectional sample of the hard coating film was prepared using an ultrathin slicer, and the cross-section was observed using SEM to calculate the thicknesses of the hard coating, the hybrid layer, and the scratch-resistant layer.

[0340] [Examples 8-25] The types of substrate, epoxy compounds and polyfunctional acrylate compounds in the mixed layer forming composition and their mixing ratio, and the types of polysiloxane and polyfunctional acrylate compounds in the hard coating forming composition were changed to those listed in Table 1, and the film thickness of each layer was changed to the thickness listed in Table 1. Otherwise, hard coating films 8 to 25 were obtained using the same method as in Example 7.

[0341] CEL2021P: The following compound. Manufactured by Daicel Corporation. [Chemical Formula 19] DPCA20: KAYARAD DPCA20, the following compound. Manufactured by Nippon Kayaku Co., Ltd. [Chemical Formula 20] [Example 26] <Preparation of Hard Coating> Using a die-coating machine, a hard coating composition HC-1 was applied to substrate S-1. After drying at 120°C for 1 minute, the substrate was irradiated with an air-cooled mercury lamp at 25°C with an illuminance of 18 mW / cm². 2 The radiation dose is 10 mJ / cm. 2 The ultraviolet light causes the hard coating to partially cure.

[0342] Using a die coater, the scratch-resistant layer-forming composition SR-2 was applied to a semi-cured hard coating. After drying at 120°C for 1 minute, it was irradiated with an air-cooled mercury lamp at 25°C and an oxygen concentration of 100 ppm, with an illuminance of 60 mW / cm². 2 The radiation dose is 600 mJ / cm. 2 Following ultraviolet light, the mercury lamp was used to irradiate the area at 80°C and an oxygen concentration of 100 ppm, with an illuminance of 60 mW / cm². 2 The radiation dose is 600 mJ / cm. 2 The ultraviolet light is used to completely cure the hard coating, the hybrid layer formed by penetration, and the scratch-resistant layer. Then, by heat-treating the obtained film at 120°C for 1 hour, a hard coating film 26 with a scratch-resistant layer of 1.0 μm thickness is obtained.

[0343] [Examples 27-29] The composition for forming the scratch-resistant layer was changed to the composition described in Table 1, and hard coatings 27-29 were obtained in the same manner as in Example 26.

[0344] [Comparative Example 1] Using a die-coating machine, a hard coating composition HC-1 was applied to substrate S-1. After drying at 120°C for 1 minute, the substrate was irradiated with an air-cooled mercury lamp at 25°C and an oxygen concentration of 100 ppm, with an illuminance of 60 mW / cm². 2 The radiation dose is 600 mJ / cm. 2 Following ultraviolet light, the mercury lamp was used to irradiate the area at 80°C and an oxygen concentration of 100 ppm, with an illuminance of 60 mW / cm². 2 The radiation dose is 600 mJ / cm. 2 The ultraviolet light was used to completely cure the hard coating. Then, by heat-treating the obtained film at 120°C for 1 hour, a comparative hard coating film 1 with a thickness of 11.0 μm on the substrate was obtained.

[0345] [Comparative Examples 2-4] Compound (A) in the hard coating forming composition HC-1 was replaced with a mixture of compound (A) and DPHA in the ratio shown in Table 1. Otherwise, comparative hard coatings 2 to 4 were obtained in the same manner as in Comparative Example 1.

[0346] [Comparative Example 5] Without coating the mixed layer composition M-1 and semi-curing the mixed layer, a relatively hard coating film 5 was obtained using the same method as in Example 7.

[0347] <Condensation Rate> use 29The condensation rate of the hard coatings obtained in Examples 1-24 was calculated from the results of Si NMR spectroscopy measurements. Specifically, based on... 29 The area ratios of T3, T2, T1, and T0 were calculated using the results of Si NMR spectroscopy (apparatus: Bruker Biospin AVANCE400, solvent: CDCl3), and the condensation rate was calculated using the following formula. Additionally, in 29 In the Si NMR spectroscopy results, T3 is the peak value originating from the structure where all three hydrolyzable groups bonded to Si are fully condensed, T2 and T1 are the peak values ​​originating from the structures where two and one hydrolyzable groups bonded to Si are condensed, respectively, and T0 is the peak value originating from the structure where the hydrolyzable groups bonded to Si are not condensed.

[0348] Condensation rate (%) = (0 T0+1 T1+2 T2+3 T3) / (3(T0+T1+T2+T3))×100 The condensation rate of the hard coatings obtained in Examples 1-24 was 96%.

[0349] <Surface ring opening rate> The surface ring-opening rate of the polysiloxane contained in the hard coating was calculated as follows: The peak value originating from the epoxy groups was measured by FT-IR single-reflectance ATR for both uncured and cured products (for compounds (A) and (C) with alicyclic epoxy groups, it was 883 cm⁻¹). -1 Regarding compound (B) containing a glycidyl ether group, the value is 910 cm. -1 The height of ) is calculated according to the following formula.

[0350] Surface ring opening rate (%) = (1 - peak height after curing / peak height before curing) × 100 Films were prepared by coating the hard coating composition containing the polysiloxane used in Examples 1 to 24 to the film thicknesses described in Table 1 and drying them (uncured products), and films were prepared by subjecting the uncured products to complete curing and heat treatment without imparting a mixing layer and a scratch-resistant layer (cured products).

[0351] The aforementioned complete curing treatment refers to the process performed at 25°C and an oxygen concentration of 100 ppm, using an air-cooled mercury lamp with an irradiance of 60 mW / cm². 2 The radiation dose is 600 mJ / cm. 2 Following ultraviolet light, the mercury lamp was used to irradiate the area at 80°C and an oxygen concentration of 100 ppm, with an illuminance of 60 mW / cm². 2 The radiation dose is 600 mJ / cm. 2In the case of ultraviolet radiation, heat treatment refers to treating a fully cured film at 120°C for 1 hour.

[0352] The surface ring-opening rates of compounds (A) and (C) in the hard coating of the above samples, calculated based on FT-IR single-reflection ATR measurements, were 70%. The surface ring-opening rate of compound (B) was 67%.

[0353] <Thickness Analysis of the Hybrid Layer Formed by Infiltration> Using the Ulvac-PHI TRIFT V Nano TOF (primary ion Bi3) mass analysis device ++ Using an Ar-GCIB gun (15kV, 2.5nA, 500μm square), with an accelerating voltage of 30kV, fragment ions were analyzed while etching from the scratch-resistant layer side of the hard coating film. The thickness of the mixed layer of the hard coating film obtained in Examples 26-29 was thus determined. The region where fragments originating from both the scratch-resistant layer component and the hard coating component were detected was defined as the mixed layer. The thickness of the mixed layer was calculated based on the time of detection of the mixed layer and the pre-determined etching depth per unit time of the scratch-resistant layer. The thicknesses of the mixed layer of the hard coating film obtained in Examples 26-29 were 0.15μm, 0.08μm, 0.12μm, and 0.10μm, respectively.

[0354] [Evaluation of Hard Coating] The prepared hard coating was evaluated using the following method.

[0355] (Pencil hardness) The measurements were performed according to JIS K 5600-5-4 (1999).

[0356] (Resistance to repeated bending) Sample films, 15 mm wide and 150 mm long, were cut from the hard-coated films manufactured in the various embodiments and comparative examples, and left to stand for more than 1 hour at a temperature of 25°C and a relative humidity of 65%. Then, a flexural endurance test was repeatedly performed using a flexural endurance tester (Imoto machinery Co., LTD., IMC-0755 model, flexural radius 1.0 mm), with the substrate facing outwards. The evaluation was based on the number of times cracks or fractures occurred on the sample film, according to the following criteria.

[0357] A: More than 500,000 times B: More than 100,000 times but less than 500,000 times C: Less than 100,000 times (Abrasion resistance) Using a friction testing machine, friction tests were performed on the surface of the hard coating film manufactured in each embodiment and comparative example, opposite to the substrate, under the following conditions, thereby serving as an indicator of scratch resistance.

[0358] Evaluation environmental conditions: 25℃, relative humidity 60% Friction material: steel wool (manufactured by NIHON STEEL WOOL Co., Ltd., No. 0000) Wrap the 1cm x 1cm strip around the friction front end of the tester that contacts the sample, and secure it with a strap. Distance traveled (one way): 13cm Friction speed: 13 cm / s Load capacity: 1000g / cm 2 Front end contact area: 1cm × 1cm Number of friction cycles: 100 round trips, 1000 round trips, 5000 round trips After the test, oily black ink was applied to the side of the hard coating film opposite to the friction surface of each embodiment and comparative example. The number of frictions when scratches were generated in the part in contact with steel wool was measured by visual observation using reflected light, and the results were evaluated in the following four stages.

[0359] A: No scratches were produced even after 5000 rubs.

[0360] B: No scratches were produced even after 1000 rubs, but scratches appeared before 5000 rubs.

[0361] C: No scratches were produced even after 100 rubs, but scratches appeared before 1000 rubs.

[0362] D: Scratches appear before 100 rubs.

[0363] The evaluation results are shown in Table 1 below.

[0364] [Table 1]

[0365] As shown in Table 1, the hard coating films of the embodiments exhibit excellent hardness, scratch resistance, and resistance to repeated bending. On the other hand, the hard coating films of Comparative Examples 1, 4, and 5 have poor scratch resistance because they lack a mixing layer. Furthermore, compared to the hard coating films of Comparative Examples 2 and 3, the hard coating films of Comparative Examples 1, 4, and 5, which have a lower amount of polyfunctional acrylate compounds in the hard coating layer, exhibit superior hardness compared to the hard coating films of Comparative Examples 2 and 3.

Claims

1. A hard coating film, comprising sequentially a substrate, a hard coating layer, and a mixing layer, The hard coating contains a cured product of an epoxy-based polyorganosilyl sesquioxane (a1). The mixed layer contains a cured compound (b1) having an epoxy group and a cured compound (b2) having two or more (meth)acryloyl groups in one molecule. The content of the cured compound (b2) having two or more (meth)acryloyl groups per molecule in the mixed layer is 10% by mass or more relative to the total amount of the cured compound (b1) having epoxy groups and the cured compound (b2) having two or more (meth)acryloyl groups per molecule. The epoxy-containing polyorganosilicone sesquioxane (a1) is an epoxy-containing polyorganosilicone sesquioxane. The epoxy-containing compound (b1) is a polyorganosilyl sesquioxane with alicyclic epoxy groups. The surface of the hybrid layer opposite to the hard coating side has a scratch-resistant layer. The scratch-resistant layer comprises a cured compound (c1) having two or more (meth)acryloyl groups in one molecule.

2. The hard coating film according to claim 1, wherein, The thickness of the hybrid layer is 0.05 μm to 10 μm.

3. The hard coating film according to claim 1, wherein, The combined thickness of the hybrid layer and the scratch-resistant layer is 0.1 μm to 10 μm.

4. The hard coating film according to claim 1 or 2, wherein, The hard coating does not contain cured products of compounds with (meth)acrylyl groups, or the content of cured products of compounds with (meth)acrylyl groups is less than 10% by mass relative to the total amount of cured products of the epoxy-based polysiloxane (a1) and the cured products of the compounds with (meth)acrylyl groups.

5. The hard coating film according to claim 1 or 2, wherein, The substrate comprises an imide-based polymer.

6. An article comprising the hard coating of any one of claims 1 to 5.

7. An image display device comprising a hard coating film as any one of claims 1 to 5 as a surface protective film.

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