Films without hard coating, laminates, multilayer laminates, and display devices

Abstract

[Problem] This invention provides a coating-free film that is relatively lightweight and exhibits excellent mechanical strength and heat resistance, even when free of PFAS (per- and polyfluoroalkyl substances) regulated substances. [Solution] The coating-free film of this invention satisfies at least one of the following conditions: an elastic-plastic ratio of 70% or more in an indentation test; a glass transition temperature and melting point of not less than 200°C; and a Young's modulus of 1000 MPa or more in an indentation test and a Young's modulus of 1000 to 5000 MPa in a tensile test.

Description

[Technical Field]

[0001] This invention relates to a film without hard coating, a laminate, a multilayer laminate, and a display device. Specifically, this invention relates to a film without hard coating, a laminate having the film without hard coating, a multilayer laminate, and a display device. [Previous Technology]

[0002] A protective film or a hard coating is applied to the liquid crystal screen of liquid crystal displays, organic EL displays, plasma displays, etc., thereby preventing damage to the screen or making it difficult for fingerprints to adhere to the screen, and achieving the effect of easy removal of stains adhering to the screen.

[0003] In recent years, with the development of mobile devices such as smartphones or PCs, the industry has demanded the thinning and miniaturization of optical substrates such as display substrates. Therefore, the thinning or miniaturization of substrates used for applying hard coatings has also been developed.

[0004] As the aforementioned substrate, glass, polyimide, or polyethylene terephthalate (PET) are commonly used. However, glass has the problem that its weight increases the weight of mobile machinery and it is easily broken by impact. Furthermore, polyimide often contains alkyl fluorine in its structure, which complies with recent regulations on per- and polyfluoroalkyl substances (PFAS), potentially restricting its use in some regions. Additionally, PET has the problem of lower heat resistance.

[0005] Furthermore, from the viewpoint of thin-film technology, a single-layer film with excellent scratch resistance on the surface that does not require a hard coating or supporting substrate is proposed. For example, Patent Document 1 discloses a hardened coating film comprising a crosslinked polymer containing urethane acrylate oligomers, and Patent Document 2 discloses a substrate-free flexible display device cover window comprising a polysiloxane containing epoxy functional groups and an elastomer. [Prior Art Documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2017-214553 [Patent Document 2] Korean Patent Publication No. 10-2023-0050843 [Summary of the Invention]

[0007] [Problems to be Solved by the Invention] However, the crosslinking density of the membrane in Patent Document 1 is about 60%, which is insufficient in mechanical strength. Furthermore, since the cover window in Patent Document 2 contains an elastomer, its mechanical strength is also insufficient. Moreover, even when using a single-layer membrane, heat resistance is sometimes required.

[0008] Therefore, the object of the present invention is to provide a coating-free film that is relatively lightweight and has excellent mechanical strength and heat resistance, even when it does not contain PFAS-controlled substances. Furthermore, the object of the present invention is to provide a laminate, a multilayer laminate, and a display device having the above-mentioned coating-free film. [Technical Means for Solving the Problem]

[0009] The inventors of this invention conducted in-depth research to solve the above-mentioned problems and discovered that, based on specific physical properties, uncoated films are relatively lightweight and have excellent mechanical strength even when they do not contain PFAS-regulated substances. This invention was made based on these insights.

[0010] That is, the present invention provides a film without hard coating, which satisfies the following conditions: the elastic-plastic ratio in the indentation test is 70% or more, and the glass transfer temperature and melting point are not below 200°C; and satisfies at least one of the following conditions: the Young's modulus in the indentation test is 1000 MPa or more, and the Young's modulus in the tensile test is 1000 to 5000 MPa.

[0011] Preferably, the above-mentioned uncoated film has a thickness of 1 to 1000 μm and an indentation hardness of 100 MPa or more obtained from the indentation test.

[0012] Preferably, the above-mentioned film without hard coating is formed from a hardened material of a hardening composition, and the glass transition temperature of the hardened material is 300°C or higher.

[0013] Preferably, the above-mentioned film without hard coating is formed from a hardened material of a hardening composition, and the pencil hardness of the hardened material is 2H or higher.

[0014] Preferably, the above-mentioned curing composition is a free radical curing polyorganosiloxane.

[0015] Preferably, the above-mentioned curing composition contains a cationic polymerizable silsesquioxane.

[0016] Preferably, the above-mentioned curing composition further includes a curing compound having a polymerizable functional group with active energy lines.

[0017] Furthermore, the present invention provides a laminate comprising the above-mentioned uncoated film and a functional layer laminated on the above-mentioned uncoated film.

[0018] Furthermore, the present invention provides a multilayer laminate, which is formed by stacking a plurality of the above-mentioned laminates.

[0019] Furthermore, the present invention provides a display device comprising the aforementioned multilayer laminate. [Effects of the Invention]

[0020] According to the present invention, a film without hard coating that is relatively light and has excellent mechanical strength and heat resistance even when it does not contain PFAS controlled substances, as well as a laminate having the above-mentioned film without hard coating, a multilayer laminate, and a display device can be provided.

Implementation Method

[0021] [Film without hard coating] The film without hard coating of the present invention satisfies the following conditions: the elastic-plastic ratio in the indentation test is 70% or more, and the glass transfer temperature and melting point are not below 200°C; and satisfies at least one of the following conditions: the Young's modulus in the indentation test is 1000 MPa or more, and the Young's modulus in the tensile test is 1000 to 5000 MPa. Preferably, both conditions are satisfied.

[0022] In this specification, "film without hard coating" refers to a film (sheet) that has no hard coating formed on both sides, but has hard coating properties on a single layer. The above-mentioned film without hard coating does not require the additional hard coating, which makes it relatively lighter.

[0023] The elastic-plastic ratio in the indentation test of the above-mentioned uncoated film is 70% or more, preferably 75% or more, and even more preferably 80% or more. When the above elastic-plastic ratio is 70% or more, it is not easy to cause damage when stress is applied, and the mechanical strength of the film is excellent. Furthermore, the above elastic-plastic ratio is preferably 95% or less, even more preferably 95% or less, and even more preferably 90% or less. When the above elastic-plastic ratio is 95% or less, it has excellent flexibility and excellent bending resistance.

[0024] Preferably, the above-mentioned uncoated film has a Young's modulus of 1000 MPa or more, more preferably 2000 MPa or more, and even more preferably 3000 MPa or more in the indentation test. When the Young's modulus in the indentation test is 1000 MPa or more, a hardness that is not easily damaged is achieved, and the mechanical strength of the film is excellent. Furthermore, the Young's modulus in the indentation test is preferably 10000 MPa or less, more preferably 9000 MPa or less, and even more preferably 8000 MPa or less. When the Young's modulus in the indentation test is 10000 MPa or less, excellent flexibility and excellent bending resistance are achieved.

[0025] Preferably, the indentation hardness obtained from the indentation test of the above-mentioned uncoated film is 100 MPa or more, more preferably 300 MPa or more, and even more preferably 700 MPa or more. When the indentation hardness is 100 MPa or more, the surface hardness is high, making it less prone to dents or damage, and the mechanical strength of the film is excellent. Furthermore, the indentation hardness is preferably 1000 MPa or less, more preferably 900 MPa or less, and even more preferably 800 MPa or less. When the indentation hardness is 1000 MPa or less, the flexibility and bending resistance are excellent.

[0026] The above-mentioned indentation test can be performed, for example, by nanoindentation. As the indenter, a triangular cone indenter can be used.

[0027] Preferably, the Young's modulus of the above-mentioned uncoated film in the tensile test is 1000-5000 MPa, more preferably 1200-4000 MPa, and even more preferably 1500-3000 MPa. When the Young's modulus in the tensile test is 1000 MPa or higher, the rigidity required for film formation is maintained, and the film has excellent mechanical strength. When the Young's modulus in the tensile test is 5000 MPa or lower, rigidity is maintained while also taking into account elongation or flexural strength, and the film has excellent mechanical strength.

[0028] The above tensile test can be performed using a known or commonly used tensile testing machine. The Young's modulus is the value measured using a No. 7 dumbbell-shaped uncoated film as the test piece, under normal temperature conditions, with an initial clamping distance of 20 mm, a mark spacing of 12 mm, and a tensile speed of 2 mm / min. Furthermore, the Young's modulus in the tensile test can be obtained as the average value after removing the maximum and minimum values ​​from the measured values ​​of n=5 or higher.

[0029] The above-mentioned uncoated film does not have a glass transition temperature (Tg) and melting point (Tm) below 200°C, and preferably does not have them below 300°C. When the glass transition temperature and melting point are not below 200°C, the uncoated film exhibits excellent heat resistance. The above-mentioned glass transition temperature and melting point are values ​​measured by DSC (differential scanning calorimetry).

[0030] The thickness of the above-mentioned uncoated film is preferably 1 to 1000 μm, more preferably 10 to 600 μm, and even more preferably 30 to 400 μm. When the thickness is 1 μm or more, the mechanical strength and scratch resistance are superior. When the thickness is 1000 μm or less, it is lighter and has excellent bending resistance.

[0031] (Curing composition) The aforementioned film without a hard coating is preferably formed from a cured product of a curing composition. That is, the aforementioned curing composition preferably contains a curing compound. Only one type of curing compound may be used, or two or more types may be used.

[0032] The curing compound described above is preferably a cationic polymerizable silsesquioxane. By including the above-mentioned cationic polymerizable silsesquioxane, the curing composition is less prone to shrinkage during curing, and a relatively thick uncoated film can be easily obtained, thereby forming an uncoated film with superior scratch resistance. The above-mentioned cationic polymerizable silsesquioxane is preferably a photocationically polymerizable silsesquioxane.

[0033] The above-mentioned cationic polymerizable silsesquioxane has a cationic polymerizable functional group within its molecule. Examples of such cationic polymerizable functional groups include hydroxyl, epoxy, oxetane, vinyl ether, and vinylphenyl groups. Among these, epoxy groups are preferred from the viewpoint of enabling higher surface hardness of the film without hard coating.

[0034] As a group containing the above-mentioned epoxy group, a well-known or conventional group having an ethylene oxide ring can be cited as an example, and there is no particular limitation. From the viewpoint of the curability of the curable composition and the heat resistance of the film without hard coating, it is preferred to be a group represented by the following formula (1a), a group represented by the following formula (1b), a group represented by the following formula (1c), a group represented by the following formula (1d), more preferably a group represented by the following formula (1a), a group represented by the following formula (1c), and even more preferably a group represented by the following formula (1a).

[0035] In the above formula (1a), R1a represents a straight-chain or branched alkyl group. Examples of straight-chain or branched alkyl groups include: methylene, methylmethylene, dimethylmethylene, ethyl alkyl group, propyl alkyl group, trimethylene, tetramethylene, pentamethylene, hexamethylene, decamethylene, etc., which are straight-chain or branched alkyl groups with 1 to 10 carbon atoms. Among these, from the viewpoint of the curability of the curable composition, R1a is preferably a straight-chain alkyl group with 1 to 4 carbon atoms, or a branched alkyl group with 3 or 4 carbon atoms, more preferably ethyl alkyl group, trimethylene group, or propyl alkyl group, and even more preferably ethyl alkyl group or trimethylene group.

[0036] In the above formula (1b), R1b represents a straight-chain or branched alkyl group, and can be exemplified by the same group as R1a. Among them, as R1b, from the viewpoint of the curability of the curable composition, it is more preferably a straight-chain alkyl group having 1 to 4 carbons, a branched alkyl group having 3 or 4 carbons, more preferably ethyl, trimethylene, or propyl, and even more preferably ethyl or trimethylene.

[0037] In the above formula (1c), R1c represents a straight-chain or branched alkyl group, and can be exemplified by the same group as R1a. Among them, as R1c, from the viewpoint of the curability of the curable composition, it is more preferably a straight-chain alkyl group having 1 to 4 carbons, a branched alkyl group having 3 or 4 carbons, more preferably ethyl, trimethylene, or propyl, and even more preferably ethyl or trimethylene.

[0038] In the above formula (1d), R1d represents a straight-chain or branched alkyl group, and can be exemplified by the same group as R1a. Among them, as R1d, from the viewpoint of the curability of the curable composition, it is more preferably a straight-chain alkyl group with 1 to 4 carbons, a branched alkyl group with 3 or 4 carbons, more preferably ethyl, trimethylene, or propyl, and even more preferably ethyl or trimethylene.

[0039] R1 in formula (1) is preferably represented by the above formula (1a) and R1a is an ethyl group [wherein, 2-(3,4-epoxycyclohexyl)ethyl].

[0040] As the above-mentioned cationic polymerizable silsesquioxane, examples can be cited of compounds having structural units represented by the following formula (1): [R1SiO3 / 2] (1)

[0041] The structural unit represented by the above formula (1) is usually represented by the silsesquioxane structural unit (so-called T unit) represented by [RSiO3 / 2]. Furthermore, R in the above formula represents a hydrogen atom or a monobasic organic group, and the same applies below. The structural unit represented by the above formula (1) is formed by the hydrolysis and condensation reaction of the corresponding hydrolytic trifunctional silane compound. Furthermore, in this specification, a compound having the structural unit represented by the above formula (1) is sometimes referred to as "silsesquioxane (X)". R1 in formula (1) represents a group containing the above-mentioned cationic polymerizable functional group (monobasic group).

[0042] Silsesquioxane (X) may be a structure having only one structural unit represented by the above formula (1), or it may be a structure having two or more structural units represented by the above formula (1).

[0043] As a silsesquioxane structural unit [RSiO3 / 2], in addition to the structural unit represented by the above formula (1), silsesquioxane (X) may also have a structural unit represented by the following formula (2). [R2SiO3 / 2] (2)

[0044] The structural unit represented by the above formula (2) is a silsesquioxane structural unit (T unit) usually represented by [RSiO3 / 2]. That is, the structural unit represented by the above formula (2) is formed by the hydrolysis and condensation reaction of the corresponding hydrolytic trifunctional silane compound.

[0045] In formula (2) above, R2 represents a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, or a substituted or unsubstituted alkyl group. Examples of the above aryl groups include phenyl, tolyl, and naphthyl. Examples of the above aralkyl groups include benzyl and phenethyl. Examples of the above cycloalkyl groups include cyclobutyl, cyclopentyl, and cyclohexyl. Examples of the above alkyl groups include straight-chain or branched alkyl groups such as methyl, ethyl, propyl, n-butyl, isopropyl, isobutyl, secondary butyl, tertiary butyl, and isopentyl.

[0046] As the above-mentioned substituted aryl, substituted aralkyl, substituted cycloalkyl, substituted alkyl, can be exemplified by a group in which one or more of the hydrogen atoms or the main chain skeleton of each of the above-mentioned aryl, aralkyl, cycloalkyl, and alkyl are replaced with at least one group selected from the group consisting of alkyl (especially straight-chain or branched alkyl with 1 to 10 carbon atoms), ether, ester, carbonyl, siloxyalkyl, halogen atom (fluorine atom, etc.), mercapto, amino and hydroxyl (hydroxyl).

[0047] Wherein, R2 is preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, more preferably a substituted or unsubstituted aryl group, and even more preferably a phenyl group.

[0048] The ratio of the above-mentioned silsesquioxane structural units (the structural units represented by formula (1) and the structural units represented by formula (2)) in the silsesquioxane (X) can be appropriately adjusted by the composition of the raw materials (hydrolyzable trifunctional silanes) used to form such structural units.

[0049] The silsesquioxane (X) preferably contains at least one structural unit represented by formula (1) above, where R1 is a group containing an alicyclic epoxy group, and R2 is a structural unit represented by formula (2) above, where R2 may have a substituent aryl group. In this case, the non-hard-coated film tends to have better surface hardness, flexibility, processability, and flame retardancy.

[0050] In addition to the structural units represented by equation (1) and equation (2) above as T units, silsesquioxane (X) may further have at least one siloxane structural unit selected from the group consisting of structural units represented by [R3SiO1 / 2] (so-called M unit), structural units represented by [R2SiO2 / 2] (so-called D unit), and structural units represented by [SiO4 / 2] (so-called Q unit). Furthermore, R in the above-mentioned M unit and D unit may be the same as R1 in the structural unit represented by equation (1) above and R2 in the structural unit represented by equation (2) above. As a silsesquioxane structural unit other than the structural units represented by equation (1) and equation (2) above, for example, the structural unit represented by the following equation (3) may be cited. [HSiO3 / 2] (3)

[0051] Silsesquioxane (X) comprises a structural unit (T3 body) represented by formula (I) below. It may further comprise a structural unit (T2 body) represented by formula (II) below. [RaSiO3 / 2] (I) [RbSiO2 / 2(ORc)] (II)

[0052] Furthermore, if the structural unit represented by the above formula (I) is described in more detail, it is represented by the following formula (I'). Also, if the structural unit represented by the above formula (II) is described in more detail, it is represented by the following formula (II'). The three oxygen atoms bonded to the silicon atom shown in the structure represented by the following formula (I') are bonded to other silicon atoms (silicon atoms not shown in formula (I')). On the other hand, the two oxygen atoms located above and below the silicon atom shown in the structure represented by the following formula (II') are bonded to other silicon atoms (silicon atoms not shown in formula (II')). That is, the above T3 and T2 bodies are structural units (T units) formed by the hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compounds.

[0053] Ra in formula (I) above (Ra in formula (I') is the same) and Rb in formula (II) above (Rb in formula (II') are the same) respectively represent a group containing a cationic polymerizable functional group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkyl group, or a hydrogen atom. As specific examples of Ra and Rb, those that are the same as R1 in formula (1) above and R2 in formula (2) above can be shown. Furthermore, Ra in formula (I) and Rb in formula (II) are respectively derived from the groups (excluding alkoxy and halogen atoms) of the silicon atoms in the hydrolyzable trifunctional silane compound used as a raw material for silsesquioxane (X), or, for example, in the case where the above-mentioned cationic polymerizable functional group is an epoxy group, the groups are obtained by epoxidation of the groups (excluding alkoxy and halogen atoms) of the silicon atoms in the hydrolyzable trifunctional silane compound used as a raw material for silsesquioxane (X).

[0054] Rc in formula (II) above (and Rc in formula (II') also represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of alkyl groups having 1 to 4 carbon atoms include straight-chain or branched alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, and isobutyl. Among these, methyl and ethyl are preferred, and methyl is even more preferred. The alkyl group in Rc in formula (II) is usually derived from the alkyl group of the alkoxy group in the hydrolyzable silane compound used as a raw material for silsesquioxane (X).

[0055] The molar ratio [structure unit represented by formula (I) / structure unit represented by formula (II)] (sometimes referred to as "T3 body / T2 body") of the structural unit (T3 body) represented by formula (II) in the silsesquioxane (X) is not particularly limited, but is preferably 5 or more, more preferably 5 to 20, further preferably 5 to 18, further preferably 6 to 16, further preferably 7 to 15, and especially preferably 8 to 14. By making the above molar ratio [T3 body / T2 body] 5 or more, there is a tendency to further improve the surface hardness of the non-hard coating film.

[0056] The above molar ratio [T3 body / T2 body] in silsesquioxane (X) can be determined, for example, by 29Si-NMR spectroscopy. In the 29Si-NMR spectrum, silicon atoms in the structural unit (T3 body) represented by the above formula (I) and silicon atoms in the structural unit (T2 body) represented by the above formula (II) show signals (peaks) at different positions (chemical shifts). Therefore, the above molar ratio [T3 body / T2 body] can be determined by calculating the integral ratio of the peaks of each of them. Specifically, for example, when a silsesquioxane (X) has a structural unit represented by formula (1) above and R1 is 2-(3,4-epoxycyclohexyl)ethyl, the signal of silicon atoms in the structure represented by formula (I) above (T3 body) appears at -64 to -70 ppm, and the signal of silicon atoms in the structure represented by formula (II) above (T2 body) appears at -54 to -60 ppm. Therefore, in this case, by calculating the integral ratio of the signal at -64 to -70 ppm (T3 body) and the signal at -54 to -60 ppm (T2 body), the above molar ratio [T3 body / T2 body] can be obtained.

[0057] The 29Si-NMR spectrum of silsesquioxane (X) can be measured, for example, by means of the following apparatus and conditions. Apparatus: Trade name "JNM-ECA500NMR" (manufactured by Nippon Electronics Co., Ltd.) Solvent: Deuterium chloroform Number of measurements: 1800 Measurement temperature: 25°C

[0058] A molar ratio [T3 body / T2 body] of 5 or more for silsesquioxane (X) means that, relative to the T3 body, there is a fixed amount or more of T2 body in silsesquioxane (X). Examples of such T2 body include: structural units represented by the following formula (4), structural units represented by the following formula (5), and structural units represented by the following formula (6). R1 ​​in the following formula (4) and R2 in the following formula (5) are the same as R1 in the following formula (1) and R2 in the following formula (2). Rc in the following formulas (4) to (6) are the same as Rc in formula (II), representing hydrogen atoms or alkyl groups having 1 to 4 carbon atoms. [R1SiO2 / 2(ORc)] (4) [R2SiO2 / 2(ORc)] (5) [HSiO2 / 2(ORc)] (6)

[0059] The cationic polymerizable silsesquioxane (especially silsesquioxane (X)) can be a silsesquioxane having a cage-like shape (cage-like silsesquioxane). Cage-like silsesquioxanes include fully cage-like silsesquioxanes and incompletely cage-like silsesquioxanes, wherein incompletely cage-like silsesquioxanes are preferred.

[0060] Typically, a fully cage-like silsesquioxane is a polyorganosilsesquioxane composed solely of the T3 body, with no T2 body present in the molecule. That is, it implies the following: silsesquioxanes with a molar ratio [T3 body / T2 body] of 5 or higher, and which, as described below, have an intrinsic absorption peak near 1100 cm⁻¹ in the FT-IR spectrum, have an incomplete cage-like silsesquioxane structure.

[0061] Whether silsesquioxane (X) has a cage-like (incomplete cage-like) silsesquioxane structure can be confirmed using FT-IR spectroscopy [Reference: RHRaney, M. Itoh, A. Sakakibara and T. Suzuki, Chem. Rev. 95, 1409 (1995)]. Specifically, in the FT-IR spectrum, the case where "there are no intrinsic absorption peaks near 1050 cm⁻¹ and 1150 cm⁻¹, respectively, and there is an intrinsic absorption peak near 1100 cm⁻¹" can be identified as silsesquioxane (X) having a cage-like (incomplete cage-like) silsesquioxane structure. In contrast, the case where "there are intrinsic absorption peaks near 1050 cm⁻¹ and 1150 cm⁻¹ in the FT-IR spectrum" is usually identified as having a ladder-like silsesquioxane structure. Furthermore, the FT-IR spectrum of silsesquioxane (X) can be measured, for example, using the following apparatus and conditions. Apparatus: Trade name "FT-720" (manufactured by Horiba Manufacturing Co., Ltd.) Measurement method: Transmission method Resolution: 4 cm⁻¹ Wavenumber range: 400–4000 cm⁻¹ Number of measurements: 16

[0062] The ratio (total amount) of the structural units having cationic polymerizable functional groups (e.g., structural units represented by formula (1) above, structural units represented by formula (4) above, etc.) to the total amount of siloxane structural units in the cationic polymerizable silsesquioxane [total amount of all siloxane structural units; M units, D units, T units and Q units] (100 mol%) is not particularly limited, but is preferably 50 mol% or more (e.g., 50 to 100 mol%), more preferably 55 to 100 mol%, more preferably 65 to 99.9 mol%, and even more preferably 80 to 99 mol%, and most preferably 90 to 98 mol%. By having a ratio of 50 mol% or more, the curability of the curable composition is improved, and the surface hardness of the film without hard coating is significantly increased. Furthermore, the ratio of each siloxane structural unit in cationic polymerizable silsesquioxanes can be calculated, for example, by means of the composition of the raw materials or by NMR spectroscopy.

[0063] The ratio of the structural unit (T3 body) represented by the above formula (I) to the total amount of siloxane structural units in the silsesquioxane (X) [total amount of all siloxane structural units; M units, D units, T units and Q units] (100 mol%) is not particularly limited, but is preferably 50 mol% or more, more preferably 60 to 99 mol%, and even more preferably 70 to 98 mol%, even more preferably 80 to 95 mol%, and even more preferably 85 to 92 mol%. It is speculated that by making the ratio of the structural unit of the T3 body 50 mol% or more, it becomes easier to form an incomplete cage shape with an appropriate molecular weight, and therefore there is a tendency to further improve the surface hardness of the film without hard coating.

[0064] The ratio (total amount) of the structural unit represented by the above formula (2) and the structural unit represented by the above formula (5) relative to the total amount of siloxane structural units in silsesquioxane (X) [total amount of all siloxane structural units; M unit, D unit, T unit and Q unit] (100 mol%) is not particularly limited, but is preferably 0 to 50 mol%, more preferably 0 to 40 mol%, and even more preferably 0 to 30 mol%, and even more preferably 1 to 15 mol%. By making the above ratio 50 mol% or less, the ratio of structural units with cationic polymerizable functional groups can be relatively increased, thereby improving the curability of the curable composition and tending to further increase the surface hardness of the film without hard coating.

[0065] The ratio (total amount) of the structural unit represented by formula (I) and the structural unit represented by formula (II) above relative to the total amount of siloxane structural units in the silsesquioxane (X) [total amount of all siloxane structural units; M units, D units, T units and Q units] (100 mol%) (especially the combined ratio of T3 body and T2 body) is not particularly limited, but preferably 60 mol% or more (e.g., 60 to 100 mol%), more preferably 70 mol% or more, further preferably 80 mol% or more, and especially preferably 90 mol% or more. It is speculated that by making the above ratio 60 mol% or more, it becomes easier to form an incomplete cage shape with an appropriate molecular weight, and therefore there is a tendency to further improve the surface hardness of the film without hard coating. It is particularly desirable that the ratio (total amount) of the structural unit represented by the above formula (1), the structural unit represented by the above formula (2), the structural unit represented by the above formula (4), and the structural unit represented by the above formula (5) is within the above range.

[0066] The number average molecular weight (Mn) of silsesquioxane (X) converted from standard polystyrene using gel permeation chromatography is not particularly limited, but is preferably 1000-3000, more preferably 1000-2800, even more preferably 1100-2600, and particularly preferably 1500-2500. By having a number average molecular weight of 1000 or more, there is a tendency to further improve the surface hardness of the uncoated film. Furthermore, there is a tendency to improve the heat resistance and scratch resistance of the uncoated film. On the other hand, by having a number average molecular weight of 3000 or less, there is a tendency to improve compatibility with other components in the curing composition, and to improve the heat resistance of the uncoated film.

[0067] The molecular weight dispersion (Mw / Mn) of silsesquioxane (X) based on gel permeation chromatography converted from standard polystyrene is not particularly limited, but is preferably 1.0 to 3.0, more preferably 1.1 to 2.0, even more preferably 1.2 to 1.9, even more preferably 1.3 to 1.8, and particularly preferably 1.45 to 1.80. By making the molecular weight dispersion 3.0 or less, there is a tendency to further increase the surface hardness of the non-hard-coated film. On the other hand, by making the molecular weight dispersion 1.0 or more (especially 1.1 or more), there is a tendency to make it easier to become liquid, and the processability is improved.

[0068] Furthermore, the number-average molecular weight and molecular weight dispersion of silsesquioxane (X) can be determined using the following apparatus and conditions. Apparatus: Trade name "LC-20AD" (manufactured by Shimadzu Corporation) Columns: Shodex KF-801×2, KF-802, and KF-803 (manufactured by Showa Denko Corporation) Measurement temperature: 40℃ Solution: THF, sample concentration 0.1–0.2% by weight Flow rate: 1 mL / min Detector: UV-VIS detector (trade name "SPD-20A" (manufactured by Shimadzu Corporation) Molecular weight: converted from standard polystyrene

[0069] Cationic polymerizable silsesquioxanes can be manufactured by known or conventional methods of manufacturing silsesquioxanes without particular limitation. For example, they can be manufactured by hydrolyzing and condensing one or more hydrolyzable silane compounds.

[0070] The content ratio of the cationic polymerizable silsesquioxane in the above-mentioned curing composition is not particularly limited, but it is preferably more than 50% by mass (e.g., more than 50% by mass and less than 98% by mass) relative to the total amount of the curing compound (100% by mass), more preferably 60 to 95% by mass, further preferably 70 to 93% by mass, and even more preferably 80 to 90% by mass. When the above-mentioned content ratio exceeds 50% by mass, there is a tendency to further improve the surface hardness of the non-hardened coating film. When the above-mentioned content ratio is less than 98% by mass, there is a tendency to contain other components, thereby further improving the effects obtained by containing them. Furthermore, there is a tendency to contain a curing catalyst, thereby enabling more efficient curing of the curing composition.

[0071] Preferably, the curing compound described above is a curing compound containing a polymerizable functional group with active energy lines (sometimes referred to as an "active energy line curing compound"). In this case, the dispersibility in the curing composition of the free radical curing polyorganosiloxane and in films without hard coating can be improved. Furthermore, the above-mentioned active energy line curing compound is not a compound belonging to the above-mentioned cationic polymerizable silsesquioxanes.

[0072] Examples of polymerizable functional groups for the above-mentioned active energy lines include vinyl, propenyl, isopropenyl, (meth)acrylyl (acryl, methacryl), etc. Among them, (meth)acrylyl is preferred.

[0073] The number of unsaturated bonds in the above-mentioned active energy line hardening compound is 1 or more, preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 to 2, and even more preferably 1.

[0074] The above-mentioned active energy line hardening compound may have a cationic polymerizable functional group within its molecule. In this case, the above-mentioned active energy line hardening compound has reactivity with the above-mentioned cationic polymerizable silsesquioxane, and can obtain a film without a hard coating with higher mechanical strength and surface hardness. As the cationic polymerizable functional group that the above-mentioned active energy line hardening compound may have, examples of cationic polymerizable functional groups that are present in the above-mentioned cationic polymerizable silsesquioxane can be exemplified and described, among which epoxy groups are preferred.

[0075] The number of the above-mentioned cationic polymerizable functional groups in the above-mentioned active energy line hardening compound is 1 or more, preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2.

[0076] The functional group equivalent of the polymerizable functional groups of the above-mentioned active energy line hardening compound is not particularly limited, but is preferably 50 to 500, more preferably 80 to 480, and even more preferably 120 to 450. When the functional group equivalent is 50 or more, the bending resistance of the uncoated film is superior. When the functional group equivalent is 500 or less, the surface hardness of the uncoated film is further increased. Furthermore, the functional group equivalent can be calculated by the following formula: [Functional group equivalent of polymerizable functional groups] = [Molecular weight of the above-mentioned active energy line hardening compound] / [Number of active energy line polymerizable functional groups possessed by the above-mentioned active energy line hardening compound]

[0077] The functional group equivalent of the cationic polymerizable functional group in the above-mentioned active energy line hardening compound is not particularly limited, but is preferably 50 to 500, more preferably 80 to 480, and even more preferably 120 to 450. When the functional group equivalent is 50 or more, the bending resistance of the uncoated film is superior. When the functional group equivalent is 500 or less, the surface hardness of the uncoated film is further increased. Furthermore, the functional group equivalent can be calculated by the following formula: [Functional group equivalent of cationic polymerizable functional group] = [Molecular weight of the above-mentioned active energy line hardening compound] / [Number of cationic polymerizable functional groups possessed by the above-mentioned active energy line hardening compound]

[0078] Preferably, the above-mentioned active energy line hardening compound has a polyether backbone such as a polyethylene glycol backbone, a polypropylene glycol backbone, or a polyglycerol backbone.

[0079] Specifically, examples of the above-mentioned active energy line hardening compounds include: 3,4-epoxycyclohexyl methyl methacrylate, glycidyl methacrylate, tripropylene glycol diglycidyl ether di(meth)acrylate (a compound obtained by reacting (meth)acrylate with two epoxy groups of tripropylene glycol diglycidyl ether), tripropylene glycol diglycidyl ether hemi(meth)acrylate (a compound obtained by reacting (meth)acrylate with one epoxy group of tripropylene glycol diglycidyl ether), bisphenol A epoxy di(meth)acrylate (a compound obtained by reacting (meth)acrylate with two epoxy groups of bisphenol A diglycidyl ether), bisphenol A epoxy hemi(meth)acrylate (a compound obtained by reacting (meth)acrylate or its derivative with one epoxy group of bisphenol A diglycidyl ether), bisphenol F epoxy di(meth)acrylate, bisphenol F epoxy hemi(meth)acrylate, bisphenol S epoxy di(meth)acrylate, bisphenol S epoxy A hemi(meth)acrylate is a compound having an epoxy group and / or a hydroxyl group and a (meth)acrylic acid group within one molecule; 3-oxetane butyl methyl methacrylate, 3-methyl-3-oxetane butyl methyl methacrylate, 3-ethyl-3-oxetane butyl methyl methacrylate, 3-butyl-3-oxetane butyl methyl methacrylate, and 3-hexyl-3-oxetane butyl methyl methacrylate are compounds having an oxetane butyl group and a (methyl) group within one molecule. Acrylic acid compounds; 2-ethoxyethyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, 1-methyl-2-ethoxyethyl (meth)acrylate, 2-ethoxypropyl (meth)acrylate, 4-ethoxybutyl (meth)acrylate, 1-methyl-3-ethoxypropyl (meth)acrylate, 1-ethoxymethylpropyl (meth)acrylate, 2-methyl-3-ethoxypropyl (meth)acrylate, 1,1-Dimethyl-2-ethyleneoxyethyl ester, 3-ethyleneoxybutyl acrylate, 1-methyl-2-ethyleneoxypropyl acrylate, 2-ethyleneoxybutyl acrylate, 4-ethyleneoxycyclohexyl acrylate, 6-ethyleneoxyhexyl acrylate, 4-ethyleneoxymethylcyclohexyl acrylate, 3-ethyleneoxymethylcyclohexyl acrylate, 2-ethyleneoxycyclohexyl acrylate, p-ethyleneoxymethylphenyl acrylate, m-ethyleneoxymethylphenyl acrylate, o-ethyleneoxymethylphenyl acrylate 2-(ethoxyethoxy)ethyl methacrylate, 2-(ethoxyisopropoxy)ethyl methacrylate, 2-(ethoxyethoxy)propyl methacrylate, 2-(ethoxyethoxy)isopropyl methacrylate, 2-(ethoxyisopropoxy)propyl methacrylate, 2-(ethoxyisopropoxy)isopropyl methacrylate, 2-(ethoxyethoxyethoxy)ethyl methacrylate, 2-(ethoxyethoxyisopropoxy)ethyl methacrylate, 2-(ethoxyisopropoxyethoxy)ethyl methacrylate, 2-(ethoxyethoxyethoxy)ethyl methacrylate, 2-(ethoxyethoxy)isopropoxyethoxy)ethyl methacrylate, 2-(ethoxyethoxy)ethyl methacrylate 2-(ethyleneoxyethoxyethoxy)propyl acrylate, 2-(ethyleneoxyethoxyethoxy)propyl acrylate, 2-(ethyleneoxyethoxyisopropoxy)propyl acrylate, 2-(ethyleneoxyisopropoxyethoxy)propyl acrylate, 2-(ethyleneoxyisopropoxyisopropoxy)propyl acrylate, 2-(ethyleneoxyethoxyethoxy)isopropyl acrylate, 2-(ethyleneoxyethoxyisopropoxy)isopropyl acrylate, 2-(ethyleneoxyisopropoxyethoxy)isopropyl acrylate, 2-(ethyleneoxyisopropoxyethoxy)isopropyl acrylate, 2-(ethyleneoxyisopropoxyisopropoxy)isopropyl acrylate, 2-(ethyleneoxyisopropoxyisopropoxy)isopropyl acrylate, 2-(ethyleneoxyisopropoxyisopropoxy)isopropyl acrylate, 2-(ethyleneoxyisopropoxyisopropoxy)isopropyl acrylate, 2-(ethyleneoxyisopropoxyisopropoxy)isopropyl acrylate, 2-(ethyleneoxyisopropoxyisopropoxy)isopropyl acrylate, 2-(ethyleneoxyisopropoxyisopropoxy)isopropyl acrylate, 2-(ethyleneoxyisopropoxyisopropoxy)isopropyl acrylate, 2-(ethyleneoxyisopropoxyisopropoxy)isopropyl acrylate, 2-(ethyleneoxyisopropoxyisopropoxy)isopropyl acrylate, 2-(ethyleneoxyisopropoxy) ... Compounds containing both an vinyl ether group and a (meth)acrylic acid group within one molecule include 2-(vinyloxyethoxyethoxyethoxy)ethyl acrylate, 2-(vinyloxyethoxyethoxyethoxy)ethyl acrylate, 2-(isopropenyloxyethoxyethoxy)ethyl acrylate, 2-(isopropenyloxyethoxyethoxyethoxy)ethyl acrylate, 2-(isopropenyloxyethoxyethoxyethoxyethoxy)ethyl acrylate, polyethylene glycol monovinyl ether of methacrylic acid, and polyethylene glycol monovinyl ether of methacrylic acid.

[0080] From the viewpoint of the bending resistance and surface hardness of the uncoated film, the above-mentioned active energy line curing compound is preferably a compound having an epoxy group and / or a hydroxyl group as a cationic polymerizable functional group within one molecule, and having a (meth)acrylic group as an active energy line polymerizable functional group. Specifically, it is preferably 3,4-epoxycyclohexyl methyl methacrylate, glycidyl methacrylate, tripropylene glycol diglycidyl ether hemi(meth)acrylate, bisphenol A epoxy hemi(meth)acrylate, bisphenol F epoxy hemi(meth)acrylate, bisphenol S epoxy hemi(meth)acrylate, etc.

[0081] The above-mentioned active energy line hardening compound can be manufactured by known methods, such as by reacting a portion of the cationic polymerizable functional group of a compound having two or more cationic polymerizable functional groups (e.g., epoxy group, hydroxyl group) within one molecule with a carboxylic acid (e.g., acrylic acid, methacrylic acid, etc.) or its derivative having an active energy line polymerizable functional group. Furthermore, as the above-mentioned compound A, commercially available products such as "LIGHT ESTER G", "EPOXYESTER 200PA", "EPOXYESTER 200PA-E5" (manufactured by Kyoei Chemical Co., Ltd.), and "NK OLIGO EA1010N" (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) can also be used.

[0082] The content ratio of the above-mentioned active energy line hardening compound in the above-mentioned hardening composition is not particularly limited, but it is preferably 0.1 to 5% by mass, more preferably 0.3 to 4% by mass, and even more preferably 0.6 to 3% by mass, relative to the total amount of hardening compound (100% by mass). When the above-mentioned content ratio is within the above-mentioned range, there is a tendency for the dispersibility of the free radical hardening polyorganosiloxane to be further improved.

[0083] The content of the above-mentioned active energy line hardening compound is not particularly limited, but is preferably 0.01 to 5 parts by mass relative to 100 parts by mass of the above-mentioned cationic polymerizable silsesquioxane, more preferably 0.05 to 4 parts by mass, and even more preferably 0.1 to 3 parts by mass. When the above content is within the above range, there is a tendency for the dispersibility of the free radical hardening polyorganosiloxane to be further improved.

[0084] Preferably, the curing compound described above is an aliphatic compound containing a cationic polymerizable functional group (cationic curing aliphatic compound). In this case, it can impart flexibility to the uncoated film, resulting in higher flexibility and bending resistance. Furthermore, the cationic curing aliphatic compound described above is not a compound belonging to the cationic polymerizable silsesquioxane or the active energy line curing compound described above.

[0085] As the cationic polymerizable functional group of the above-mentioned cationic hardening aliphatic compound, examples of the cationic polymerizable functional group of the above-mentioned cationic polymerizable silsesquioxane can be cited and described, wherein an epoxy group is preferred, and from the viewpoint of reactivity, an epoxypropyl group is more preferred.

[0086] The number of cationic polymerizable functional groups in one molecule of the above-mentioned cationic hardening aliphatic compound is preferably 2 or more, more preferably 2 to 5, further preferably 2 to 3, and even more preferably 2.

[0087] The functional group equivalent of the cationic polymerizable functional group of the above-mentioned cationic hardening aliphatic compound is not particularly limited, but is preferably 50 to 500, more preferably 80 to 480, and even more preferably 120 to 450. When the functional group equivalent is 50 or more, the bending resistance of the uncoated film is more excellent. When the functional group equivalent is 500 or less, the surface hardness of the uncoated film is further increased. Furthermore, the functional group equivalent can be calculated by the following formula: [Functional group equivalent of cationic polymerizable functional group] = [Molecular weight of the above-mentioned cationic hardening aliphatic compound] / [Number of cationic polymerizable functional groups possessed by the above-mentioned cationic hardening aliphatic compound]

[0088] The "aliphatic compound" in the above-mentioned cationic hardening aliphatic compounds refers to an aliphatic compound that does not have a cyclic structure, except for the above-mentioned cationic polymerizable functional group. Examples of the above-mentioned cationic hardening aliphatic compounds include: glycidyl ether of alcohols with two or more non-cyclic structures; glycidyl ester of carboxylic acids with two or more components [e.g., adipic acid, sebacic acid, maleic acid, itaconic acid, etc.]. Examples of non-cyclic alcohols with two or more constituent parts include: 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 tri- or higher polyols such as glycerol, diglycerol, erythritol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and sorbitol. Furthermore, alcohols with two or more constituent parts can also be polyether polyols, polyester polyols, polycarbonate polyols, and polyolefin polyols.

[0089] As the above-mentioned cationic hardening aliphatic compound, it is preferred to be a compound having two cationic polymerizable functional groups at both ends of the above-mentioned aliphatic compound, specifically, it is preferred to be a compound represented by the following formula (A).

[0090] In the above formula (A), M represents a straight-chain or branched alkyl group having 2 to 10 carbon atoms. Examples of straight-chain or branched alkyl groups having 2 to 10 carbon atoms include ethyl alkyl group, propyl alkyl group, trimethylene alkyl group, tetramethylene alkyl group, pentamethylene alkyl group, hexamethylene alkyl group, and decamethylene alkyl group. Among these, from the viewpoint that the surface hardness, flexibility, and flexural resistance of the uncoated film are improved, and the antifouling performance is less likely to decrease, it is preferable to use a straight-chain or branched alkyl group having 3 to 8 carbon atoms, more preferably a straight-chain alkyl group having 5 to 7 carbon atoms, and even more preferably a straight-chain alkyl group having 6 carbon atoms (hexamethylene alkyl group).

[0091] In the above formula (A), E1 and E2 represent cationic polymerizable functional groups in the same or different ways. From the viewpoint that the reactivity, surface hardness, flexibility, and bending resistance of the film without hard coating are improved, and the antifouling performance is less likely to be reduced, the group represented by the following formula (E) is preferred.

[0092] In formula (E), RA represents a straight-chain or branched alkyl group having 1 to 6 carbon atoms. Examples of straight-chain or branched alkyl groups having 1 to 6 carbon atoms include methylene, methylmethylene, dimethylmethylene, ethyl, propyl, trimethylene, tetramethylene, pentamethylene, hexamethylene, decamethylene, etc. Among these, from the viewpoint that reactivity, surface hardness of the uncoated film, flexibility, and flexural resistance are improved, and antifouling performance is less likely to decrease, RA is preferably a straight-chain alkyl group having 1 to 4 carbon atoms, more preferably methylene or ethyl, and even more preferably methylene. RB is a hydrogen atom or a straight-chain or branched alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

[0093] Specifically, examples of the above-mentioned cationic hardening aliphatic compounds include: ethylene glycol diglycidyl ether, 1,3-propanediol diglycidyl ether, 2-methyl-1,3-propanediol diglycidyl ether, 2-butyl-2-ethyl-1,3-propanediol diglycidyl ether, 1,4-butanediol diglycidyl ether (tetramethylenediol diglycidyl ether), neopentyl glycol diglycidyl ether, 3-methyl-2,4-pentanediol diglycidyl ether, 2,4-pentanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether (pentamethylenediol diglycidyl ether), and 3-methyl-1,5-pentanediol diglycidyl ether. Oxypropyl ether, 2-methyl-2,4-pentanediol diglypropyl ether, 2,4-diethyl-1,5-pentanediol diglypropyl ether, 1,6-hexanediol diglypropyl ether (hexamethylenediol diglypropyl ether), 1,7-heptanediol diglypropyl ether, 3,5-heptanediol diglypropyl ether, 1,8-octanediol diglypropyl ether, 2-methyl-1,8-octanediol diglypropyl ether, 1,9-nonanediol diglypropyl ether, and other alkylene glycol diglypropyl ethers (alkylene glycol diglypropyl ether); diethylene glycol diglypropyl ether, propylene glycol diglypropyl ether, triethylene glycol diglypropyl ether, and other (poly)alkylene glycol diglypropyl ethers, etc. From the viewpoint that the reactivity, surface hardness, flexibility, and flexural resistance of the uncoated film are improved, and the antifouling performance is less likely to be reduced, 1,6-hexanediol diglycidyl ether is preferred.

[0094] Examples of commercially available cationic hardening aliphatic compounds include: trade names such as "EPOLIGHT 40E", "EPOLIGHT 100E", "EPOLIGHT 200E", "EPOLIGHT 400E", "EPOLIGHT 1600", "EPOLIGHT 1600N" (manufactured by Kyoei Chemical Co., Ltd.), and trade name "YH-300" (manufactured by Nippon Steel Chemical & Material Co., Ltd.).

[0095] The content ratio of the above-mentioned cationic curable aliphatic compound in the above-mentioned curable composition is not particularly limited, but it is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and even more preferably 3 to 12% by mass, relative to the total amount of curable compound (100% by mass). When the above-mentioned content ratio is within the above-mentioned range, the flexibility and bending resistance of the film without hard coating become more suitable.

[0096] The content of the above-mentioned cationic curable aliphatic compound is not particularly limited, but is preferably 1 to 30 parts by weight, more preferably 3 to 20 parts by weight, and even more preferably 5 to 15 parts by weight, and particularly preferably 6 to 13 parts by weight, relative to 100 parts by weight of the above-mentioned cationic polymerizable silsesquioxane. When the above content is within the above range, the flexibility and bending resistance of the uncoated film become more suitable.

[0097] Preferably, the curing component described above includes a free radical curable polyorganosiloxane. By using the aforementioned free radical curable polyorganosiloxane, the smoothness of the uncoated film surface is improved, its resistance to sebum adhesion is excellent, and fingerprints are less likely to adhere to the uncoated film surface. Furthermore, the aforementioned active energy line curable polyorganosiloxane is preferably not a PFAS-regulated substance; in this case, although it is not a PFAS-regulated substance, it still exhibits the aforementioned effects. The aforementioned free radical curable polyorganosiloxane possesses free radical curing properties and therefore also belongs to the aforementioned curing compounds. Only one type of the aforementioned free radical curable polyorganosiloxane may be used, or two or more types may be used.

[0098] The above-mentioned free radical curing polyorganosiloxane has a free radical polymerizable functional group within its molecule. As an example of the above-mentioned free radical curing functional group, a photoradical polymerizable functional group can be cited.

[0099] Examples of the above-mentioned photoradical polymerizable functional groups include: (meth)acrylyl, (meth)acrylamide, vinyl, ethylene thioyl, etc. Among them, (meth)acrylyl is preferred.

[0100] As for the above-mentioned free radical curable polyorganosiloxanes, from the viewpoint of further exerting the effect as a leveling agent, linear polyorganosiloxanes are preferred.

[0101] The content ratio of the free radical curable polyorganosiloxane in the above-mentioned curable composition is not particularly limited, but is preferably 0.01 to 5% by mass, more preferably 0.03 to 3% by mass, and even more preferably 0.04 to 1% by mass, relative to the total amount of curable compound (100% by mass). When the above content ratio is within the above range, the surface of the film without hard coating has better resistance to sebum adhesion.

[0102] The content of the above-mentioned free radical curable polyorganosiloxane is not particularly limited, but it is preferably 0.01 to 5 parts by weight, more preferably 0.03 to 3 parts by weight, and even more preferably 0.04 to 1 part by weight, relative to 100 parts by weight of the above-mentioned cationic polymerizable silsesquioxane. When the above content is within the above range, the surface of the film without hard coating has better resistance to sebum adhesion.

[0103] Regarding the content ratio of the curing compound in the above-mentioned curing composition, it is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 97% by mass or more, relative to 100% by mass of the total amount of non-volatile components (excluding solvents) in the above-mentioned curing composition. When the content ratio is 90% by mass or more, the mechanical strength of the uncoated film is more superior. Furthermore, in this specification, the ratio of each component to the total amount of non-volatile components in the curing composition is equivalent to the ratio of the component derived from that component in the above-mentioned uncoated film.

[0104] Preferably, the curing composition includes a curing catalyst. The curing catalyst is a compound capable of initiating or promoting the polymerization reaction of the aforementioned cationic polymerizable silsesquioxane or the aforementioned active energy line curing compound, the aforementioned cationic polymerizable aliphatic compound, or other curing compounds. Only one type of curing catalyst may be used, or two or more types may be used.

[0105] The curing catalyst described above can be selected based on the type of curing functional groups possessed by the curing compound, wherein a cationic polymerization initiator and / or a free radical polymerization initiator is preferred. The cationic polymerization initiator is a compound that generates cationic species by irradiation with heat or active energy lines, thereby initiating the curing reaction of the curing compound.

[0106] As the above-mentioned cationic polymerization initiators, examples include photocationic polymerization initiators (photoacid generators) and thermal cationic polymerization initiators (thermal acid generators).

[0107] As the above-mentioned photocationic polymerization initiator, well-known or conventional photocationic polymerization initiators can be used, such as: strontium salt (salt of strontium ion and anion), ferrous salt (salt of ferrous ion and anion), selenium salt (salt of selenium ion and anion), ammonium salt (salt of ammonium ion and anion), phosphonium salt (salt of phosphonium ion and anion), salt of transition metal complex ion and anion, etc.

[0108] Examples of the above-mentioned strontium salts include: triphenylstrontium salt, tri-p-tolylstrontium salt, tri-o-tolylstrontium salt, tris(4-methoxyphenyl)strontium salt, 1-naphthyldiphenylstrontium salt, 2-naphthyldiphenylstrontium salt, tris(4-fluorophenyl)strontium salt, tri-1-naphthylstrontium salt, tri-2-naphthylstrontium salt, tris(4-hydroxyphenyl)strontium salt, diphenyl[4-(phenylthio)phenyl]strontium salt, and 4-(p-tolylthio)phenyl Triaryl strontium salts such as di-(p-phenyl)strontium salt; diaryl strontium salts such as diphenylbenzylmethyl strontium salt, diphenyl-4-nitrobenzylmethyl strontium salt, diphenylbenzyl strontium salt, and diphenylmethyl strontium salt; monoaryl strontium salts such as phenylmethylbenzyl strontium salt, 4-hydroxyphenylmethylbenzyl strontium salt, and 4-methoxyphenylmethylbenzyl strontium salt; and trialkyl strontium salts such as dimethylbenzylmethyl strontium salt, benzomethyltetrahydrothiophenonium salt, and dimethylbenzyl strontium salt.

[0109] Examples of the above-mentioned diphenyl[4-(phenylthio)phenyl]sulphine salt include diphenyl[4-(phenylthio)phenyl]sulphine tetra(pentafluorophenyl)borate and diphenyl[4-(phenylthio)phenyl]sulphine hexafluorophosphate. Alternatively, commercially available products such as "CPI-100P" (manufactured by SAN-APRO Co., Ltd., 50% propylene carbonate solution of diphenyl[4-(phenylthio)phenyl]sulphine hexafluorophosphate) may also be used.

[0110] Examples of the above-mentioned monoxide salts include: trade name "RHODORSIL PHOTOINITIATOR 2074" (manufactured by RHODIA JAPAN Co., Ltd., tetra(pentafluorophenyl)borate-[(1-methylethyl)phenyl](methylphenyl)monoxide), trade name "WPI-124" (manufactured by Wako Pure Chemical Industries Co., Ltd.), diphenyl monoxide, di-p-tolyl monoxide, bis(4-dodecylphenyl) monoxide, bis(4-methoxyphenyl) monoxide, etc.

[0111] Examples of the above-mentioned selenium salts include: triphenylselenate, tri-p-tolylselenate, tri-o-tolylselenate, tris(4-methoxyphenyl)selenate, 1-naphthyldiphenylselenate, and other triaryl selenium salts; diphenylbenzylselenate, diphenylbenzylselenate, diphenylmethylselenate, and other diaryl selenium salts; monoaryl selenium salts such as phenylmethylbenzylselenate; and trialkylselenates such as dimethylbenzylselenate.

[0112] Examples of the above-mentioned ammonium salts include: tetramethylammonium salt, ethyltrimethylammonium salt, diethyldimethylammonium salt, triethylmethylammonium salt, tetraethylammonium salt, trimethyl-n-propylammonium salt, trimethyl-n-butylammonium salt, and other tetraalkylammonium salts; pyrrolidone onium salts such as N,N-dimethylpyrrolidone onium salt and N-ethyl-N-methylpyrrolidone onium salt; imidazoline onium salts such as N,N'-dimethylimidazoline onium salt and N,N'-diethylimidazoline onium salt; N,N'-dimethyltetrahydropyrimidine onium salt, N,N'-diethyl... Tetrahydropyrimidine onion salts, such as methyltetrahydropyrimidine onion salts; N,N-dimethylpyridine onion salts, N,N-diethylpyridine onion salts, and other pyridine onion salts; N,N-dimethylpiperidine onion salts, N,N-diethylpiperidine onion salts, and other piperidine onion salts; N-methylpyridinium onion salts, N-ethylpyridinium onion salts, and other pyridinium onion salts; N,N'-dimethylimidazolium onion salts, and other imidazolium onion salts; N-methylquinoline onion salts, and other quinoline onion salts; N-methylisoquinoline onion salts, and other isoquinoline onion salts; benzylbenzothiazolium onion salts, and other thiazolium onion salts; benzyl acridine onion salts, and other acridine onion salts, etc.

[0113] Examples of the above-mentioned phosphonium salts include: tetraphenylphosphonium salt, tetra-p-tolylphosphonium salt, tetra(2-methoxyphenyl)phosphonium salt, and other tetraarylphosphonium salts; triphenylbenzylphosphonium salt, and other triarylphosphonium salts; triethylbenzylphosphonium salt, tributylbenzylphosphonium salt, tetraethylphosphonium salt, tetrabutylphosphonium salt, triethylbenzomethylphosphonium salt, and other tetraalkylphosphonium salts.

[0114] Examples of salts of the aforementioned transition metal complex ions include: salts of chromium complex cations such as (η5-cyclopentadienyl)(η6-toluene)Cr+ and (η5-cyclopentadienyl)(η6-xylene)Cr+; and salts of iron complex cations such as (η5-cyclopentadienyl)(η6-toluene)Fe+ and (η5-cyclopentadienyl)(η6-xylene)Fe+.

[0115] Examples of anions constituting the above salts include: PF6-, BF4-, (C6F5)4B-, (C6F5)4Ga-, sulfonate anions (trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion, methanesulfonate anion, benzenesulfonate anion, p-toluenesulfonate anion, etc.), perhalate anion, halosulfonate anion, sulfate anion, carbonate anion, aluminate anion, carboxylate anion, arylborate anion, thiocyanate anion, nitrate anion, etc.

[0116] Examples of the above-mentioned thermal cationic polymerization initiators include: aryl strontium salts, aryl styrene salts, aromatic hydrocarbon-ion complexes, quaternary ammonium salts, aluminum chelates, and boron trifluoride amine complexes. Furthermore, examples of anions constituting the above-mentioned salts include those identical to the anions in the photocationic polymerization initiators.

[0117] Examples of the above-mentioned aryl strontium salts include pentafluorophenyl borate and hexafluorophosphate. In the curing composition of the present invention, for example, commercially available products such as "SP-66" and "SP-77" (manufactured by ADEKA Co., Ltd.); and "SAN-AID SI-150L", "SAN-AID SI-110", "SAN-AID SI-360", "SAN-AID SI-300", "SAN-AID SI-B4", "SAN-AID SI-B5", "SAN-AID SI-B3", "SAN-AID SI-B3A", "SAN-AID SI-B7", and "SAN-AID SI-B2A" (manufactured by San-Shin Chemical Industry Co., Ltd.) can be used. Examples of the aforementioned aluminum chelates include ethyl aluminum acetate diisopropyl ester and tris(ethyl) aluminum acetate. Examples of the aforementioned boron trifluoride amine complexes include boron trifluoride monoethylamine complexes, boron trifluoride imidazole complexes, and boron trifluoride piperidine complexes.

[0118] The above-mentioned free radical polymerization initiator is a compound that generates free radicals by irradiation with heat or active energy lines, thereby initiating a hardening reaction in the hardening compound.

[0119] Examples of free radical polymerization initiators include photoradical polymerization initiators and thermal free radical polymerization initiators. Examples of photoradical polymerization initiators include: alkyl phenyl ketone-based photoradical polymerization initiators, acetylsphin oxide-based photoradical polymerization initiators, oxime ester-based photoradical polymerization initiators, and α-hydroxyketone-based photoradical polymerization initiators.

[0120] Examples of alkyl benzophenone-based photoradical polymerization initiators include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-benzyl-2-dimethylamino-1-(4-hydroxylinylphenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-[4-(4-hydroxylinyl)phenyl]-1-butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-hydroxylinylpropane-1-one, benzophenone, methyl benzophenone, o-benzoylbenzoic acid, benzoyl ethyl ether, and 2,2-diethylbenzoic acid. Oligomers of oxyacetophenone, 2,4-diethyl-9-oxosulfuron, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl-(2,4,6-trimethylbenzoyl)phenyl hypophosphite, 4,4'-bis(diethylamino)benzophenone, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, and 2-hydroxy-1-(4-isopropenylphenyl)-2-methylpropane-1-one, etc.

[0121] Examples of 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide are examples of photoradical polymerization initiators of the above-mentioned phosphine oxide.

[0122] Examples of oxime ester photoradical polymerization initiators include 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime), 1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazole-3-yl]acetone O-acetylgoxime, etc.

[0123] Examples of the above-mentioned α-hydroxy ketone photoradical polymerization initiators include: benzoin, benzoin methyl ether, benzoin butyl ether, 1-hydroxycyclohexylphenyl ketone, 1-phenyl-2-hydroxy-2-methylpropane-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, etc.

[0124] The content (admixture amount) of the curing catalyst in the above-mentioned curing composition is not particularly limited. It is preferably 0.01 to 10 parts by mass relative to 100 parts by mass of the total amount of the curing compound, more preferably 0.05 to 5 parts by mass, further preferably 0.1 to 3 parts by mass, further preferably 0.3 to 2.7 parts by mass, and even more preferably 0.5 to 2.5 parts by mass. When the content of the curing catalyst is 0.01 parts by mass or more, the curing reaction tends to proceed efficiently and sufficiently, and the surface hardness of the cured product is further improved. On the other hand, when the content of the curing catalyst is 10 parts by mass or less, the retention of the curing composition tends to be improved, or the coloring of the cured product tends to be suppressed.

[0125] The content (admixture amount) of the cationic polymerization initiator in the above-mentioned curing composition is not particularly limited, but is preferably 0.01 to 10 parts by mass relative to 100 parts by mass of the total amount of the curing compound, more preferably 0.05 to 5 parts by mass, and even more preferably 0.1 to 3 parts by mass, and particularly preferably 0.3 to 2 parts by mass. When the above content is 0.01 parts by mass or more, the curing reaction tends to proceed efficiently and sufficiently, and the surface hardness of the cured product is further improved. When the above content is 10 parts by mass or less, the retention of the curing composition tends to be improved, or the coloring of the cured product tends to be suppressed.

[0126] The content (admixture amount) of the free radical polymerization initiator in the above-mentioned curing composition is not particularly limited. Relative to 100 parts by mass of the total curing compound, it is preferably 0.005 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, further preferably 0.05 to 2 parts by mass, and even more preferably 0.1 to 1 part by mass. When the content is 0.005 parts by mass or more, the curing reaction tends to proceed efficiently and sufficiently, and the surface hardness of the cured product is further improved. When the content is 5 parts by mass or less, the retention of the curing composition tends to be improved, or the coloring of the cured product tends to be suppressed.

[0127] In addition to the various components mentioned above, the above-mentioned hardening composition may further contain other components. Other components may include: inorganic fillers such as precipitated silica, wet silica, fuming silica, calcined silica, titanium dioxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate, carbon black, silicon carbide, silicon nitride, and boron nitride; and inorganic fillers prepared by treating such fillers with organohalosilanes, organoalkoxysilanes, organosilazanes, or other organosilane compounds; fine powders of organic resins such as polyoxyethylene resins, epoxy resins, and fluororesins; fillers, curing agents (amine-based curing agents, polyamide-based curing agents, anhydride-based curing agents, phenol-based curing agents, etc.) of conductive metal powders such as silver and copper; curing aids; and curing accelerators (imidazolium compounds, alkali metal or alkaline earth metal alkoxides, phosphine compounds, amide compounds, Lewis acid complexes, sulfur compounds, boron compounds, etc.). The following are commonly used additives: condensed organometallic compounds, solvents (water, organic solvents, etc.), stabilizers (antioxidants, UV absorbers, light stabilizers, heat stabilizers, heavy metal deactivators, etc.), flame retardants (phosphorus-based flame retardants, halogen-based flame retardants, inorganic flame retardants, etc.), flame retardant additives, reinforcing materials (other fillers, etc.), nucleating agents, coupling agents (silane coupling agents, etc.), lubricants, waxes, plasticizers, mold release agents, impact modifiers, color modifiers, transparent agents, rheology modifiers (flow modifiers, etc.), processability modifiers, colorants (dyes, pigments, etc.), antistatic agents, dispersants, surface modifiers (antifoaming agents, etc.), surface modifiers (slip agents, etc.), matting agents, defoamers, foam inhibitors, defoaming agents, antibacterial agents, preservatives, viscosity modifiers, tackifiers, photosensitizers, foaming agents, surfactants, etc. Only one of the above-mentioned components may be used, or two or more may be used. The content (admixture amount) of the other components mentioned above is not particularly limited, but is preferably less than 100 parts by mass relative to the total amount of the curing compound, more preferably less than 30 parts by mass (e.g., 0.01 to 30 parts by mass), and even more preferably less than 10 parts by mass (e.g., 0.1 to 10 parts by mass).

[0128] As the above-mentioned organic solvents, well-known or commonly used organic solvents can be cited, such as: ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ethers (dimethyl ether, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (benzene, etc.), halogenated hydrocarbons (dichloromethane, dichloroethane, etc.), esters, alcohols (ethanol, cyclohexanol, etc.), cellosols (methyl cellosol, ethyl cellosol, etc.), acetic acid cellosols, acetamides (dimethylformamide, dimethylacetamide, etc.), etc.

[0129] The above-mentioned hardening components are not particularly limited and can be prepared by heating and stirring the various components at room temperature or as needed.

[0130] (Curing material, film without hard coating) The above-mentioned hardening component can be hardened to obtain the above-mentioned hardened material (film without hard coating). The pencil hardness of the surface of the above-mentioned film without hard coating is not particularly limited, but it is preferably H or higher (e.g., H to 9H), more preferably 2H or higher, further preferably 3H or higher, further preferably 4H or higher, further preferably 5H or higher, further preferably 6H or higher, further preferably 7H or higher, further preferably 8H or higher, and especially preferably 9H. Furthermore, the pencil hardness can be evaluated according to the method described in JIS K5600-5-4.

[0131] For purposes such as improving adhesion to other layers, roughening treatment, easy adhesion treatment, antistatic treatment, sandblasting treatment (grinding treatment), discharge treatment (e.g., corona discharge treatment or glow discharge treatment), plasma treatment, chemical etching treatment, water mat treatment, flame treatment, acid treatment, alkali treatment, oxidation treatment, ultraviolet irradiation treatment, silane coupling agent treatment, and other well-known or conventional surface treatments may be applied to part or all of the above-mentioned uncoated film surface.

[0132] The above-mentioned uncoated film is obtained by: applying the above-mentioned curing composition to the demolding surface of a temporary substrate such as a separator, removing the solvent by drying as needed, allowing the curing compound in the above-mentioned curing composition to undergo a polymerization reaction to harden the above-mentioned curing composition to obtain a hardened product, and peeling the above-mentioned hardened product off the above-mentioned temporary substrate.

[0133] As a coating method for the aforementioned hardening composition, well-known or conventional coating methods can be used. Examples of coating apparatus include: roller coaters, air knife coaters, doctor blade coaters, bar coaters, reverse coaters, rod coaters, comma coaters, dip / extrusion coaters, die coaters, gravure coaters, microgravure coaters, screen coaters, and spray coaters. Furthermore, as a coating method, in addition to using a coating apparatus, examples include dip coating and spin coating. Among these, coating using a spray coater (spray coating) is particularly suitable.

[0134] The hardening method may be appropriately selected from well-known methods and is not particularly limited. It may be appropriately selected according to the type of hardening functional group possessed by the hardening compound. For example, methods such as irradiation with an active energy line or heating may be used. As the aforementioned active energy line, for example, any one of infrared rays, visible light, ultraviolet rays, X-rays, electron beams, alpha rays, beta rays, and gamma rays may be used. Among these, ultraviolet rays are preferred in terms of superior processability. Irradiation with the aforementioned active energy line (especially an electron beam) is preferably carried out in an inactive gas environment such as a nitrogen environment, an argon environment, or a helium environment.

[0135] When removing the solvent after applying the above-mentioned curable composition, heating may be performed. The temperature for removing the solvent is not particularly limited, but preferably 40–200°C, more preferably 50–170°C, and even more preferably 60–150°C, and most preferably 80–140°C. Furthermore, the time for maintaining the above temperature is not particularly limited, but preferably approximately 30 seconds to 5 hours.

[0136] The conditions for curing the aforementioned curable composition by irradiation with active energy lines (irradiation conditions of active energy lines, etc.) can be appropriately adjusted according to the type or energy of the irradiated active energy lines, the shape or size of the uncoated film, etc., and are not particularly limited. In the case of irradiation with ultraviolet light, it is preferably set to about 1 to 10,000 mJ / cm2 (preferably 50 to 5,000 mJ / cm2, more preferably 70 to 3,000 mJ / cm2, and even more preferably 100 to 1,000 mJ / cm2). Furthermore, the irradiation with active energy lines can be performed using, for example, deep UV lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, low-pressure mercury lamps, xenon lamps, carbon arc lamps, metal halide lamps, sunlight, LED lamps, halogen lamps, lasers (e.g., helium-cadmium lasers, excimer lasers, etc.). After irradiation with active energy lines, heat treatment (annealing, aging) can be performed to further carry out the curing reaction.

[0137] The irradiation dose used for hardening with an electron beam is not particularly limited, but is preferably 1 to 200 kGy, more preferably 5 to 150 kGy, even more preferably 10 to 100 kGy, and particularly preferably 20 to 80 kGy. The accelerating voltage is not particularly limited, but is preferably 10 to 1000 kV, more preferably 50 to 500 kV, and even more preferably 100 to 300 kV.

[0138] In the above-mentioned aging process, the heating temperature is not particularly limited, but is preferably 30 to 200°C, more preferably 50 to 190°C, and even more preferably 60 to 180°C. The heating time is not particularly limited, but is preferably 10 minutes to 10 hours, more preferably 30 minutes to 5 hours, and even more preferably 45 minutes to 3 hours.

[0139] [Laminated body] A laminated body is obtained by laminating other layers onto the aforementioned uncoated film. Examples of these other layers include functional layers that impart various functions. The laminated body comprises the aforementioned uncoated film and functional layers laminated onto the uncoated film. These other layers may be a single layer or two or more layers.

[0140] Examples of the aforementioned functional layers include: surface protective films protecting the surface of films without hard coatings, hard coatings, anti-reflective layers, anti-glare layers, fingerprint-resistant layers, anti-fouling layers, scratch-resistant layers, scratch-resistant fingerprint layers, antibacterial layers, bonding layers, polarizing layers, and optical substrates. Furthermore, the aforementioned functional layers are preferably formed of thermosetting resin compositions or active energy line curing resin compositions, and more preferably formed of active energy line curing resin compositions. They can then be bonded to substrates such as glass.

[0141] When the above-mentioned surface protective film is present, there is a tendency for the stamping processability or handling properties of the film without hard coating to be improved. When such a surface protective film is present, for example, even if the hardness of the film without hard coating is very high, and it is easy to peel off from the support or crack during stamping, it is possible to use a Thomson cutter for stamping without such problems.

[0142] As the aforementioned surface protective film, any known or conventional surface protective film may be used, without particular limitation. For example, it may be used on the surface of a plastic film having an adhesive layer. Examples of the aforementioned plastic film include plastic films formed from plastic materials such as polyester (polyethylene terephthalate, polyethylene naphthalate, etc.), polyolefin (polyethylene, polypropylene, cyclic polyolefin, etc.), polystyrene, acrylic resin, polycarbonate, epoxy resin, fluororesin, polysiloxane resin, diacetate resin, triacetate resin, polyarylate, polyvinyl chloride, polyurethane, polyether ether etherimide, polyimide, and polyamide. Examples of adhesive layers include those formed from one or more well-known or conventional adhesives such as acrylic adhesives, natural rubber adhesives, synthetic rubber adhesives, ethylene-vinyl acetate copolymer adhesives, ethylene-(meth)acrylate copolymer adhesives, styrene-isoprene block copolymer adhesives, and styrene-butadiene block copolymer adhesives. These adhesive layers may contain various additives (e.g., antistatic agents, slip agents, etc.). Furthermore, the plastic film and adhesive layer may each have a single-layer or multi-layer (multi-layer) structure. Also, the thickness of the surface protective film is not particularly limited and can be appropriately selected.

[0143] As a surface protective film, commercially available products such as the "SUNYTECT" series (manufactured by Sun A.Kaken Co., Ltd.), the "E-MASK" series (manufactured by Nitto Denko Co., Ltd.), the "MASTACK" series (manufactured by Fujimori Kogyo Co., Ltd.), the "HITALEX" series (manufactured by Hitachi Chemical Co., Ltd.), and the "ALPHAN" series (manufactured by Oji F-Tex Co., Ltd.) are available from the market.

[0144] Specifically, examples of the above-mentioned laminate include [uncoated film / bonding layer / surface protective film], [uncoated film / bonding layer / anti-reflective layer], [uncoated film / anti-glare layer / surface protective film], [uncoated film / substrate / bonding layer], [glass / uncoated film / surface protective film], [glass / uncoated film / bonding layer], [uncoated film / fingerprint resistant layer / scratch-resistant layer] The laminate consists of layers such as [layer], [uncoated film / antifouling layer / surface protective film], [uncoated film / anti-glare layer / anti-reflective layer], [uncoated film / anti-reflective layer / fingerprint resistant layer], [uncoated film / bonding layer / glass], [uncoated film / bonding layer / polarizing layer], [glass / uncoated film / polarizing layer], [glass / uncoated film / bonding layer / polarizing layer], and [glass / uncoated film / anti-reflective layer]. Furthermore, a multilayer laminate is obtained by laminating multiple of the above-mentioned laminates.

[0145] Regarding the aforementioned multilayer laminates, various products or components thereof can be used as constituent materials for the parts. Examples of such products include various household appliances, various electrical / electronic products, and various optical machines, such as: display devices such as liquid crystal displays and organic EL displays; input devices such as touch panels; solar cells; portable electronic terminals such as game consoles, computers, tablets, smartphones, and mobile phones; display devices such as displays in automobiles; lenses for eyeglasses; and transparent components used outdoors or in harsh environments such as high temperature and high humidity, such as headlights, cameras, and surveillance cameras. The aforementioned uncoated film is preferably a layer that protects the surface of the aforementioned products.

[0146] The various configurations disclosed in this specification can be combined with any other feature disclosed in this specification. The various components and combinations thereof in each embodiment are examples, and appropriate additions, omissions, substitutions, and other modifications can be made to the configuration without departing from the spirit of the invention. Furthermore, the inventions disclosed herein are not limited to the embodiments or the following examples, but only to the scope of the claims. [Examples]

[0147] Hereinafter, one embodiment of the present invention will be described in more detail based on examples. Furthermore, the molecular weight of the product was determined using the following method: Alliance HPLC System 2695 (manufactured by Waters), Refractive Index Detector 2414 (manufactured by Waters), column: Tskgel GMHHR-M×2 (manufactured by Tosoh Corporation), guard column: Tskgel guard column HHRL (manufactured by Tosoh Corporation), column oven: COLUMN HEATER U-620 (manufactured by Sugai), solvent: THF, measurement conditions: 40°C, molecular weight: converted from standard polystyrene. Also, the ratio of T2 to T3 in the product [T3 / T2] was determined using 29Si-NMR spectroscopy with a JEOL ECA500 (500 MHz). The Td5 (5% weight loss temperature) of the product was determined by TGA (thermogravimetric analysis) in air at a heating rate of 5°C / min.

[0148] Example 1 (Preparation of Epoxy-Containing Silsesquioxanes) 161.5 mmol (39.79 g) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 9 mmol (1.69 g) of phenyltrimethoxysilane, and 165.9 g of acetone were added to a 300 mL flask (reaction vessel) equipped with a thermometer, stirrer, reflux condenser, and nitrogen inlet tube under a nitrogen atmosphere, and the temperature was raised to 50°C. 4.70 g (1.7 mmol based on potassium carbonate) of a 5% potassium carbonate aqueous solution was added dropwise to the mixture obtained in this manner over 5 minutes, followed by the addition of 1700 mmol (30.60 g) of water over 20 minutes. Furthermore, no significant temperature rise occurred during the addition. Subsequently, the polycondensation reaction was carried out for 4 hours under a nitrogen atmosphere at 50°C. Analysis of the product in the reaction solution after the polycondensation reaction revealed a number average molecular weight of 1911 and a molecular weight dispersion of 1.47. The ratio of T2 to T3 phases [T3 / T2] calculated from the 29Si-NMR spectrum of the product was 10.3. The reaction solution was then cooled and washed with water until the lower layer became neutral. The upper layer was separated, and the solvent was removed by distillation at 1 mmHg and 40°C, yielding a colorless, transparent, liquid product (a silsesquioxane containing epoxy groups, with a solid content of 77% by mass). The Td5 of this product was 370°C.

[0149] (Preparation of curing compound 1) As curing compound 1, the following were mixed: 66.8 parts by weight of the epoxy-containing silsesquioxane obtained above (77% by weight of active ingredient), 1.5 parts by weight of "EPOXYESTER 200PA-E5" (a compound having an acrylonitrile, epoxy group and polyglycerol backbone, manufactured by Kyoei Chemical Co., Ltd.), 6.2 parts by weight of 1,6-hexanediol diglycidyl ether (trade name "EPOLIGHT 1600" (manufactured by Kyoei Chemical Co., Ltd.), and a polyorganosiloxane containing a free radical curing functional group (trade name "MEGAFAC RS-57" (20% by weight of active ingredient), which is not a PFAS (per- and polyfluoroalkyl substances). The controlled substance (manufactured by DIC Corporation, active ingredient 20% by mass) is mixed with 0.2 parts by mass as a curing catalyst, along with 0.5 parts by mass of a photocationic polymerization initiator (a salt of triarylstrom and tetrafluorophenyl gallium) and 0.2 parts by mass of a photoradical polymerization initiator (trade name "Omnirad 127", manufactured by IGM Resins), along with 0.4 parts by mass of an antioxidant (trade name "AO-20", manufactured by ADEKA Corporation), and 8.4 parts by mass of methyl isobutyl ketone (MIBK) and 15.8 parts by mass of methyl ethyl ketone (MEK) as a solvent to prepare the curing composition. Furthermore, the content ratios shown in Table 1 are the blending ratios of each component. For silsesquioxane and RS-57, the values ​​are for the solution; for the other components, the values ​​are for the active ingredient.

[0150] (Preparation of a film without hard coating) Using a handheld spray gun (manufactured by ANEST IWATA Co., Ltd.), the above-mentioned curing component 1 was sprayed onto the release surface of the separator placed on a Teflon (registered trademark) frame. Then, it was dried (80°C, 2 hours) and irradiated with UV (300 mJ / cm²). Afterwards, the Teflon (registered trademark) frame was removed, and it was aged at 120°C for 1 hour to harden it, obtaining a hardened material (film without hard coating) with a thickness of approximately 0.150 mm.

[0151] Example 2 (Preparation of Curable Composition 2) Curable composition 2 was prepared in the same manner as curable composition 1, except that the content ratio of each component was changed as shown in Table 1. "EPOLIGHT 400E" shown in Table 1 is the trade name "EPOLIGHT 400E" (manufactured by Kyoei Chemical Co., Ltd., polyethylene glycol #400 diglycidyl ether).

[0152] (Preparation of film without hard coating) Except for using the above-mentioned curing component 2, the cured material of Example 2 (thickness of about 0.150 mm) (film without hard coating) was prepared in the same manner as in Example 1.

[0153] Example 3 (Preparation of curing composition 3) Curing composition 3 was prepared in the same manner as curing composition 1, except that the content ratio of each component was changed as shown in Table 1.

[0154] (Preparation of film without hard coating) Except for using the above-mentioned curing component 3, the hardened material of Example 3 (thickness of about 0.150 mm) (film without hard coating) was prepared in the same manner as in Example 1.

[0155] The hardened products (films without hard coating) obtained in Examples 1 to 3 were evaluated as follows. The results are shown in Table 1.

[0156] (1) Surface hardness (pencil hardness) The pencil hardness of the uncoated film surface obtained above was evaluated according to JIS K5600-5-4.

[0157] (2) Tensile test: The uncoated film obtained above was stamped into the shape of a No. 7 dumbbell (JIS K6251) to make test pieces. Using a Tensilon universal testing machine (trade name "RTF-1350", manufactured by A&D Corporation), the test was conducted according to JIS K7161 (1994) with a tensile speed of 2 mm / min, a clamping distance of 20 mm, and a mark distance of 12 mm. For n=8, the tensile test was conducted, and the average value of the obtained Young's modulus after removing the upper and lower limits was used as the evaluation result Young's modulus.

[0158] (3)Indentation test For the uncoated film obtained above, a nano indenter (trade name 'ENT-2100', manufactured by ELIONIX Co., Ltd.) was used as a triangular cone indenter, and 10 indentations were measured with a maximum load of 500 μN. The average values ​​of indentation hardness and Young's modulus were measured.

[0159] (4) Glass transition temperature and melting point: For the hardened materials obtained above, DSC measurements were performed using a differential scanning calorimeter (trade name "DSC-6220", manufactured by Hitachi High-Tech Science Co., Ltd.) in a temperature range from room temperature to 300°C. As a result, for any of Examples 1 to 3, no shift of the baseline originating from the glass transition temperature or a peak originating from the melting point was observed in the range below 300°C.

[0160] ◎[Table 1] Table 1 Example 1 Example 2 Example 3 Hardening components (1) (2) (3) hardening compounds Silsesquioxane 66.8 65.6 65.6 200PA-E5 1.5 1.5 1.5 EPOLIGHT 1600 6.2 1.5 1.2 EPOLIGHT 400E - 5.9 6.2 RS-57 0.2 0.2 0.2 hardened catalyst Salts of triarylstrom and tetrapentafluorophenyl gallium 0.5 0.5 0.5 Omnirad 127 0.2 0.2 0.2 antioxidants AO-20 0.4 0.4 0.4 solvent MIBK 8.4 8.4 8.4 MEK 15.8 15.8 15.8 Evaluation results Pencil hardness 7H 4H 3H Young's modulus (tensile test) [MPa] 1878 1820 1028 Indentation hardness (indentation test) [MPa] 740 236 151 Young's modulus (indentation test) [MPa] 4572 3409 2592 Elastic-plastic ratio (indentation test) [%] 85 77 72

[0161] As shown in the evaluation results in Table 1, the uncoated film of Example 1, even without the use of PFAS-controlled substances, exhibited an appropriate Young's modulus in the tensile test, a sufficiently high elastic-plastic ratio in the indentation test, and excellent mechanical strength. Furthermore, the uncoated film of Example 1 was not made of glass but of resin, making it lighter than glass. Also, the glass transition temperature and melting point were not confirmed below 300°C, indicating excellent heat resistance.

[0162] Hereinafter, variations of the invention disclosed herein will be described. [Note 1] A film without a hard coating satisfies the following: an elastic-plastic ratio of 70% or more in an indentation test, a glass transition temperature and melting point of not less than 200°C, and at least one of the following: a Young's modulus of 1000 MPa or more in an indentation test, and a Young's modulus of 1000 to 5000 MPa in a tensile test. [Note 2] The film without a hard coating as described in Note 1 has a thickness of 1 to 1000 μm and an indentation hardness of 100 MPa or more obtained from an indentation test. [Note 3] The film without a hard coating as described in Note 1 or 2 is formed from a hardened product of a hardening composition, and the glass transition temperature of the hardened product is 300°C or more. [Note 4] The uncoated film described in any of Notes 1 to 3 is formed from a hardened form of a hardening composition, wherein the hardened form has a pencil hardness of 2H or higher. [Note 5] The uncoated film described in Notes 3 or 4, wherein the hardening composition comprises a free radical hardening polyorganosiloxane. [Note 6] The uncoated film described in any of Notes 3 to 5, wherein the hardening composition comprises a cationic polymerizable silsesquioxane. [Note 7] The uncoated film described in any of Notes 3 to 6, wherein the hardening composition further comprises a hardening compound having a polymerizable functional group with an active energy line. [Note 8] A laminate comprising an uncoated film described in any of Notes 1 to 7, and a functional layer laminated on the uncoated film. [Note 9] A multilayer laminate, which is formed by stacking a plurality of the multilayer laminates described in Note 8. [Note 10] A display device having the multilayer laminate described in Note 9.

Claims

1. A film without a hard coating, satisfying at least one of the following: an elastic-plastic ratio of 70% or more in an indentation test, a glass transition temperature and melting point not below 200°C, a Young's modulus of 1000 MPa or more in an indentation test, and a Young's modulus of 1000 to 5000 MPa in a tensile test; wherein the film without a hard coating is formed from a cured product of a curing composition, the curing composition containing a cationic polymeric silsesquioxane and a cationic curing aliphatic compound as curing compounds, wherein the content of the cationic polymeric silsesquioxane in the curing composition is more than 50% by mass relative to 100% of the total amount of the curing compound, and the content of the cationic curing aliphatic compound in the curing composition is 1 to 20% by mass relative to 100% of the total amount of the curing compound.

2. The uncoated film of Request 1 has a thickness of 1 to 1000 μm and an indentation hardness of 100 MPa or more as obtained by indentation test.

3. The uncoated film as requested in item 1 or 2, wherein, The glass transition temperature of the above-mentioned hardened material is above 300°C.

4. The uncoated film as requested in item 1 or 2, wherein, The pencil hardness of the above-mentioned hardened material is 2H or higher.

5. As in request item 1, the uncoated film, wherein, The aforementioned curing components include free radical curing polyorganosiloxanes.

6. As in claim 1, the uncoated film, wherein, The aforementioned curing components further include curing compounds having polymerizable functional groups with active energy lines.

7. A laminate comprising a film without hard coating as claimed in claim 1 or 2, and a functional layer laminated on the film without hard coating.

8. A multilayer stack, which is formed by stacking a plurality of stacks of claim 7.

9. A display device having the multilayer stack of claim 8.