Hardcoat-less film, laminate, multilayer laminate, and display device

Abstract

To provide a hardcoat-less film that is relatively lightweight, has excellent mechanical strength, and has excellent heat resistance even without regulated PFAS substance.SOLUTION: A hardcoat-less film fulfills a condition that an elastic-to-plastic ratio is 70% or more in an indentation test and a glass transition temperature and a melting point each are neither lower than nor equal to 200°C, and fulfills at least one of a condition that a Young's modulus is 1000 MPa or more in an indentation test or a condition that a Young's modulus is from 1000 to 5000 MPa in a tensile test.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a hard coat-less film, a laminate, a multilayer laminate, and a display device. Specifically, the present disclosure relates to a hard coat-less film, and a laminate, a multilayer laminate, and a display device including the hard coat-less film. [Background technology]

[0002] Liquid crystal monitors such as liquid crystal displays, organic EL displays, and plasma displays have protective films or hard coating layers attached to them, which have the effect of preventing scratches on the screen, making it less likely for fingerprints to appear on the screen, and making it easier to wipe off any dirt that has adhered to the screen.

[0003] In recent years, with the development of mobile devices such as smartphones and tablet PCs, there has been a demand for thinner and slimmer optical substrates, such as substrates for displays, which has led to the need for thinner and slimmer substrates for coating hard coat layers.

[0004] Glass, polyimide, and polyethylene terephthalate (PET) are commonly used as the substrates. However, glass is heavy, which increases the weight of mobile devices and makes them susceptible to breakage upon impact. Furthermore, polyimide often contains alkyl fluorine within its structure, which falls under recent regulations on fluorinated organic compounds (PFAS), and its use may be restricted in some regions. PET also has the problem of poor heat resistance.

[0005] Furthermore, from the viewpoint of thinning, single-layer films have been proposed that have excellent surface scratch resistance and do not require a hard coat layer or a supporting substrate. For example, Patent Document 1 discloses a hard coating film containing a crosslinked polymer of a urethane acrylate oligomer, and Patent Document 2 discloses a substrate-less cover window for a flexible display device that contains a polysiloxane and an elastomer that have an epoxy group-containing functional group. [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 [Problem to be solved by the invention]

[0007] However, the film of Patent Document 1 has a crosslinking density of about 60%, and therefore has insufficient mechanical strength. Furthermore, the cover window of Patent Document 2 also has insufficient mechanical strength because it contains an elastomer. Even when a monolayer film is used, heat resistance may be required.

[0008] Therefore, an object of the present disclosure is to provide a hard-coat-less film that is relatively lightweight, has excellent mechanical strength, and is excellent in heat resistance, even if it does not contain PFAS-regulated substances.An object of the present disclosure is also to provide a laminate, a multilayer laminate, and a display device that include the hard-coat-less film. [Means for solving the problem]

[0009] As a result of intensive research to solve the above problems, the inventors of the present disclosure have found that a hard coat-less film having specific physical properties is relatively lightweight and has excellent mechanical strength, even when it does not contain PFAS-regulated substances. The present invention was completed based on these findings.

[0010] That is, the present disclosure provides a hardcoat-less film that satisfies at least one of the following: an elastic-plastic ratio in an indentation test of 70% or more, a glass transition temperature and a melting point not lower than 200°C, a Young's modulus in an indentation test of 1000 MPa or more, and a Young's modulus in a tensile test of 1000 to 5000 MPa.

[0011] The above-mentioned hard coat-less film preferably has a thickness of 1 to 1000 μm and an indentation hardness of 100 MPa or more in an indentation test.

[0012] The hard coat-less film is preferably formed from a cured product of a curable composition, and the cured product preferably has a glass transition temperature of 300° C. or higher.

[0013] The hard coat-less film is preferably formed from a cured product of a curable composition, and the cured product preferably has a pencil hardness of 2H or more.

[0014] The curable composition preferably contains a radical-curable polyorganosiloxane.

[0015] The curable composition preferably contains a cationically polymerizable silsesquioxane.

[0016] The curable composition preferably further contains a curable compound having an active energy ray-polymerizable functional group.

[0017] The present disclosure also provides a laminate comprising the above-mentioned hard coat-less film and a functional layer laminated on the above-mentioned hard coat-less film.

[0018] The present disclosure also provides a multilayer laminate in which a plurality of the above laminates are stacked.

[0019] The present disclosure also provides a display device including the multilayer laminate. [Effects of the Invention]

[0020] According to the present disclosure, it is possible to provide a hard coat-less film that is relatively lightweight, has excellent mechanical strength, and is excellent in heat resistance, even when it does not contain PFAS-regulated substances, as well as a laminate, a multilayer laminate, and a display device that include the above hard coat-less film. DETAILED DESCRIPTION OF THE INVENTION

[0021] [Hard coat-less film] The hard coat-less film of the present disclosure satisfies the following requirements: an elastic-plastic ratio in an indentation test of 70% or more, a glass transition temperature and a melting point not lower than 200°C, a Young's modulus in an indentation test of 1000 MPa or more, and a Young's modulus in a tensile test of 1000 to 5000 MPa. Of these, it is preferable to satisfy two of these requirements.

[0022] In this specification, the term "hard coat-less film" refers to a film (sheet) that does not have a hard coat layer formed on both sides of the film and has hard coat properties as a single film layer. The hard coat-less film does not require a separate hard coat layer and can be relatively lightweight.

[0023] The hard coat-less film has an elastic-plastic ratio in an indentation test of 70% or more, preferably 75% or more, and more preferably 80% or more. When the elastic-plastic ratio is 70% or more, the film is less likely to be damaged when stress is applied, and the mechanical strength of the film is excellent. Furthermore, the elastic-plastic ratio is preferably 95% or less, more preferably 95% or less, and even more preferably 90% or less. When the elastic-plastic ratio is 95% or less, the film has excellent flexibility and bending resistance.

[0024] The hard coat-less film preferably has a Young's modulus in an indentation test of 1000 MPa or more, more preferably 2000 MPa or more, and even more preferably 3000 MPa or more. When the Young's modulus in an indentation test is 1000 MPa or more, the film has a hardness that is resistant to scratches and has excellent mechanical strength. Furthermore, the Young's modulus in an 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 an indentation test is 10000 MPa or less, the film has excellent flexibility and excellent bending resistance.

[0025] The hard coat-less film preferably has an indentation hardness of 100 MPa or more, more preferably 300 MPa or more, and even more preferably 700 MPa or more, as measured by an indentation test. When the indentation hardness is 100 MPa or more, the surface hardness is high, making it less susceptible to dents and scratches, 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 film has excellent flexibility and bending resistance.

[0026] The indentation test can be performed by, for example, a nanoindentation method, etc. A Berkovich indenter can be used as the indenter.

[0027] The hard coat-less film preferably has a Young's modulus in a tensile test of 1000 to 5000 MPa, more preferably 1200 to 4000 MPa, and even more preferably 1500 to 3000 MPa. When the Young's modulus in a tensile test is 1000 MPa or more, the rigidity required for film formation is maintained, and the film has excellent mechanical strength. When the Young's modulus in a tensile test is 5000 MPa or less, the film can achieve both elongation and flex resistance while maintaining rigidity, and the film has excellent mechanical strength.

[0028] The tensile test can be carried out using a known or commonly used tensile tester. The Young's modulus is measured using a No. 7 dumbbell-shaped hard-coat-less film as a test piece under conditions of room temperature, initial chuck distance of 20 mm, gauge length of 12 mm, and tensile speed of 2 mm / min. The Young's modulus in the tensile test can be calculated as the average value obtained by excluding the maximum and minimum values ​​from the measured values ​​of n=5 or more.

[0029] The hard coat-less film has a glass transition temperature (Tg) and melting point (Tm) of not lower than 200°C, and preferably not lower than 300°C. If the glass transition temperature and melting point are not lower than 200°C, the hard coat-less film will have excellent heat resistance. The glass transition temperature and melting point are values ​​measured by DSC (differential scanning calorimetry).

[0030] The thickness of the hard coat-less 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 film has better mechanical strength and scratch resistance. When the thickness is 1000 μm or less, the film is lighter and has better flex resistance.

[0031] (Curable composition) The hard coat-less film is preferably formed from a cured product of a curable composition. That is, the curable composition preferably contains a curable compound. The curable compound may be used alone or in combination of two or more.

[0032] The curable compound is preferably a cationically polymerizable silsesquioxane. By including the cationically polymerizable silsesquioxane, the curable composition is less likely to shrink during curing, and a relatively thick hard coat-less film can be easily obtained, thereby making it possible to obtain a hard coat-less film with better scratch resistance. The cationically polymerizable silsesquioxane is preferably a photocationically polymerizable silsesquioxane.

[0033] The cationically polymerizable silsesquioxane has a cationically polymerizable functional group in the molecule. Examples of the cationically polymerizable functional group include a hydroxyl group, an epoxy group, an oxetane group, a vinyl ether group, and a vinylphenyl group. Among these, an epoxy group is preferred from the viewpoint of increasing the surface hardness of the hard coat-less film.

[0034] The group containing an epoxy group includes, but is not limited to, known or commonly used groups having an oxirane ring. From the viewpoint of the curability of the curable composition and the heat resistance of the hard coat-less film, preferred are groups represented by the following formula (1a), (1b), (1c), and (1d), more preferred are groups represented by the following formula (1a) and (1c), and even more preferred are groups represented by the following formula (1a). [ka] [ka] [ka] [ka]

[0035] In the above formula (1a), R 1a represents a linear or branched alkylene group. Examples of the linear or branched alkylene group include linear or branched alkylene groups having 1 to 10 carbon atoms, such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, and decamethylene. Among these, R 1a From the viewpoint of the curability of the curable composition, the alkylene group is preferably a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms, more preferably an ethylene group, a trimethylene group, or a propylene group, and even more preferably an ethylene group or a trimethylene group.

[0036] In the above formula (1b), R 1b represents a linear or branched alkylene group, and R 1a Among them, R 1b From the viewpoint of the curability of the curable composition, the alkylene group is preferably a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms, more preferably an ethylene group, a trimethylene group, or a propylene group, and even more preferably an ethylene group or a trimethylene group.

[0037] In the above formula (1c), R 1c represents a linear or branched alkylene group, and R 1a Among them, R 1c From the viewpoint of the curability of the curable composition, the alkylene group is preferably a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms, more preferably an ethylene group, a trimethylene group, or a propylene group, and even more preferably an ethylene group or a trimethylene group.

[0038] In the above formula (1d), R 1d represents a linear or branched alkylene group, and R 1a Among them, R 1d From the viewpoint of the curability of the curable composition, the alkylene group is preferably a linear alkylene group having 1 to 4 carbon atoms or a branched alkylene group having 3 or 4 carbon atoms, more preferably an ethylene group, a trimethylene group, or a propylene group, and even more preferably an ethylene group or a trimethylene group.

[0039] R in formula (1) 1 As the group represented by the formula (1a), R 1a is an ethylene group [particularly, a 2-(3,4-epoxycyclohexyl)ethyl group] is preferred.

[0040] Examples of the cationically polymerizable silsesquioxane include compounds having a constitutional unit represented by the following formula (1). [R 1 SiO3 / 2 ] (1)

[0041] The structural unit represented by the above formula (1) is generally [RSiO 3 / 2 ] is a silsesquioxane structural unit (so-called T unit) represented by the formula (1). In the above formula, R represents a hydrogen atom or a monovalent organic group, and the same applies hereinafter. The structural unit represented by the formula (1) is formed by the hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compound. In this specification, a compound having a structural unit represented by the formula (1) may be referred to as "silsesquioxane (X)". R in formula (1) 1 represents a group (monovalent group) containing the above-mentioned cationically polymerizable functional group.

[0042] The silsesquioxane (X) may have only one type of constitutional unit represented by the above formula (1), or may have two or more types of constitutional units represented by the above formula (1).

[0043] Silsesquioxane (X) is a silsesquioxane building block [RSiO 3 / 2 In addition to the constitutional unit represented by the above formula (1), the following constitutional unit represented by the following formula (2) may be contained as the constitutional unit represented by the above formula (1). [R 2 SiO 3 / 2 ] (2)

[0044] The structural unit represented by the above formula (2) is generally [RSiO 3 / 2 That is, the constitutional unit represented by the above formula (2) is formed by the hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compound.

[0045] R in the above formula (2) 2represents 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 aryl group include a phenyl group, a tolyl group, and a naphthyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the cycloalkyl group include a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the alkyl group include a straight-chain or branched-chain alkyl group such as a methyl group, an ethyl group, a propyl group, an n-butyl group, an isopropyl group, an isobutyl group, an s-butyl group, a t-butyl group, and an isopentyl group.

[0046] Examples of the above-mentioned substituted aryl group, substituted aralkyl group, substituted cycloalkyl group, and substituted alkyl group include groups in which the hydrogen atoms or part or all of the main chain skeleton of the above-mentioned aryl group, aralkyl group, cycloalkyl group, and alkyl group are substituted with at least one selected from the group consisting of alkyl groups (particularly, linear or branched alkyl groups having 1 to 10 carbon atoms), ether groups, ester groups, carbonyl groups, siloxane groups, halogen atoms (such as fluorine atoms), mercapto groups, amino groups, and hydroxy groups (hydroxyl groups).

[0047] Among them, R 2 As the alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group is preferable, a substituted or unsubstituted aryl group is more preferable, and a phenyl group is even more preferable.

[0048] The proportion of each of the above-mentioned silsesquioxane structural units (structural unit represented by formula (1) and structural unit represented by formula (2)) in the silsesquioxane (X) can be appropriately adjusted by changing the composition of the raw material (hydrolyzable trifunctional silane) for forming these structural units.

[0049] Silsesquioxane (X) is, among others, R 1 a structural unit represented by the above formula (1) in which R is a group containing an alicyclic epoxy group, and 2is an optionally substituted aryl group. In this case, the surface hardness, flexibility, processability, and flame retardancy of the hard coat-less film tend to be better.

[0050] Silsesquioxane (X) further contains, in addition to the constitutional unit represented by the above formula (1) which is a T unit and the constitutional unit represented by the above formula (2), [RSiO 1 / 2 ] (so-called M unit), [R2SiO 2 / 2 ] (so-called D unit), and [SiO 4 / 2 In addition, R in the M unit and the D unit may be selected from the group consisting of R in the structural unit represented by the formula (1) above. 1 and the structural unit R represented by the above formula (2) 2 Examples of silsesquioxane structural units other than the structural unit represented by the above formula (1) and the structural unit represented by the above formula (2) include structural units represented by the following formula (3): [HSiO 3 / 2 ] (3)

[0051] The silsesquioxane (X) contains a structural unit (T3 form) represented by the following formula (I), and may further contain a structural unit (T2 form) represented by the following formula (II). [R a SiO 3 / 2 ] (I) [R b SiO 2 / 2 (OR c )] (II)

[0052] The structural unit represented by formula (I) above can be described in more detail as represented by formula (I') below. The structural unit represented by formula (II) above can be described in more detail as represented by formula (II') below. Each of the three oxygen atoms bonded to the silicon atom in the structure represented by formula (I') below is bonded to another silicon atom (a silicon atom not shown in formula (I')). Meanwhile, each of the two oxygen atoms located above and below the silicon atom in the structure represented by formula (II') below is bonded to another silicon atom (a silicon atom not shown in formula (II')). That is, the T3 and T2 structures are both structural units (T units) formed by the hydrolysis and condensation reaction of the corresponding hydrolyzable trifunctional silane compounds. [ka] [ka]

[0053] R in the above formula (I) a (R in formula (I') a (the same applies to R in formula (II)) b (R in formula (II') b and (the same applies to R and R) 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. a and R b Specific examples of R in the above formula (1) include 1 , R in the above formula (2) 2 Examples of the R a and R in formula (II) bare each a group derived from a group (a group other than an alkoxy group or a halogen atom) bonded to a silicon atom in the hydrolyzable trifunctional silane compound used as a raw material for the silsesquioxane (X), or, for example, when the cationically polymerizable functional group is an epoxy group, a group obtained by epoxidizing a group (a group other than an alkoxy group or a halogen atom) bonded to a silicon atom in the hydrolyzable trifunctional silane compound used as a raw material for the silsesquioxane (X).

[0054] R in the above formula (II) c (R in formula (II') c (The same applies to R in formula (II)) represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a linear or branched alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. Of these, a methyl group and an ethyl group are preferred, and a methyl group is more preferred. c The alkyl group in the formula (I) is generally derived from an alkyl group that forms an alkoxy group in the hydrolyzable silane compound used as a raw material for the silsesquioxane (X).

[0055] The molar ratio of the structural unit represented by formula (I) (T3 isomer) to the structural unit represented by formula (II) (T2 isomer) in the silsesquioxane (X) [structural unit represented by formula (I) / structural unit represented by formula (II)] (sometimes referred to as "T3 isomer / T2 isomer") is not particularly limited, but is preferably 5 or more, more preferably 5 to 20, even more preferably 5 to 18, even more preferably 6 to 16, still more preferably 7 to 15, and particularly preferably 8 to 14. By setting the molar ratio [T3 isomer / T2 isomer] to 5 or more, the surface hardness of the hard coat-less film tends to be further improved.

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

[0057] Silsesquioxane (X) 29 The Si-NMR spectrum can be measured, for example, using the following apparatus and conditions. Measurement equipment: Product name "JNM-ECA500NMR" (manufactured by JEOL Ltd.) Solvent: deuterated chloroform Accumulation count: 1800 times Measurement temperature: 25℃

[0058] The molar ratio [T3 / T2] of silsesquioxane (X) being 5 or more means that a certain amount of T2 isomers is present relative to the T3 isomers in silsesquioxane (X). Examples of such T2 isomers include a structural unit represented by the following formula (4), a structural unit represented by the following formula (5), and a structural unit represented by the following formula (6). R in the following formula (4) 1 and R in the following formula (5) 2 are R in the above formula (1), respectively. 1 and R in the above formula (2) 2 The same as R in the following formulas (4) to (6): c is R in formula (II)c As with the above, it represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. [R 1 SiO 2 / 2 (OR c )] (4) [R 2 SiO 2 / 2 (OR c )] (5) [HSiO 2 / 2 (OR c )] (6)

[0059] The cationically polymerizable silsesquioxane (particularly, the silsesquioxane (X)) may be a silsesquioxane having a cage shape (a cage silsesquioxane). The cage silsesquioxane includes a complete cage silsesquioxane and an incomplete cage silsesquioxane, and among these, an incomplete cage silsesquioxane is preferred.

[0060] Generally, a complete cage silsesquioxane is a polyorganosilsesquioxane composed only of T3 isomers, and no T2 isomers are present in the molecule. That is, the molar ratio [T3 isomer / T2 isomer] is 5 or more, and as described later, the peak at 1100 cm in the FT-IR spectrum is -1 When a silsesquioxane has one characteristic absorption peak in the vicinity, it is suggested that the silsesquioxane has an incomplete cage silsesquioxane structure.

[0061] Whether or not silsesquioxane (X) has a cage (incomplete cage) silsesquioxane structure can be confirmed by FT-IR spectroscopy [Reference: R.H. Raney, M. Itoh, A. Sakakibara and T. Suzuki, Chem. Rev. 95, 1409 (1995)]. Specifically, in the FT-IR spectrum, -1 Near and 1150cm -1 There is no specific absorption peak near 1100 cm -1In contrast, when there is a specific absorption peak in the vicinity of 1050 cm in the FT-IR spectrum, the silsesquioxane (X) can be identified as having a cage (incomplete cage) silsesquioxane structure. -1 Near and 1150cm -1 When the silsesquioxane (X) has a characteristic absorption peak in the vicinity of the FT-IR spectrum, it is identified as having a ladder-type silsesquioxane structure. The FT-IR spectrum of the silsesquioxane (X) can be measured, for example, using the following apparatus and conditions. Measuring device: Product name "FT-720" (manufactured by Horiba Ltd.) Measurement method: transmission method Resolution: 4cm -1 Measurement wave number range: 400~4000cm -1 Accumulation count: 16 times

[0062] The proportion (total amount) of structural units having a cationically polymerizable functional group (e.g., structural units represented by the above formula (1) and structural units represented by the above formula (4)) relative to the total amount of siloxane structural units (total siloxane structural units; the total amount of M units, D units, T units, and Q units) in the cationically polymerizable silsesquioxane (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%, even more preferably 80 to 99 mol%, and particularly preferably 90 to 98 mol%. A proportion of 50 mol% or more improves the curability of the curable composition and significantly increases the surface hardness of the hardcoat-less film. The proportion of each siloxane structural unit in the cationically polymerizable silsesquioxane can be calculated, for example, from the composition of the raw materials or NMR spectroscopy.

[0063] The proportion of the structural units represented by the above formula (I) (T3 isomer) relative to the total amount of siloxane structural units in the silsesquioxane (X) [total siloxane structural units; total amount of 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%, even more preferably 70 to 98 mol%, even more preferably 80 to 95 mol%, and particularly preferably 85 to 92 mol%. It is presumed that by making the proportion of T3 structural units 50 mol% or more, it becomes easier to form an incomplete cage structure with an appropriate molecular weight, and the surface hardness of the hard coat-less film tends to be further improved.

[0064] The proportion (total amount) of the structural units represented by the above formula (2) and the structural units represented by the above formula (5) relative to the total amount of siloxane structural units in the silsesquioxane (X) [total siloxane structural units; total amount of M units, D units, T units, and Q units] (100 mol%) is not particularly limited, but is preferably 0 to 50 mol%, more preferably 0 to 40 mol%, even more preferably 0 to 30 mol%, and particularly preferably 1 to 15 mol%. By setting the proportion to 50 mol% or less, the proportion of structural units having cationically polymerizable functional groups can be relatively increased, which improves the curability of the curable composition and tends to increase the surface hardness of the hardcoat-less film.

[0065] The proportion (total amount) of the structural units represented by the above formula (I) and the structural units represented by the above formula (II) (particularly, the total proportion of the T3 and T2 isomers) relative to the total amount of siloxane structural units in the silsesquioxane (X) [total siloxane structural units; the total amount of M units, D units, T units, and Q units] (100 mol%) is not particularly limited, but is preferably 60 mol% or more (e.g., 60 to 100 mol%), more preferably 70 mol% or more, even more preferably 80 mol% or more, and particularly preferably 90 mol% or more. It is presumed that by setting the proportion at 60 mol% or more, it becomes easier to form an incomplete cage structure having an appropriate molecular weight, which tends to further improve the surface hardness of the hard coat-less film. In particular, it is preferable that the proportions (total amount) of the structural units represented by the above formula (1), the structural units represented by the above formula (2), the structural units represented by the above formula (4), and the structural units represented by the above formula (5) are within the above range.

[0066] The number average molecular weight (Mn) of the silsesquioxane (X) in terms of standard polystyrene determined by gel permeation chromatography is not particularly limited, but is preferably 1000 to 3000, more preferably 1000 to 2800, even more preferably 1100 to 2600, and particularly preferably 1500 to 2500. By adjusting the number average molecular weight to 1000 or more, the surface hardness of the hard coat-less film tends to be further improved. In addition, the heat resistance and scratch resistance of the hard coat-less film tend to be improved. On the other hand, by adjusting the number average molecular weight to 3000 or less, the compatibility with other components in the curable composition is improved, and the heat resistance of the hard coat-less film tends to be improved.

[0067] The molecular weight dispersity (Mw / Mn) of the silsesquioxane (X) in terms of standard polystyrene as determined by gel permeation chromatography 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 setting the molecular weight dispersity to 3.0 or less, the surface hardness of the hard coat-less film tends to be higher. On the other hand, by setting the molecular weight dispersity to 1.0 or more (particularly 1.1 or more), the film tends to be easily liquid, and handleability tends to be improved.

[0068] The number average molecular weight and molecular weight dispersity of the silsesquioxane (X) can be measured using the following apparatus and conditions. Measuring device: Product name "LC-20AD" (Shimadzu Corporation) Columns: Shodex KF-801 x 2, KF-802, and KF-803 (Showa Denko K.K.) Measurement temperature: 40℃ Eluent: THF, sample concentration 0.1~0.2% by weight Flow rate: 1mL / min Detector: UV-VIS detector (product name "SPD-20A", manufactured by Shimadzu Corporation) Molecular weight: Standard polystyrene equivalent

[0069] The cationically polymerizable silsesquioxane can be produced by a known or conventional method for producing silsesquioxane, and is not particularly limited. For example, the cationically polymerizable silsesquioxane can be produced by a method in which one or more hydrolyzable silane compounds are hydrolyzed and condensed.

[0070] The content of the cationically polymerizable silsesquioxane in the curable composition is not particularly limited, but is preferably greater than 50% by mass (e.g., greater than 50% by mass but not greater than 98% by mass) relative to the total amount of curable compounds (100% by mass), more preferably 60 to 95% by mass, even more preferably 70 to 93% by mass, and particularly preferably 80 to 90% by mass. When the content is greater than 50% by mass, the surface hardness of the hardcoat-less film tends to be further improved. When the content is 98% by mass or less, other components can be contained, and the effects obtained by containing these components tend to be further improved. Furthermore, a curing catalyst can be contained, which tends to more efficiently promote curing of the curable composition.

[0071] The curable compound preferably contains a curable compound having an active energy ray-polymerizable functional group (sometimes referred to as an "active energy ray-curable compound"). In this case, the dispersibility of the radically curable polyorganosiloxane described below in the curable composition and hard coat-less film can be increased. Note that the active energy ray-curable compound is a compound that does not fall under the category of the cationically polymerizable silsesquioxane.

[0072] Examples of the active energy ray-polymerizable functional group include a vinyl group, a propenyl group, an isopropenyl group, a (meth)acryloyl group (an acryloyl group, a methacryloyl group), etc. Among these, a (meth)acryloyl group is preferred.

[0073] The active energy ray-curable compound has one or more unsaturated bonds, preferably one to six, more preferably one to three, even more preferably one to two, and particularly preferably one.

[0074] The active energy ray-curable compound may have a cationically polymerizable functional group in the molecule. In this case, the active energy ray-curable compound is reactive with the cationically polymerizable silsesquioxane, and a hard coat-less film having higher mechanical strength and surface hardness can be obtained. The cationically polymerizable functional group that the active energy ray-curable compound may have includes those exemplified and explained as the cationically polymerizable functional group that the cationically polymerizable silsesquioxane has, and among them, an epoxy group is preferred.

[0075] The number of the cationically polymerizable functional groups that the active energy ray-curable compound has is 1 or more, preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1 or 2.

[0076] The functional group equivalent of the active energy ray-polymerizable functional group of the active energy ray-curable 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 hard coat-less film has better flex resistance. When the functional group equivalent is 500 or less, the hard coat-less film has higher surface hardness. The functional group equivalent can be calculated using the following formula. [Functional group equivalent of active energy ray-polymerizable functional group]=[Molecular weight of the active energy ray-curable compound] / [Number of active energy ray-polymerizable functional groups in the active energy ray-curable compound]

[0077] The functional group equivalent of the cationically polymerizable functional group of the active energy ray-curable 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 hard coat-less film has better flex resistance. When the functional group equivalent is 500 or less, the hard coat-less film has higher surface hardness. The functional group equivalent can be calculated using the following formula. [Functional group equivalent of cationically polymerizable functional group]=[Molecular weight of the active energy ray-curable compound] / [Number of cationically polymerizable functional groups contained in the active energy ray-curable compound]

[0078] The active energy ray-curable compound preferably has a polyether skeleton such as a polyethylene glycol skeleton, a polypropylene glycol skeleton, or a polyglycerin skeleton.

[0079] Specific examples of the active energy ray-curable compound include 3,4-epoxycyclohexylmethyl(meth)acrylate, glycidyl(meth)acrylate, tripropylene glycol diglycidyl ether di(meth)acrylate (a compound obtained by reacting both epoxy groups of tripropylene glycol diglycidyl ether with (meth)acrylic acid), tripropylene glycol diglycidyl ether half(meth)acrylate (a compound obtained by reacting one epoxy group of tripropylene glycol diglycidyl ether with (meth)acrylic acid), bisphenol A epoxy di(meth)acrylate (a compound obtained by reacting both epoxy groups of bisphenol A diglycidyl ether with (meth)acrylic acid), bisphenol A epoxy half(meth)acrylate (a compound obtained by reacting one epoxy group of bisphenol A diglycidyl ether with (meth)acrylic acid or a derivative thereof), bisphenol F epoxy di(meth)acrylate, bisphenol F epoxy half(meth)acrylate, bisphenol S epoxy di(meth)acrylate, bisphenol B epoxy di(meth)acrylate, bisphenol C epoxy di(meth)acrylate, bisphenol D epoxy di(meth)acrylate, bisphenol E epoxy di(meth)acrylate, bisphenol F epoxy half(meth)acrylate, bisphenol F epoxy di(meth)acrylate, bisphenol F epoxy di(meth)acrylate, bisphenol F epoxy di(meth)acrylate, bisphenol H ... Compounds having an epoxy group and / or a hydroxyl group and a (meth)acryloyl group in one molecule, such as phenol S epoxy half (meth)acrylate; compounds having an oxetanyl group and a (meth)acryloyl group in one molecule, such as 3-oxetanylmethyl (meth)acrylate, 3-methyl-3-oxetanylmethyl (meth)acrylate, 3-ethyl-3-oxetanylmethyl (meth)acrylate, 3-butyl-3-oxetanylmethyl (meth)acrylate, and 3-hexyl-3-oxetanylmethyl (meth)acrylate; 2-vinyl (meth)acrylate vinyloxyethyl, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate, 4-vinyloxybutyl (meth)acrylate, 1-methyl-3-vinyloxypropyl (meth)acrylate, 1-vinyloxymethylpropyl (meth)acrylate, 2-methyl-3-vinyloxypropyl (meth)acrylate, 1,1-dimethyl-2-vinyloxyethyl (meth)acrylate, 3-vinyloxybutyl (meth)acrylate, 1-methyl-2-vinyloxypropyl (meth)acrylate2-vinyloxybutyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, 3-vinyloxymethylcyclohexylmethyl (meth)acrylate, 2-vinyloxycyclohexylmethyl (meth)acrylate, p-vinyloxymethylphenylmethyl (meth)acrylate, m-vinyloxymethylphenylmethyl (meth)acrylate, o-vinyloxymethylphenylmethyl (meth)acrylate, 2-(vinyloxy)(meth)acrylate (meth)acrylate 2-(vinyloxyethoxy)ethyl, (meth)acrylate 2-(vinyloxyisopropoxy)propyl, (meth)acrylate 2-(vinyloxyethoxy)isopropyl, (meth)acrylate 2-(vinyloxyisopropoxy)propyl, (meth)acrylate 2-(vinyloxyisopropoxy)isopropyl, (meth)acrylate 2-(vinyloxyethoxyethoxy)ethyl, (meth)acrylate 2-(vinyloxyethoxyisopropoxy)ethyl, (meth)acrylate 2-(vinyloxyisopropoxy)ethyl, (meth)acrylate 2-(vinyloxyisopropoxy)ethyl (meth)acrylate 2-(vinyloxyisopropoxyisopropoxy)ethyl, (meth)acrylate 2-(vinyloxyethoxyethoxy)propyl, (meth)acrylate 2-(vinyloxyethoxyisopropoxy)propyl, (meth)acrylate 2-(vinyloxyisopropoxyethoxy)propyl, (meth)acrylate 2-(vinyloxyisopropoxyisopropoxy)propyl, (meth)acrylate 2-(vinyloxyethoxyethoxy)isopropyl, (meth)acrylate 2-(vinyloxyethoxyisopropoxy)isopropyl, (meth)acrylate 2-(vinyloxyethoxyisopropoxy)isopropyl acrylate, 2-(vinyloxyisopropoxyethoxy)isopropyl (meth)acrylate, 2-(vinyloxyisopropoxyisopropoxy)isopropyl (meth)acrylate, 2-(vinyloxyethoxyethoxyethoxy)ethyl (meth)acrylate, 2-(vinyloxyethoxyethoxyethoxyethoxy)ethyl (meth)acrylate, 2-(isopropenoxyethoxy)ethyl (meth)acrylate, 2-(isopropenoxyethoxyethoxy)ethyl (meth)acrylate, 2-(isopropenoxyethoxyethoxy)ethyl (meth)acrylate,Examples include compounds having a vinyl ether group and a (meth)acryloyl group in one molecule, such as 2-(isopropenoxyethoxyethoxyethoxyethoxy)ethyl (meth)acrylate, polyethylene glycol monovinyl ether (meth)acrylate, and polypropylene glycol monovinyl ether (meth)acrylate.

[0080] From the viewpoint of the flex resistance and surface hardness of the hard coat-less film, the active energy ray-curable compound is preferably a compound having an epoxy group and / or a hydroxy group as a cationically polymerizable functional group and a (meth)acryloyl group as an active energy ray-polymerizable functional group in one molecule, and specifically, preferred examples include 3,4-epoxycyclohexylmethyl(meth)acrylate, glycidyl(meth)acrylate, tripropylene glycol diglycidyl ether half(meth)acrylate, bisphenol A epoxy half(meth)acrylate, bisphenol F epoxy half(meth)acrylate, and bisphenol S epoxy half(meth)acrylate.

[0081] The active energy ray-curable compound can be produced by a known method, for example, by reacting a portion of the cationically polymerizable functional groups of a compound having two or more cationically polymerizable functional groups (e.g., epoxy groups, hydroxy groups) in one molecule with a carboxylic acid (e.g., acrylic acid, methacrylic acid, etc.) having an active energy ray-polymerizable functional group or a derivative thereof. Furthermore, as the compound A, for example, commercially available products such as "Light Ester G," "Epoxy Ester 200PA," and "Epoxy Ester 200PA-E5" (all manufactured by Kyoeisha Chemical Co., Ltd.), and "NK OLIGO EA1010N" (manufactured by Shin-Nakamura Chemical Co., Ltd.) can also be used.

[0082] The content of the active energy ray-curable compound in the curable composition is not particularly limited, but is preferably 0.1 to 5 mass%, more preferably 0.3 to 4 mass%, and even more preferably 0.6 to 3 mass%, relative to the total amount (100 mass%) of the curable compounds. When the content is within the above range, the dispersibility of the radical-curable polyorganosiloxane tends to be further improved.

[0083] The content of the active energy ray-curable compound is not particularly limited, but is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, and even more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the cationically polymerizable silsesquioxane. When the content is within the above range, the dispersibility of the radical-curable polyorganosiloxane tends to be further improved.

[0084] The curable compound preferably contains an aliphatic compound having a cationically polymerizable functional group (cationically curable aliphatic compound). In this case, flexibility can be imparted to the hard coat-less film, and the flexibility and flex resistance can be further improved. Note that the cationically curable aliphatic compound is a compound that does not fall under the category of the cationically polymerizable silsesquioxane and the active energy ray-curable compound.

[0085] Examples of the cationically polymerizable functional group possessed by the cationically curable aliphatic compound include those exemplified and explained as the cationically polymerizable functional group possessed by the above-mentioned cationically polymerizable silsesquioxane. Among these, an epoxy group is preferred, and a glycidyl group is more preferred from the viewpoint of reactivity.

[0086] The number of cationically polymerizable functional groups that the cationically curable aliphatic compound has in one molecule is preferably 2 or more, more preferably 2 to 5, even more preferably 2 to 3, and particularly preferably 2.

[0087] The functional group equivalent of the cationically polymerizable functional group of the cationically curable 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 hard coat-less film has better flex resistance. When the functional group equivalent is 500 or less, the hard coat-less film has higher surface hardness. The functional group equivalent can be calculated using the following formula. [Functional group equivalent of cationically polymerizable functional group]=[Molecular weight of the cationically curable aliphatic compound] / [Number of cationically polymerizable functional groups in the cationically curable aliphatic compound]

[0088] The "aliphatic compound" in the cationically curable aliphatic compound refers to an aliphatic compound that does not have a cyclic structure other than the cationically polymerizable functional group. Examples of the cationically curable aliphatic compound include glycidyl ethers of alcohols that do not have a divalent or higher cyclic structure; and glycidyl esters of divalent or higher carboxylic acids (e.g., adipic acid, sebacic acid, maleic acid, itaconic acid, etc.). Examples of the alcohols that do not have a divalent or higher cyclic structure include dihydric alcohols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol; and trivalent or higher polyhydric alcohols such as glycerin, diglycerin, erythritol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, and sorbitol. The dihydric or higher alcohol may be a polyether polyol, a polyester polyol, a polycarbonate polyol, a polyolefin polyol, or the like.

[0089] The cationically curable aliphatic compound is preferably a compound having two cationically polymerizable functional groups at both ends of the aliphatic compound, and specifically, a compound represented by the following formula (A) is preferred. [ka]

[0090] In the above formula (A), M represents a linear or branched alkylene group having 2 to 10 carbon atoms. Examples of the linear or branched alkylene group having 2 to 10 carbon atoms include linear or branched alkylene groups having 2 to 10 carbon atoms, such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, and decamethylene. Among these, from the viewpoints of improving the surface hardness, flexibility, and flex resistance of the hard coat-less film and preventing a decrease in antifouling performance, M is preferably a linear or branched alkylene group having 3 to 8 carbon atoms, more preferably a linear alkylene group having 5 to 7 carbon atoms, and even more preferably a linear alkylene group having 6 carbon atoms (hexamethylene group).

[0091] In the above formula (A), E 1 and E 2 are the same or different and represent a cationically polymerizable functional group, and are preferably a group represented by the following formula (E) from the viewpoints of improving the reactivity, surface hardness, flexibility, and flex resistance of the hard coat-less film, and making it difficult for the antifouling performance to decrease. [ka]

[0092] In formula (E), R A represents a linear or branched alkylene group having 1 to 6 carbon atoms. Examples of the linear or branched alkylene group having 1 to 6 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and a decamethylene group. Among these, R A As R, from the viewpoints of improving the reactivity, surface hardness, flexibility, and flex resistance of the hard coat-less film, and preventing deterioration of the antifouling performance, a linear alkylene group having 1 to 4 carbon atoms is preferred, more preferably a methylene group or an ethylene group, and even more preferably a methylene group.B is a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

[0093] Specific examples of the cationically curable aliphatic compound 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 (tetramethylene glycol diglycidyl ether), neopentyl glycol diglycidyl ether, 3-methyl-2,4-pentanediol diglycidyl ether, 2,4-pentanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether (pentamethylene glycol diglycidyl ether), 3-methyl-1,5-pentanediol diglycidyl ether, and 2-methyl-2,4-pentanediol. Examples of the alkylene glycol diglycidyl ether (alkanediol diglycidyl ether) include diglycidyl ether, 2,4-diethyl-1,5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether (hexamethylene glycol diglycidyl ether), 1,7-heptanediol diglycidyl ether, 3,5-heptanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 2-methyl-1,8-octanediol diglycidyl ether, and 1,9-nonanediol diglycidyl ether, and (poly)alkylene glycol diglycidyl ethers such as diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and triethylene glycol diglycidyl ether. Among these, 1,6-hexanediol diglycidyl ether is preferred from the viewpoints of improving the reactivity, surface hardness, flexibility, and flex resistance of the hard coat-less film, and preventing deterioration of antifouling performance.

[0094] Commercially available products of the cationically curable aliphatic compound include those under the trade names "EPOLITE 40E," "EPOLITE 100E," "EPOLITE 200E," "EPOLITE 400E," "EPOLITE 1600," and "EPOLITE 1600N" (manufactured by Kyoeisha Chemical Co., Ltd.), and those under the trade name "YH-300" (manufactured by Nippon Steel Chemical & Material Co., Ltd.).

[0095] The content of the cationically curable aliphatic compound in the curable composition is not particularly limited, but is preferably 1 to 20 mass %, more preferably 2 to 15 mass %, and even more preferably 3 to 12 mass %, relative to the total amount (100 mass %) of the curable compounds. When the content is within the above range, the flexibility and bending resistance of the hard coat-less film become more appropriate.

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

[0097] The curable composition preferably contains a radically curable polyorganosiloxane. Use of the radically curable polyorganosiloxane improves the smoothness of the hardcoat-less film surface, provides excellent sebum adhesion resistance, and makes the hardcoat-less film surface less susceptible to fingerprints. Furthermore, the active energy ray-curable polyorganosiloxane is preferably not a PFAS-regulated substance. In this case, the above-mentioned effects are exhibited despite not being a PFAS-regulated substance. Since the radically curable polyorganosiloxane has radical curability, it also falls under the category of the curable compound. The radically curable polyorganosiloxane may be used alone or in combination of two or more types.

[0098] The radically curable polyorganosiloxane has a radically polymerizable functional group in the molecule, such as a photoradical polymerizable functional group.

[0099] Examples of the photoradical polymerizable functional group include a (meth)acryloyl group, a (meth)acrylamide group, a vinyl group, a vinylthio group, etc. Among these, a (meth)acryloyl group is preferred.

[0100] As the polyorganosiloxane in the radical-curable polyorganosiloxane, a linear polyorganosiloxane is preferred from the viewpoint of exhibiting a greater effect as a leveling agent.

[0101] The content of the radical-curable polyorganosiloxane in the curable composition is not particularly limited, but is preferably 0.01 to 5 mass%, more preferably 0.03 to 3 mass%, and even more preferably 0.04 to 1 mass%, relative to the total amount (100 mass%) of the curable compounds. When the content is within the above range, the surface of the hard coat-less film has better resistance to sebum adhesion.

[0102] The content of the radical-curable polyorganosiloxane is not particularly limited, but is preferably 0.01 to 5 parts by mass, more preferably 0.03 to 3 parts by mass, and even more preferably 0.04 to 1 part by mass, relative to 100 parts by mass of the cationically polymerizable silsesquioxane. When the content is within the above range, the surface of the hard coat-less film has better resistance to sebum adhesion.

[0103] The content of the curable compound in the curable composition 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 nonvolatile content in the curable composition (total amount excluding the solvent). When the content is 90% by mass or more, the mechanical strength of the hard coat-less film is superior. In this specification, the proportion of each component relative to the total amount of nonvolatile content in the curable composition corresponds to the proportion of the component derived from that component in the hard coat-less film.

[0104] The curable composition preferably contains a curing catalyst. The curing catalyst is a compound that can initiate or accelerate the polymerization reaction of a curable compound such as the cationically polymerizable silsesquioxane, the active energy ray-curable compound, or the cationically polymerizable aliphatic compound. Only one type of curing catalyst may be used, or two or more types may be used.

[0105] The curing catalyst is selected depending on the type of curable functional group possessed by the curable compound, and among them, a cationic polymerization initiator and / or a radical polymerization initiator is preferred. The cationic polymerization initiator is a compound that generates cationic species upon exposure to heat or active energy rays, thereby initiating the curing reaction of the curable compound.

[0106] The cationic polymerization initiator includes a photo-cationic polymerization initiator (photo-acid generator) and a thermal cationic polymerization initiator (thermal acid generator).

[0107] As the cationic photopolymerization initiator, known or commonly used cationic photopolymerization initiators can be used, and examples thereof include sulfonium salts (salts of sulfonium ions and anions), iodonium salts (salts of iodonium ions and anions), selenium salts (salts of selenium ions and anions), ammonium salts (salts of ammonium ions and anions), phosphonium salts (salts of phosphonium ions and anions), and salts of transition metal complex ions and anions.

[0108] Examples of the sulfonium salt include triphenylsulfonium salt, tri-p-tolyl sulfonium salt, tri-o-tolyl sulfonium salt, tris(4-methoxyphenyl)sulfonium salt, 1-naphthyldiphenylsulfonium salt, 2-naphthyldiphenylsulfonium salt, tris(4-fluorophenyl)sulfonium salt, tri-1-naphthylsulfonium salt, tri-2-naphthylsulfonium salt, tris(4-hydroxyphenyl)sulfonium salt, diphenyl[4-(phenylthio)phenyl]sulfonium salt, and 4-(p-tolylthio)phenyldi-(p-phenyl)sulfonium. salts; diaryl sulfonium salts such as diphenylphenacylsulfonium salt, diphenyl 4-nitrophenacylsulfonium salt, diphenylbenzylsulfonium salt, and diphenylmethylsulfonium salt; monoaryl sulfonium salts such as phenylmethylbenzylsulfonium salt, 4-hydroxyphenylmethylbenzylsulfonium salt, and 4-methoxyphenylmethylbenzylsulfonium salt; and trialkylsulfonium salts such as dimethylphenacylsulfonium salt, phenacyltetrahydrothiophenium salt, and dimethylbenzylsulfonium salt.

[0109] Examples of the diphenyl[4-(phenylthio)phenyl]sulfonium salt include diphenyl[4-(phenylthio)phenyl]sulfonium tetrakis(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate, etc. Commercially available products such as "CPI-100P" (manufactured by San-Apro Co., Ltd., diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate 50% propylene carbonate solution) can also be used.

[0110] Examples of the iodonium salt include the trade name "RHODORSIL PHOTOINITIATOR 2074" (manufactured by Rhodia Japan, tetrakis(pentafluorophenyl)borate·[(1-methylethyl)phenyl](methylphenyl)iodonium), the trade name "WPI-124" (manufactured by Wako Pure Chemical Industries, Ltd.), diphenyliodonium salt, di-p-tolyliodonium salt, bis(4-dodecylphenyl)iodonium salt, and bis(4-methoxyphenyl)iodonium salt.

[0111] Examples of the selenium salt include triarylselenium salts such as triphenylselenium salt, tri-p-tolylselenium salt, tri-o-tolylselenium salt, tris(4-methoxyphenyl)selenium salt, and 1-naphthyldiphenylselenium salt; diarylselenium salts such as diphenylphenacylselenium salt, diphenylbenzylselenium salt, and diphenylmethylselenium salt; monoarylselenium salts such as phenylmethylbenzylselenium salt; and trialkylselenium salts such as dimethylphenacylselenium salt.

[0112] Examples of the ammonium salt include tetraalkylammonium salts such as tetramethylammonium salt, ethyltrimethylammonium salt, diethyldimethylammonium salt, triethylmethylammonium salt, tetraethylammonium salt, trimethyl-n-propylammonium salt, and trimethyl-n-butylammonium salt; pyrrolidium salts such as N,N-dimethylpyrrolidinium salt and N-ethyl-N-methylpyrrolidinium salt; imidazolinium salts such as N,N'-dimethylimidazolinium salt and N,N'-diethylimidazolinium salt; N,N'-dimethyltetrahydropyrimidium salt and N,N'-diethyltetrahydropyrimidium salt; tetrahydropyrimidium salts such as tetrahydropyrimidium salts; morpholinium salts such as N,N-dimethylmorpholinium salts and N,N-diethylmorpholinium salts; piperidinium salts such as N,N-dimethylpiperidinium salts and N,N-diethylpiperidinium salts; pyridinium salts such as N-methylpyridinium salts and N-ethylpyridinium salts; imidazolium salts such as N,N'-dimethylimidazolium salts; quinolium salts such as N-methylquinolium salts; isoquinolium salts such as N-methylisoquinolium salts; thiazonium salts such as benzylbenzothiazonium salts; and acridium salts such as benzylacridium salts.

[0113] Examples of the phosphonium salt include tetraarylphosphonium salts such as tetraphenylphosphonium salts, tetra-p-tolylphosphonium salts, and tetrakis(2-methoxyphenyl)phosphonium salts; triarylphosphonium salts such as triphenylbenzylphosphonium salts; and tetraalkylphosphonium salts such as triethylbenzylphosphonium salts, tributylbenzylphosphonium salts, tetraethylphosphonium salts, tetrabutylphosphonium salts, and triethylphenacylphosphonium salts.

[0114] Examples of the salts of the transition metal complex ions include (η 5 -cyclopentadienyl)(η 6 -Toluene)Cr + , (η 5 -cyclopentadienyl)(η 6 -xylene)Cr+ Salts of chromium complex cations such as (η 5 -cyclopentadienyl)(η 6 -Toluene)Fe + , (η 5 -cyclopentadienyl)(η 6 -xylene)Fe + and the like.

[0115] The anion constituting the above salt is, for example, PF6 - , BF4 - , (C6F5)4B - , (C6F5)4Ga - , sulfonate anions (trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion, methanesulfonate anion, benzenesulfonate anion, p-toluenesulfonate anion, etc.), perhalogenate ions, halogenated sulfonate ions, sulfate ions, carbonate ions, aluminate ions, carboxylate ions, arylborate ions, thiocyanate ions, nitrate ions, etc.

[0116] Examples of the thermal cationic polymerization initiator include arylsulfonium salts, aryliodonium salts, allene-ion complexes, quaternary ammonium salts, aluminum chelates, boron trifluoride amine complexes, etc. Examples of the anions constituting the salts include the same anions as those in the photocationic polymerization initiators.

[0117] Examples of the arylsulfonium salt include pentafluorophenyl borate and hexafluorophosphate salt. In the curable composition of the present invention, commercially available products such as those sold under the trade names "SP-66" and "SP-77" (both manufactured by ADEKA Corporation) and those sold under the trade names "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" (all manufactured by Sanshin Chemical Industry Co., Ltd.) can be used. Examples of the aluminum chelate include ethyl acetoacetate aluminum diisopropylate and aluminum tris(ethyl acetoacetate). Examples of the boron trifluoride amine complex include a boron trifluoride monoethylamine complex, a boron trifluoride imidazole complex, and a boron trifluoride piperidine complex.

[0118] The radical polymerization initiator is a compound that generates radicals when exposed to heat or active energy rays, thereby initiating the curing reaction of the curable compound.

[0119] The radical polymerization initiator includes a photoradical polymerization initiator and a thermal radical polymerization initiator, such as an alkylphenone-based photoradical polymerization initiator, an acylphosphine oxide-based photoradical polymerization initiator, an oxime ester-based photoradical polymerization initiator, and an α-hydroxyketone-based photoradical polymerization initiator.

[0120] Examples of the alkylphenone-based photoradical polymerization initiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-[4-(4-morpholinyl)phenyl]-1-butanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, benzophenone, methylbenzophenone, o-benzoylbenzoic acid, benzoyl ethyl ether, 2,2-diethoxyacetophenone, 2, Examples of such compounds include 4-diethylthioxanthone, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl-(2,4,6-trimethylbenzoyl)phenylphosphinate, 4,4'-bis(diethylamino)benzophenone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, and oligomers of 2-hydroxy-1-(4-isopropenylphenyl)-2-methylpropan-1-one.

[0121] Examples of the acylphosphine oxide-based photoradical polymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

[0122] Examples of the oxime ester-based photoradical polymerization initiator include 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxime), 1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone O-acetyloxime, and the like.

[0123] Examples of the α-hydroxyketone-based photoradical polymerization initiator include benzoin, benzoin methyl ether, benzoin butyl ether, 1-hydroxycyclohexyl phenyl ketone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-(4-i-propylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, and 1-hydroxycyclohexyl phenyl ketone.

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

[0125] The content (amount) of the cationic polymerization initiator in the curable composition is not particularly limited, but is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, even more preferably 0.1 to 3 parts by mass, and particularly preferably 0.3 to 2 parts by mass, per 100 parts by mass of the total amount of the curable compounds. When the content is 0.01 part by mass or more, the curing reaction can proceed efficiently and sufficiently, and the surface hardness of the cured product tends to be further improved. When the content is 10 parts by mass or less, the storage stability of the curable composition tends to be improved and discoloration of the cured product tends to be suppressed.

[0126] The content (amount) of the radical polymerization initiator in the curable composition is not particularly limited, but is preferably 0.005 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, even more preferably 0.05 to 2 parts by mass, and particularly preferably 0.1 to 1 part by mass, per 100 parts by mass of the total amount of curable compounds. When the content is 0.005 parts by mass or more, the curing reaction can proceed efficiently and sufficiently, and the surface hardness of the cured product tends to be further improved. When the content is 5 parts by mass or less, the storage stability of the curable composition tends to be improved and discoloration of the cured product tends to be suppressed.

[0127] The curable composition may further contain other components in addition to the various components described above. These other components include inorganic fillers such as precipitated silica, wet silica, fumed silica, calcined silica, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate, carbon black, silicon carbide, silicon nitride, and boron nitride; inorganic fillers obtained by treating these fillers with organosilicon compounds such as organohalosilanes, organoalkoxysilanes, and organosilazanes; organic resin fine powders such as silicone resins, epoxy resins, and fluororesins; fillers such as conductive metal powders of silver and copper; curing agents (amine-based curing agents, polyaminoamide-based curing agents, acid anhydride-based curing agents, phenol-based curing agents, and the like); curing aids; curing accelerators (imidazoles, alkali metal or alkaline earth metal alkoxides, phosphines, amide compounds, Lewis acids, and the like); The composition may contain conventional additives such as: sulfur acid complex compounds, sulfur compounds, boron compounds, condensable organometallic compounds, etc.; solvents (water, organic solvents, etc.); stabilizers (antioxidants, ultraviolet 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 aids; reinforcing materials (other fillers, etc.); nucleating agents; coupling agents (silane coupling agents, etc.); lubricants; waxes; plasticizers; release agents; impact modifiers; color modifiers; clarifying agents; rheology modifiers (flow modifiers, etc.); processability modifiers; colorants (dyes, pigments, etc.); antistatic agents; dispersants; surface conditioners (anti-popping agents, etc.); surface modifiers (slip agents, etc.); matting agents; antifoaming agents; foam suppressors; defoaming agents; antibacterial agents; preservatives; viscosity modifiers; thickeners; photosensitizers; foaming agents; surfactants. The other components may be used singly or in combination of two or more. The content (blending amount) of the other components is not particularly limited, but is preferably 100 parts by mass or less, more preferably 30 parts by mass or less (e.g., 0.01 to 30 parts by mass), and even more preferably 10 parts by mass or less (e.g., 0.1 to 10 parts by mass) relative to 100 parts by mass of the total amount of the curable compound.

[0128] Examples of the organic solvent include known or commonly used organic solvents, such as ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ethers (dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (benzene, etc.), halogenated hydrocarbons (dichloromethane, dichloroethane, etc.), esters, alcohols (ethanol, cyclohexanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, and amides (dimethylformamide, dimethylacetamide, etc.).

[0129] The curable composition is not particularly limited, but can be prepared by stirring and mixing the various components described above at room temperature or, if necessary, while heating.

[0130] (Cured product, hard-coat-less film) The curable composition can be cured to obtain the cured product (hard coat-less film). The pencil hardness of the surface of the hard coat-less film is not particularly limited, but is preferably H or higher (for example, H to 9H), more preferably 2H or higher, even more preferably 3H or higher, even more preferably 4H or higher, even more preferably 5H or higher, even more preferably 6H or higher, even more preferably 7H or higher, even more preferably 8H or higher, and particularly preferably 9H. The pencil hardness can be evaluated according to the method described in JIS K5600-5-4.

[0131] A part or all of the surface of the above-mentioned hard coat-less film may be subjected to a known or conventional surface treatment such as a roughening treatment, an easy-adhesion treatment, an antistatic treatment, a sandblasting treatment (sand matting treatment), a discharge treatment (for example, a corona discharge treatment or a glow discharge treatment), a plasma treatment, a chemical etching treatment, a water matting treatment, a flame treatment, an acid treatment, an alkali treatment, an oxidation treatment, an ultraviolet irradiation treatment, or a silane coupling agent treatment, for the purpose of improving adhesion to other layers.

[0132] The hard coat-less film is obtained by applying the curable composition to a release-treated surface of a temporary substrate such as a separator, removing the solvent by drying as necessary, and then curing the curable composition by allowing a polymerization reaction of the curable compound in the curable composition to proceed, thereby obtaining a cured product, and then peeling the cured product from the temporary substrate.

[0133] The curable composition can be applied by any known or conventional coating method. Examples of coating devices include a roll coater, air knife coater, blade coater, rod coater, reverse coater, bar coater, comma coater, dip-squeeze coater, die coater, gravure coater, microgravure coater, silk screen coater, and spray coater. Coating methods include methods using a coating device, as well as a dip method (dipping coating) and a spinner method. Among these, application using a spray coater (spray coating) is preferred.

[0134] The curing method can be appropriately selected from known methods and is not particularly limited, and is appropriately selected depending on the type of curable functional group possessed by the curable compound. For example, methods such as irradiation with active energy rays and heating can be used. As the active energy rays, for example, any of infrared rays, visible light, ultraviolet rays, X-rays, electron beams, α rays, β rays, and γ rays can be used. Among them, ultraviolet rays are preferred in terms of excellent handleability. The irradiation with the active energy rays (particularly electron beams) is preferably carried out under an inert gas atmosphere such as a nitrogen atmosphere, an argon atmosphere, or a helium atmosphere.

[0135] The curable composition may be heated to remove the solvent after application. The temperature at which the solvent is removed is not particularly limited, but is preferably 40 to 200° C., more preferably 50 to 170° C., even more preferably 60 to 150° C., and particularly preferably 80 to 140° C. The time for which the temperature is maintained is not particularly limited, but is preferably about 30 seconds to 5 hours.

[0136] The conditions for curing the curable composition by irradiation with active energy rays (such as irradiation conditions for active energy rays) can be appropriately adjusted depending on the type and energy of the active energy rays to be irradiated, the shape and size of the hard coat-less film, and are not particularly limited. When ultraviolet rays are irradiated, for example, the irradiation conditions are 1 to 10,000 mJ / cm. 2 (preferably 50 to 5000 mJ / cm 2 , more preferably 70 to 3000 mJ / cm 2 , and more preferably 100 to 1000 mJ / cm 2 ) is preferable. For example, a deep UV lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a low-pressure mercury lamp, a xenon lamp, a carbon arc, a metal halide lamp, sunlight, an LED lamp, a halogen lamp, or a laser (e.g., a helium-cadmium laser, an excimer laser, etc.) can be used for irradiating the active energy rays. After irradiating the active energy rays, a heat treatment (annealing, aging) can be further performed to further promote the curing reaction.

[0137] The dose of electron beam irradiation for curing 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 acceleration 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 aging, 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] [Laminate] A laminate can be obtained by laminating other layers onto the hard coat-less film. Examples of the other layers include functional layers that can impart various functions. The laminate includes the hard coat-less film and a functional layer laminated on the hard coat-less film. The other layer may be a single layer or two or more layers.

[0140] Examples of the functional layer include a surface protection film for protecting the surface of a hard coatless film, a hard coat layer, an anti-reflection layer, an anti-glare layer, a fingerprint-resistant layer, an antifouling layer, a scratch-resistant layer, a fingerprint-resistant layer, an antibacterial layer, a bonding layer, a polarizing layer, and an optical substrate. The functional layer is preferably formed from a thermosetting resin composition or an active energy ray-curable resin composition, and more preferably from an active energy ray-curable resin composition. Furthermore, the functional layer may be attached to a substrate such as glass.

[0141] When the surface protective film is provided, the punching processability and handling property of the hard coat-less film tend to be improved. When the surface protective film is provided in this manner, for example, even if the hard coat-less film has a very high hardness and is prone to peeling from the support or cracking during punching, punching using a Thomson blade can be performed without causing such problems.

[0142] The surface protection film may be any known or conventional surface protection film, and is not particularly limited thereto. For example, a plastic film having a pressure-sensitive adhesive layer on its surface may be used. Examples of the plastic film include plastic films made of plastic materials such as polyester (polyethylene terephthalate, polyethylene naphthalate, etc.), polyolefin (polyethylene, polypropylene, cyclic polyolefin, etc.), polystyrene, acrylic resin, polycarbonate, epoxy resin, fluororesin, silicone resin, diacetate resin, triacetate resin, polyarylate, polyvinyl chloride, polysulfone, polyethersulfone, polyetheretherimide, polyimide, and polyamide. Examples of the pressure-sensitive adhesive layer include pressure-sensitive adhesive layers made of one or more known or conventional pressure-sensitive adhesives such as acrylic pressure-sensitive adhesives, natural rubber pressure-sensitive adhesives, synthetic rubber pressure-sensitive adhesives, ethylene-vinyl acetate copolymer pressure-sensitive adhesives, ethylene-(meth)acrylate copolymer pressure-sensitive adhesives, styrene-isoprene block copolymer pressure-sensitive adhesives, and styrene-butadiene block copolymer pressure-sensitive adhesives. The pressure-sensitive adhesive layer may contain various additives (e.g., antistatic agents, slip agents, etc.). The plastic film and the pressure-sensitive adhesive layer may each have a single-layer structure or a multi-layer (multi-layer) structure. The thickness of the surface protection film is not particularly limited and can be selected appropriately.

[0143] Examples of surface protection films include commercially available products such as the "SaniTect" series (manufactured by San-A Chemical Co., Ltd.), the "E-MASK" series (manufactured by Nitto Denko Corporation), 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.).

[0144] Specific examples of the laminate include: [hard coatless film / bonding layer / surface protective film], [hard coatless film / bonding layer / anti-reflection layer], [hard coatless film / anti-glare layer / surface protective film], [hard coatless film / substrate / bonding layer], [glass / hard coatless film / surface protective film], [glass / hard coatless film / bonding layer], [hard coatless film / fingerprint-resistant layer / fingerprint-resistant layer], [hard coatless film / anti-fouling layer / surface protective film], [hard coatless film / anti-glare layer / anti-reflection layer], [hard coatless film / anti-reflection layer / fingerprint-resistant layer], [hard coatless film / bonding layer / glass], [hard coatless film / bonding layer / polarizing layer], [glass / hard coatless film / polarizing layer], [glass / hard coatless film / bonding layer / polarizing layer], [glass / hard coatless film / anti-reflection layer], and the like. Also, a multilayer laminate can be obtained by stacking multiple of the above laminates.

[0145] The laminates, such as the multilayer laminates, can be used as components of various products and their parts. Examples of such products include various home appliances, various electrical and electronic products, and various optical devices, including display devices such as liquid crystal displays and organic EL displays; input devices such as touch panels; solar cells; portable electronic devices such as game consoles, personal computers, tablets, smartphones, and mobile phones; display devices such as displays inside automobiles; eyeglass lenses; and transparent components used outdoors or in harsh environments such as high temperatures and humidity, such as automobile headlights, factory automation cameras, and camera lenses for surveillance cameras. The hard coat-less film is preferably a layer that protects the surface of the product.

[0146] Each aspect disclosed in this specification can be combined with any other feature disclosed in this specification. Each configuration and combination thereof in each embodiment is an example, and addition, omission, substitution, and other modifications of configurations are possible as appropriate within the scope of the present disclosure. Furthermore, each invention according to this disclosure is not limited by the embodiments or the following examples, but is limited only by the scope of the claims. [Example]

[0147] An embodiment of the present disclosure will be described in more detail below with reference to examples. The molecular weight of the product was measured using an Alliance HPLC System 2695 (manufactured by Waters), a Refractive Index Detector 2414 (manufactured by Waters), and a column: Tskgel GMH. HR -M×2 (manufactured by Tosoh Corporation), guard column: Tskgel guard column H HR The measurement was performed using a column oven: COLUMN HEATER U-620 (manufactured by Tosoh Corporation), a column oven: COLUMN HEATER U-620 (manufactured by Sugai), a solvent: THF, measurement conditions: 40°C, and a molecular weight calculated as standard polystyrene. The ratio of T2 to T3 isomers in the product [T3 / T2 isomer] was measured using a JEOL ECA500 (500 MHz). 29 The T of the product was determined by Si-NMR spectroscopy. d5 The (5% weight loss temperature) was measured by TGA (thermogravimetric analysis) under conditions of an air atmosphere and a temperature rise rate of 5°C / min.

[0148] Example 1 (Preparation of Epoxy Group-Containing Silsesquioxane) A 300 mL flask (reaction vessel) equipped with a thermometer, stirrer, reflux condenser, and nitrogen inlet tube was charged with 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 under a nitrogen stream and heated to 50°C. To the resulting mixture, 4.70 g of 5% aqueous potassium carbonate solution (1.7 mmol of potassium carbonate) was added dropwise over 5 minutes, followed by 1700 mmol (30.60 g) of water over 20 minutes. No significant temperature increase occurred during the addition. The polycondensation reaction was then carried out at 50°C under a nitrogen stream for 4 hours. Analysis of the product in the reaction solution after the polycondensation reaction revealed that the number average molecular weight was 1911 and the molecular weight dispersity was 1.47. 29 The ratio of T2 to T3 isomers [T3 / T2] calculated from the Si-NMR spectrum 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 from the upper layer at 1 mmHg and 40°C to obtain a colorless, transparent liquid product (epoxy-containing silsesquioxane, solid content 77% by mass). d5 was 370°C.

[0149] (Preparation of Curable Composition 1) As the curable compound 1, 66.8 parts by mass of the epoxy group-containing silsesquioxane obtained above (active ingredient 77% by mass), 1.5 parts by mass of trade name "Epoxy Ester 200PA-E5" (a compound having an acryloyl group, an epoxy group, and a polyglycerin skeleton, manufactured by Kyoeisha Chemical Co., Ltd.), 6.2 parts by mass of 1,6-hexanediol diglycidyl ether (trade name "Epolight 1600", manufactured by Kyoeisha Chemical Co., Ltd.), and 0.2 parts by mass of a radical-curable functional group-containing polyorganosiloxane (trade name "Megafac RS-57", active ingredient 20% by mass, not subject to PFAS restrictions, manufactured by DIC Corporation, active ingredient 20% by mass), were mixed with 0.5 parts by mass of a photocationic polymerization initiator (a salt of triarylsulfonium and tetrapentafluorophenylgallium) and a photoradical polymerization initiator (trade name "Omnirad127", manufactured by IGM Chemical Co., Ltd.) as a curing catalyst. A curable composition was prepared by mixing 0.2 parts by mass of a hydroxybenzoate (manufactured by Adeka Resins Co., Ltd.), 0.4 parts by mass of an antioxidant (trade name "AO-20" manufactured by Adeka Corporation), 8.4 parts by mass of methyl isobutyl ketone (MIBK) and 15.8 parts by mass of methyl ethyl ketone (MEK) as solvents. The content ratios shown in Table 1 are the blending ratios of each component, with silsesquioxane and RS-57 being solution values ​​and the values ​​of the other components being active ingredients.

[0150] (Preparation of hard-coated film) The curable composition 1 was spray-coated onto the release-treated surface of a separator placed on a Teflon (registered trademark) frame using a hand spray gun (manufactured by Anest Iwata Corporation). The resulting mixture was then dried (80°C, 2 hours) and irradiated with UV (300 mJ / cm). 2 ), after which the Teflon (registered trademark) frame was removed, and the coating was cured by aging at 120°C for 1 hour to obtain a cured product (hard coat-less film) 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. "Epolite 400E" shown in Table 1 is the trade name "Epolite 400E" (manufactured by Kyoeisha Chemical Co., Ltd., polyethylene glycol #400 diglycidyl ether).

[0152] (Preparation of hard-coated film) A cured product of Example 2 (thickness: about 0.150 mm) (hard coat-less film) was prepared in the same manner as in Example 1, except that the above-mentioned curable composition 2 was used.

[0153] Example 3 (Preparation of Curable Composition 3) Curable composition 3 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.

[0154] (Preparation of hard-coated film) A cured product (thickness: about 0.150 mm) (hard coat-less film) of Example 3 was prepared in the same manner as in Example 1, except that the above-mentioned curable composition 3 was used.

[0155] The cured products (hard coat-less films) 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 surface of the hardcoat-less film obtained above was evaluated in accordance with JIS K5600-5-4.

[0157] (2) Tensile test The hard-coated film obtained above was punched into the shape of a No. 7 dumbbell (JIS K6251) to prepare test specimens. Using a Tensilon universal testing machine (product name "RTF-1350", manufactured by A&D Co., Ltd.), tests were conducted in accordance with JIS K7161 (1994) at a tensile speed of 2 mm / min, a chuck distance of 20 mm, and a gauge length of 12 mm. Tensile tests were conducted on n=8 specimens, and the average value obtained by excluding the upper and lower limits was used as the Young's modulus of the evaluation results.

[0158] (3) Push-in test The hard coat-less film obtained above was measured at 10 points using a nanoindenter (product name "ENT-2100", manufactured by Elionix Co., Ltd.) with a Berkovich indenter at a maximum load of 500 μN, and the average values ​​of indentation hardness and Young's modulus were measured.

[0159] (4) Glass transition temperature, melting point The cured products obtained above were subjected to DSC measurement using a differential scanning calorimeter (trade name "DSC-6220", manufactured by Hitachi High-Tech Science Corporation) in the temperature range from room temperature to 300°C. As a result, for all of Examples 1 to 3, no baseline shift due to the glass transition temperature and no peak due to the melting point were observed within the range of 300°C or less.

[0160] [Table 1]

[0161] As shown in the evaluation results in Table 1, the hard coat-less film of Example 1, even without using PFAS-regulated substances, had a moderate Young's modulus in the tensile test, and the elastic-plastic ratio and Young's modulus in the indentation test were sufficiently high, and it was determined that it had excellent mechanical strength. In addition, the hard coat-less film of Example 1 is made of resin instead of glass, and is lighter than glass. In addition, the glass transition temperature and melting point were not confirmed below 300 ° C, and it was determined that it had excellent heat resistance.

[0162] Variations of the invention according to the present disclosure are described below. [Appendix 1] A hard-coat-less film that satisfies at least one of the following: an elastic-plastic ratio in an indentation test of 70% or more, a glass transition temperature and a melting point not lower than 200°C, a Young's modulus in an indentation test of 1000 MPa or more, and a Young's modulus in a tensile test of 1000 to 5000 MPa. [Appendix 2] The hard coat-less film according to Appendix 1, which has a thickness of 1 to 1000 μm and an indentation hardness of 100 MPa or more in an indentation test. [Appendix 3] A hardcoat-less film according to appendix 1 or 2, which is formed from a cured product of a curable composition, and the cured product has a glass transition temperature of 300°C or higher. [Appendix 4] The hardcoat-less film according to any one of Appendices 1 to 3, which is formed from a cured product of a curable composition, and the pencil hardness of the cured product is 2H or more. [Appendix 5] The hardcoat-less film according to Appendix 3 or 4, wherein the curable composition contains a radical-curable polyorganosiloxane. [Appendix 6] The hard coat-less film according to any one of Appendices 3 to 5, wherein the curable composition contains a cationically polymerizable silsesquioxane. [Appendix 7] The hardcoat-less film according to any one of Appendices 3 to 6, wherein the curable composition further contains a curable compound having an active energy ray-polymerizable functional group. [Appendix 8] A laminate comprising the hard coat-less film according to any one of Appendices 1 to 7 and a functional layer laminated on the hard coat-less film. [Appendix 9] A multilayer laminate in which a plurality of the laminates according to Appendix 8 are stacked. [Appendix 10] A display device comprising the multilayer stack according to Appendix 9.

Claims

1. The elastic-plastic ratio in an indentation test is 70% or more, and the glass transition temperature and melting point are not lower than 200°C, and at least one of the following is satisfied: Young's modulus in an indentation test is 1000 MPa or more, and Young's modulus in a tensile test is 1000 to 5000 MPa; A hard coat-less film that is a cured product of a curable composition containing a radical-curable polyorganosiloxane that is not a PFAS-regulated substance, a cationically polymerizable silsesquioxane, and a curable compound having an active energy ray-polymerizable functional group.

2. 2. The hardcoat-less film according to claim 1, which has a thickness of 1 to 1000 μm and an indentation hardness of 100 MPa or more in an indentation test.

3. A hardcoatless film as described in claim 1 or 2, wherein the glass transition temperature of the cured product is 300°C or higher.

4. A hardcoatless film as described in claim 1 or 2, wherein the pencil hardness of the cured product is 2H or more.

5. A laminate comprising the hard coat-less film according to claim 1 or 2 and a functional layer laminated on the hard coat-less film.

6. A multilayer laminate comprising a plurality of laminates according to claim 5 .

7. A display device comprising the multilayer stack of claim 6.

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